JPH0728213A - Solid processing agent for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a solid processing agent as a bleaching agent for a silver halide color photographic sensitive material hardly generating fine powder during transfer and handling because of its high strength and having excellent solubility to a processing soln. CONSTITUTION:This solid processing agent for a silver halide color photographic sensitive material having bleaching ability contains at least granules contg. at least one kind of ferric complex salt of aminopolycarboxylic acid and an org. acid and/or its salt in the same granules.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid processing agent for silver halide color photographic light-sensitive materials, and more specifically, the stability of the bleaching processing agent is dramatically improved, the dissolving work is eliminated, and the processing agent container The present invention relates to a solid processing agent for silver halide color photographic light-sensitive materials, which enables free use of bottles.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material is subjected to processes such as development, desilvering, washing and stabilization after exposure. When the processing is carried out by an automatic processor, a replenishing system is generally widely used and controlled so as to maintain the activity of the processing liquid in the processing tank. In the case of this replenishment system, a large amount of overflow liquid is usually discharged because the purpose is to dilute the eluate from the light-sensitive material, correct the evaporation amount, and replenish the consumption component.

[0003] In recent years, there have been increasing regulations worldwide regarding the dumping of photographic waste liquids into the ocean, and regulations regarding the disposal of plastic materials. There is a need to develop a new system that eliminates photographic waste liquid and does not use bottles for processing agents. Further, in order to ensure the safety of transportation of liquid dangerous goods, safety regulations for packaging materials have been strengthened, resulting in price increase. In the minilab, which has been increasing rapidly in recent years, part work progresses due to lack of manpower, and it is difficult to dissolve the replenisher, and many accidents due to erroneous dissolution have been complained to the replenisher system. Therefore, in the photographic industry, there is a strong demand for the development of a solid chemical replenishment system that requires almost no photographic waste liquid and no bottles and does not require dissolution work.

As a method for solving the above problems, Japanese Patent Laid-Open No.
No. 54-133332 discloses that powdered iron aminopolycarboxylate (I
II) A bleaching agent for photography using a complex salt (hereinafter sometimes referred to as APC) is disclosed. Since this method does not use a liquid processing agent, it can be packaged without using the polyvin etc. of the processing agent container, but when adjusting it to a processing solution, the powder is scattered and the contamination and working environment deteriorate. It has the drawback of causing Further, even if a tablet is prepared using the above powder, sufficient strength cannot be obtained, which is not practical.

On the other hand, JP-A-3-39379 discloses granules of an aminopolycarboxylic iron (III) complex salt containing a rehalogenating agent having an average particle size within a predetermined range. Although this method prevents the above-mentioned powder from scattering, it is exposed to various shocks in the transportation route from the manufacturer to the user's hand, so that the granules are broken during use and a large amount of fine particles are broken. It was found that powder may be generated, which poses a serious problem in practical use.

[0006]

Also, when the above granules are tableted to give tablets, similarly, when a strong impact is applied, the tablets may be cracked or chipped, resulting in a marked decrease in commercial value. To do. In particular, when directly charged into a dissolution tank or a processing tank of an automatic processor by an automatic charging device, this is the most useful use method of the present invention, but by any chance broken tablets or chipped tablets are mixed. Then, the loading device becomes clogged and the loading accuracy deteriorates, the activity of the developer fluctuates drastically, the loading operation becomes impossible, and the device malfunctions. It was found that maintaining the shape of the tablet before use was the most important issue.

The necessity of maintaining the shape of the treating agent during the transportation of such a solid treating agent is a problem that has not been considered for a liquid treating agent. However, by solving this problem, there is an advantage in transportation. Is very large, as I said, and it turns out that solving this problem is important.

The problem as described above is that the aminopolycarboxylic acid iron (III) complex salt has physical properties of very poor binding property, and therefore sufficient strength cannot be obtained even if granulation or tableting is performed. It has been found. However, in the processing of silver halide photographic light-sensitive materials, aminopolycarboxylic acid iron (III) complex salts are the most excellent bleaching agents in view of processability, effects on automatic processors, and safety. Most of the agents are used, and it is difficult to switch to other bleaching agents, and the use of aminopolycarboxylic acid iron (III) complex salts is essential. It was also found that the method disclosed in JP-A-5-100391 is not sufficient. Furthermore, the granules of JP-A-3-39379 described above have a further problem that, under high humidity conditions, so-called blocking, which causes formation of large lumps due to moisture absorption, is caused and fluidity is significantly deteriorated. For this reason, for example, there are drawbacks such that variations in weighing occur in the step of packaging the formed granules, and the weight of the granules filled in the die when used for tablet formation varies so that the tablet weight is not constant. I knew that.

Therefore, a first object of the present invention is to provide a solid photographic processing agent which eliminates a liquid processing agent which poses a danger in transportation and handling, and which does not use a resin bottle which is a large amount of waste. . A second object of the present invention is to provide a solid photographic processing agent which is excellent in strength without generation of fine powder, can maintain its initial shape during transportation, and is free from blocking and excellent in fluidity. is there.

[0010]

Such an object is achieved by the following means according to the present invention. (1) At least one iron (II) aminopolycarboxylate (II
(I) A solid processing agent for a silver halide color photographic light-sensitive material having a bleaching ability, which comprises at least particles containing a complex salt and an organic acid and / or the salt all together in the same particle.

(2) The iron (II) aminopolycarboxylate (II
I) a complex salt is a compound represented by the following general formula [I] and /
Alternatively, it is an iron (III) chelate compound of a salt thereof, which is a solid processing agent for a silver halide color photographic light-sensitive material having a bleaching ability according to (1).

[0012]

[Chemical 12]

(3) The iron (II) aminopolycarboxylate (II
I) complex salts are represented by the following general formulas [A-I], [A-II] and [A-
III], [A-IV], [A-V], [A-VI], [A-VI]
I) or a compound represented by the following compound [A ′] group and / or a salt thereof, which is an iron (III) chelate compound, and is for a silver halide color photographic light-sensitive material having a bleaching ability according to (1). It is a solid processing agent.

[0014]

[Chemical 13]

[In the formula, A _{1 to} A ₄ may be the same or different and each represents a hydrogen atom, a hydroxy group, —COOM, or —PO
₃ (M ₁ ) ₂ , —CH ₂ COOM ₂ , —CH ₂ OH or a lower alkyl group. However, at least one of A _{1 to} A ₄ is -COOM, -PO
₃ (M ₁ ) ₂ and —CH ₂ COOM ₂ . M, M ₁ and M ₂ each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. ]

[0016]

[Chemical 14]

[In the formula, A _{11 to} A ₁₄ may be the same or different and each represents —CH ₂ OH, —COOM ₃ or —PO ₃ (M ₄ ) ₂ . M
₃ , M ₄ each represents a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. X has 2 to 6 carbon atoms
Represents an alkylene group or — (B ₁ O) n—B ₂ —. n is 1 to 8
And B ₁ and B ₂ may be the same or different and each represents an alkylene group having 1 to 5 carbon atoms. ]

[0018]

[Chemical 15]

[In the formula, A _{21 to} A ₂₄ may be the same or different and each represents —CH ₂ OH, —COOM ₅ or —PO ₃ (M ₆ ) ₂ . M
₅ and M ₆ each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. X ₁ has 2 to 6 carbon atoms
Linear or branched alkylene group, an organic group of a saturated or unsaturated to form a ring _{or, - (B 11 O) n} 5 -B 12 - represents a. n ₅ represents an integer of 1 to 8, and B ₁₁ and B ₁₂ may be the same or different and each represents an alkylene group having 1 to 5 carbon atoms. n _{1 to} n ₄ represent an integer of 1 or more, and may be the same or different. ]

[0020]

[Chemical 16]

[Wherein R ₁ and R ₂ are each a hydrogen atom,
It represents an alkyl group or an aryl group which may be substituted.
L is

[0022]

[Chemical 17]

Y _{1 to} Y ₃ each represent an alkylene group or an arylene group, X ₂ and X ₃ each represent an oxygen atom or a sulfur atom, R _{3 to} R ₇ each represent a hydrogen atom, It represents an alkyl group or an aryl group. ]

[0024]

[Chemical 18]

[In the formula, R _{1 to} R ₃ each represent a hydrogen atom, an optionally substituted alkyl group or an aryl group. L
Has the same meaning as L in formula [A-IV]. W represents a divalent linking group. ]

[0026]

[Chemical 19]

[In the formula, R _{1 to} R ₃ and R _{6 to} R ₉ each represent a hydrogen atom, an optionally substituted alkyl group or an aryl group, and R ₄ and R ₅ each represent a hydrogen atom, a halogen atom,
A cyano group, a nitro group, an acyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, a sulfonyl group, a sulfinyl group, an optionally substituted alkyl group or an aryl group, and R ₄ and R ₅
May together form a 5-membered ring or a 6-membered ring.
A represents a carboxy group, a phosphono group, a sulfo group, a hydroxy group, or an alkyl metal salt or ammonium salt thereof. Y represents an alkylene group or an arylene group and may have a substituent. t and u represent 0 or 1, respectively. ]

[0028]

[Chemical 20]

[Wherein A₁~ A_FourIs −COOM₁, -OH, -PO₃
M₁M₂, -CONH₂Represents the same, but different
You may stay. M₁, M₂Is hydrogen ion, alkali metal ion
Or other cation. n₁~ N_FourIs 0, 1 or
Represents an integer of 2. R₁~ R_FourIs a hydrogen atom, lower alkyl
Group represents a hydroxy group (provided that n₁+ N₂= 1 and n
₃+ N_FourWhen = 1 R₁~ R_FourIs not a hydrogen atom).

X represents a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms or-(B ₁ O) _m --B _2- . m represents an integer of 1 to 4, 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. ] Compound [A '] group [A'-1] ethylenediaminetetraacetic acid [A'-2] trans-1,2-cyclohexanediaminetetraacetic acid [A'-3] dihydroxyethylglycine [A'-4] ethylenediaminetetrakismethylene Phosphonic acid [A'-5] Nitrilotrismethylenephosphonic acid [A'-6] Diethylenetriamine pentakismethylenephosphonic acid [A'-7] Diethylenetriaminepentaacetic acid [A'-8] Ethylenediaminedioltohydroxyphenylacetic acid [A'- 9] Hydroxyethyl ethylenediamine triacetic acid [A'-10] ethylenediaminepropionic acid [A'-11] ethylenediamine diacetic acid [A'-12] hydroxyethyliminodiacetic acid [A'-13] nitrilotriacetic acid [A'-14] Nitrilotripropionic acid [A'-15] triethylenetetramine hexa Acid [A'-16] ethylenediamine tetrapropionic acid [A'-17] 1,3-propanediamine tetraacetic acid [A'-18] glycol ether diamine tetraacetic acid (4) The aminopolycarboxylic acid iron (III) complex salt is 1,3
-Propanediaminetetraacetic acid, ethylenediaminetetraacetic acid,
Ethylenediamine-N, M'-disuccinic acid or β-alanine-
Iron (III), a compound selected from N, N-diacetic acid or its salt
A solid processing agent for a silver halide color photographic light-sensitive material having a bleaching ability according to (1), which is a chelate compound.

(5) Solid processing for silver halide color photographic light-sensitive materials having a bleaching ability according to any one of (1) to (4), characterized in that the solid processing agent is in a granular form. It is an agent.

(6) Particles containing the above-mentioned at least one aminopolycarboxylic acid iron (III) complex salt and an organic acid and / or the salt together in the same particle together with the organic acid and / or the salt. , The aminopolycarboxylic acid iron (II
I) A granulated product prepared by mixing granules of a complex salt each having a particle size of 150 μm or less, and then granulating the granulated product, characterized in that the average particle size of the granulated product is 300 to 3000 μm ( 5) A solid processing agent for a silver halide color photographic light-sensitive material, which has a bleaching ability as described in 5).

(7) The solid processing for a silver halide color photographic light-sensitive material having a bleaching ability according to (5) or (6), wherein the organic acid is a compound having at least one carboxyl group. It is an agent.

(8) The organic acid has the following general formula [II]
A solid processing agent for a silver halide color photographic light-sensitive material having a bleaching ability according to (7), which is a compound represented by:

[0035]

[Chemical 21]

(9) The organic acid is at least one compound selected from succinic acid, maleic acid, glycolic acid, adipic acid, citric acid and fumaric acid (4) or (5) It is a solid processing agent for a silver halide color photographic light-sensitive material having the bleaching ability described.

(10) The granules are granulated so that the molar ratio of the total content of the organic acid and the salt to the content of the aminopolycarboxylic acid iron (III) complex salt is 0.8 to 3.0. The solid processing agent for a silver halide color photographic light-sensitive material having a bleaching ability according to any one of (5) to (9).

(11) In the above solid processing agent, the molar ratio of the total content of the organic polyacid and the salt to the total content of the aminopolycarboxylic acid iron (III) complex salt is 0.8 to 3.0. The solid processing agent for a silver halide color photographic light-sensitive material according to any one of (5) to (10).

(12) The halogen having a bleaching ability according to any one of (5) to (11), wherein the solid processing agent contains at least one compound selected from the following compound group. Solid processing agent for silver halide color photographic light-sensitive materials.

(Group A) saccharide (Group B) water-soluble polymer (Group C) dextrin (13) The solid processing agent is a bleaching agent, which is any one of (5) to (12). The solid processing agent for a silver halide color photographic light-sensitive material having the bleaching ability described in 1.

(14) The solid processing agent for a silver halide color photographic light-sensitive material as described in any one of (1) to (4), characterized in that the solid processing agent is in the form of tablets. It is an agent.

(15) It is characterized in that it is obtained by compression molding of particles in which the at least one iron (III) aminopolycarboxylic acid complex salt and an organic acid or an organic acid salt are collectively contained in the same particle ( The solid processing agent for a silver halide color photographic light-sensitive material having the bleaching ability described in 14).

(16) Particles containing the at least one aminopolycarboxylic acid iron (III) complex salt and an organic acid or the salt together in the same particle, and the organic acid and / or the salt, Aminopolycarboxylic acid iron (III) complex salt is a granulated product prepared by mixing solids each having a particle size of 150 μm or less, and granulating the granulated product having an average particle size of 300
The solid processing agent for a silver halide color photographic light-sensitive material according to (14) or (15), which has a bleaching ability.

(17) A silver halide color photograph having a bleaching ability according to any one of (14) to (16), wherein the organic acid is a compound having at least one carboxyl group. It is a solid processing agent for photosensitive materials.

(18) The organic acid has the following general formula [II]
A solid processing agent for a silver halide color photographic light-sensitive material having a bleaching ability according to (17), which is a compound represented by:

[0046]

[Chemical formula 22]

(19) The organic acid is at least one compound selected from succinic acid, maleic acid, glycolic acid, adipic acid, citric acid and fumaric acid (14) to (16) A solid processing agent for a silver halide color photographic light-sensitive material having a bleaching ability according to any one of 1.

(20) The particles are granulated so that the molar ratio of the total content of the organic acid and the salt to the content of the aminopolycarboxylic acid iron (III) complex salt is 0.8 to 3.0. Any one of (14) to (19) characterized in that
Which is a solid processing agent for a silver halide color photographic light-sensitive material having the bleaching ability described in the item.

(21) In the tablet-shaped solid processing agent,
The iron (II) aminopolycarboxylate (II
I) The molar ratio of the total content of the organic acid and the salt to the total content of the complex salt is 0.8 to 3.0 (14)
(20) A solid processing agent for a silver halide color photographic light-sensitive material, which has a bleaching ability according to any one of

(22) The bleaching ability according to any one of (14) to (21), wherein the tablet-like solid processing agent contains at least one compound selected from the following compound group: A solid processing agent for a silver halide color photographic light-sensitive material having

(Group A) saccharides (Group B) water-soluble polymer (Group C) dextrins (23) The solid processing agent is a bleaching agent, which is any one of (14) to (22). The solid processing agent for a silver halide color photographic light-sensitive material having the bleaching ability described in 1.

The present invention will be specifically described below.

The inventors of the present invention have made extensive studies on the above-mentioned problems, and as a result, the above-mentioned iron (II) aminopolycarboxylate (II
I) Granules prepared by mixing a complex salt with a solid organic acid such as succinic acid in one particle, for example, a mixture of fine powder and pulverized product of both Two
For granules such as secondary particles, we found a truly surprising phenomenon in which the strength of the granules increased remarkably within about 24 hours after production (hereinafter sometimes simply referred to as aging effect). Further, a tablet obtained by tableting granules containing a solid organic acid such as succinic acid in one particle on the above-mentioned aminopolycarboxylic acid iron (III) complex salt is Not only the hardness was increased, but also the phenomenon that the hardness was remarkably increased by aging after tableting like the granules was observed.

Conventionally, an example of a solid processing agent using an aminopolycarboxylic acid iron (III) complex salt and an organic acid has been known, but the organic acid and the aminopolycarboxylic acid iron (III) salt are known.
The complex as a powder was mixed and tableted, or both were granulated and mixed separately, and the mixture was tableted, the aging effect as in the present invention did not appear, and the phenomenon of the present invention Is a totally unexpected thing and can be said to be a breakthrough.

The solid processing agent of the present invention is a form in which the particles are characterized by containing an organic acid or both the salt and an aminopolycarboxylic acid iron (III) complex salt in one particle. Of course, other compounds may be contained in the same particle. A tablet-like solid processing agent obtained by compression-molding the particles, which essentially comprises a group of particles having these characteristics, is also one of the preferred embodiments of the present invention. However, the particles do not mean the tablets themselves.

On the other hand, the organic acid or the salt and the aminopolycarboxylic acid iron (III) complex salt powder are simply mixed without granulation, or the mixture is partially adsorbed by blocking or the like. Is not included in the present invention because the effect of the present invention does not appear, or a granulated product obtained by granulating an organic acid granulated product or a mixture with a further compound. And a granulated product of the aminopolycarboxylic acid iron (III) complex salt or a mixture with another compound (a granulated product containing the aminopolycarboxylic acid iron (III) complex salt) The mixture obtained by mixing the above does not have a constitution in which the organic acid and the aminopolycarboxylic acid are contained in the same particle, and therefore is clearly distinguished from the solid processing agent of the present invention. However, in addition to the particles containing the aminopolycarboxylic acid and the organic acid in the same particle, the above granulated product, or a mixture further added with other compounds, or a tablet-like product obtained by tableting the mixture. Solid processing agents are included in the present invention.

There is no particular limitation on the method for producing the above-mentioned particles containing the aminopolycarboxylic acid and the organic acid in the same particle, but both compounds (and, if necessary, other additives) are pulverized, and pulverized. The particles of the present invention can be easily obtained by forming a mixture of products into a granular or pill-like form by a granulating operation.

The particle size of the crushed product in the above method is preferably 150 μm or less, more preferably 100 μm or less, further preferably 50 μm or less. The above-mentioned particle size describes the numerical value of the upper limit of the particle size, and unlike the average particle size, it is a standard that the particle size larger than the above particle size is substantially within 20%. However, if powders having these particle sizes can be obtained, powders obtained by methods other than pulverization, such as crystallization, may be used. In particular, the hardness of tablets obtained by tableting the above-mentioned granules having a particle size of 100 μm or less is remarkably improved by aging.

The granules or pill-like granules (hereinafter referred to as granules) obtained by the above-mentioned granulation operation have a weight average particle diameter of 300 to 3000 μm for handling and the present invention. It is also preferable from the viewpoint of strength of effect, and more preferably 250 to 1000 μm.

As the method for producing the granulated product, known methods such as rolling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, spray drying granulation and the like can be used. Can be used.

The tablet-type solid processing agent can be manufactured using a known compressor. For manufacturing, for example, a hydraulic press machine, a single-shot tableting machine, a rotary tableting machine, or a briquetting machine can be used. Although the tablet-type solid processing agent can take any shape, productivity,
A cylindrical type is preferable from the viewpoint of handleability. The tableting (compression) pressure is preferably in the range of 300 to 3000 Kg / cm ² , more preferably 500 to 2000 Kg / cm ² .

The solid treating agent of the present invention contains at least one iron (III) aminopolycarboxylic acid complex salt, and is a different type of aminopolycarboxylic acid iron (III) complex salt.
You may use a complex salt together.

As the aminopolycarboxylic acid iron (III) complex salt, an aminopolycarboxylic acid iron (III) complex salt known as a known bleaching agent can be used, and the following general formulas [I] and [AI] can be used. [A-II], [A-III], [A
-IV], [A-V], [A-VI], [A-VII], or a compound represented by the compound [A '] group or iron (II
I) Chelate is preferred, and the iron (III) complex salt and general formulas [I], [AI], [A-II] and [A-II] are preferred.
I], [A-IV], [A-V], [A-VI], [A-VI]
It is more preferable to use the compound represented by I] or the compound [A ′] group or a salt thereof (for example, an alkali metal salt, an ammonium salt, etc.) in combination. Especially preferred are ferric complexes of free acids of the same type as the free acids of aminopolycarboxylic acids. When the aminopolycarboxylic acid iron (III) complex salt and the aminopolycarboxylic acid or the salt are used in combination, the aminopolycarboxylic acid constituting the iron (III) complex salt may be the same as the aminopolycarboxylic acid or the salt. preferable.

The aminopolycarboxylic acid iron (III) complex salt may be used in the form of potassium salt, sodium salt, ammonium salt, lithium salt, etc., and aminopolycarboxylic acid iron (III) complex, aminopolycarboxylic acid and The salt can also be used in the form of a hydrous salt.

The aminopolycarboxylic acid of the present invention will be described below.

[0066]

[Chemical formula 23]

[0067]

[Chemical formula 24]

[0068]

[Chemical 25]

[0069]

[Chemical formula 26]

[0070]

[Chemical 27]

[0071]

[Chemical 28]

[0072]

[Chemical 29]

[0073]

[Chemical 30]

First, the compound represented by the general formula [AI] will be described. Specific examples of the compound represented by formula [AI] are shown below, but the invention is not limited thereto.

[0075]

[Chemical 31]

[0076]

[Chemical 32]

The compounds represented by the above general formula [AI] are disclosed in JP-A Nos. 63-267750 and 63-267751, and JP-A-2-115172.
No. 2-295954, etc.

Of these, preferred compounds used in the present invention are exemplified compounds [AI-1], [AI-2],
It is [AI-13].

Next, the compound represented by the general formula [A-II] will be described.

In the general formula [A-II], examples of the alkylene group represented by X include groups such as ethylene, propylene and butylene. In-(B ₁ O) n-B ₂ representing X, examples of the alkylene group represented by B ₁ and B ₂ include methylene, ethylene and trimethylene. These alkylene groups may have a lower alkyl group such as a methyl group or an ethyl group, or a hydroxy group as a substituent.

Specific examples of the compound represented by the above general formula [A-II] are shown below, but the invention is not limited thereto.

[0082]

[Chemical 33]

[0083]

[Chemical 34]

The compound represented by the above general formula [A-II] can be synthesized by a generally known method.

Of these, particularly preferred compounds are [A
-II-1], [A-II-3], and [A-II-14].

The compound represented by the general formula [A-III] will be described below.

In the general formula [A-III],-(B ₁₁ O) n ₅ -B ₁₂ representing X ₁ includes alkylene groups represented by B ₁₁ and B ₁₂ such as methylene, ethylene and trimethylene. Can be mentioned. These alkylene groups may have a lower alkyl group such as a methyl group or an ethyl group, or a hydroxy group as a substituent.

Specific examples of the compound represented by the above general formula [A-III] are shown below, but the invention is not limited thereto.

[0089]

[Chemical 35]

[0090]

[Chemical 36]

[0091]

[Chemical 37]

[0092]

[Chemical 38]

[0093]

[Chemical Formula 39]

[0094]

[Chemical 40]

[0095]

[Chemical 41]

[A-III-16] and [A-III-1]
7], [A-III-18], [A-III-19], [A-III-
20] includes both trans and cis forms.

Among the specific examples, a particularly preferred compound is [A
-III-1], [A-III-2], [A-III-6],
[A-III-35], [A-III-36], [A-III-3
7] and [A-III-38].

The effect is remarkable when the iron salts of the compounds represented by the above general formulas [AI], [A-II] and [A-III] are contained.

The compound represented by formula [A-IV] will be described below.

In the above general formula [A-IV], R ₁ , R ₂
Examples of the alkyl group represented by include linear, branched and cyclic ones having 1 to 10 carbon atoms, and a methyl group and an ethyl group are particularly preferable. The aryl group represented by R ₁ and R ₂ is preferably a phenyl group. When R ₁ and R ₂ are alkyl groups or aryl groups, they may have a substituent. Examples of the substituent of R ₁ and R ₂ include an alkyl group,
Aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group , Sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, carboxy group, phosphono group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, carbonamide group, sulfonamide group, nitro group and the like. However, preferably,

[0101]

[Chemical 42]

It is a substituent represented by: Where Ra and R
b, Rc, Rd and Re represent a hydrogen atom, an alkyl group or an aryl group.

In the above general formula [A-IV], Y _{1 to} Y ₃
Examples of the alkylene group represented by include methylene group, ethylene group, propylene group and the like, and examples of the arylene group include phenylene group. The alkylene group and arylene group represented by Y _{1 to} Y ₃ may have a substituent. As the substituent, for example, those enumerated as the substituents of R ₁ and R ₂ can be applied, and preferably —OH —COOH —CH ₂ COOM —CH ₂ OH —CONH ₂ —CH ₂ CONH ₂ —CONHCH ₃ . (M represents a hydrogen atom, an alkali metal, or an ammonium group).

Of the compounds represented by the general formula [A-IV], preferred are the following general formulas [BI] or [BI].
It is a compound represented by I].

[0105]

[Chemical 43]

[In the formula, R ₁ and R ₂ are each a hydrogen atom,
It represents an alkyl group or an aryl group, L ₁ and L ₂ each represent an alkylene group or an arylene group, and M represents a hydrogen atom, an alkali metal, an ammonium group or an organic ammonium group. ]

[0107]

[Chemical 44]

[Wherein R _{1 to} R ₄ are each represented by the general formula [B-
I] has the same meanings as R ₁ and R ₂ and L _{1 to} L ₃ and M also have the same meanings as those of the general formula [BI]. Specific examples of the compound represented by the above general formula [A-IV] are shown below, but the invention is not limited thereto.

[0109]

[Chemical formula 45]

[0110]

[Chemical formula 46]

[0111]

[Chemical 47]

[0112]

[Chemical 48]

Of these, particularly preferred compounds are [A
-IV-1], [A-IV-8], [A-IV-13], [A-
IV-19], [A-IV-20], [A-IV-21], [A-IV
-22].

The compound represented by the general formula [AV] will be described below.

In the above general formula [AV], the alkyl group and aryl group represented by R _{1 to} R ₃ are represented by the general formula [A
The groups similar to R ₁ and R ₂ of —IV] are mentioned, and the same applies to these substituents. In the formula [A-V], the alkylene group represented by Y ₁ to Y _3, as the arylene group include the same groups as Y ₁ to Y ₃ in general formula [A-IV], of The same applies to the substituents.

In the above general formula [A-V], the divalent linking group represented by W is preferably an alkylene group having a prime number of 2 to 8 (including a cyclohexylene group),
An arylene group having 6 to 10 carbon atoms,

[0117]

[Chemical 49]

[0118]

[Chemical 50]

(B ₁ and B ₂ each represent an alkylene group or an arylene group, n represents 1 to _3. Z represents a hydrogen atom, an unsubstituted or -COOM, -SO ₃ M, or -OH alkyl group. ,
Represents an aryl group, M represents a hydrogen atom, an alkali metal, or an ammonium group), and a combination thereof may be used.

Of the compounds represented by the general formula [AV], preferred are the following general formulas [B-III] or [BI].
V].

[0121]

[Chemical 51]

[In the formula, R ₁ and R ₂ are each a hydrogen atom,
It represents an alkyl group or an aryl group, L _{1 to} L ₄ each represent an alkylene group or an arylene group, and M ₁ and M ₂ each represent a hydrogen atom, an alkali metal, an ammonium group or an organic ammonium group. ]

[0123]

[Chemical 52]

[Wherein, R _{1 to} R ₄ are each represented by the general formula [B-
III] of R ₁ and R ₂ and L _{1 to} L ₄ and M ₁ and M ₂
Also has the same meaning as those in formula [B-III]. Specific examples of the compound represented by the above general formula [AV] will be shown below, but the invention is not limited thereto.

[0125]

[Chemical 53]

[0126]

[Chemical 54]

[0127]

[Chemical 55]

[0128]

[Chemical 56]

[0129]

[Chemical 57]

Of these, a particularly preferred compound is [A
-V-1], [A-V-4], [A-V-6], [A-
V-13], [A-V-16], [A-V-20], [A-V
-23], [A-V-26], [A-V-27], [A-V-
29], [A-V-30], and [A-V-33].

Next, the compound represented by the general formula [A-VI] will be described.

Specific examples of the compound represented by the general formula [A-VI] are shown below, but the invention is not limited thereto.

[0133]

[Chemical 58]

[0134]

[Chemical 59]

[0135]

[Chemical 60]

Of these compounds, particularly preferred are [A-VI-1], [A-VI-3], [A-VI-4],
It is [A-VI-16].

The compound represented by the above general formula [A-VII] will be described below.

In the formula, A _{1 to} A ₄ may be the same or different and represent --COOM ₁ , --OH, --PO ₃ M ₁ M ₂ and --CONH ₂ . M ₁ and M ₂ represent hydrogen ion, alkali metal ion (eg sodium ion, potassium ion, lithium ion) or other cation (eg ammonium ion, methylammonium ion, tetramethylammonium ion etc.).

N _{1 to} n ₄ represent an integer of 0 to 2, and may be the same or different, preferably n ₁ = 0 and n ₃ = 0. R _{1 to} R ₄ represent a hydrogen atom, a lower alkyl group or a hydroxy group and may be the same or different, but are preferably a hydrogen atom. However,
n ₁ + n ₂ = ₁ and R ₁ to R ₄ when the n ₃ + n ₄ = 1 is not a hydrogen atom.

[0140] X is a substituted or unsubstituted alkylene group or 2 to 6 carbon atoms - represents a _{- (B 1 O) m -B} 2. 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. X
Examples of the alkylene group represented by include ethylene, trimethylene, tetramethylene and the like. Also, B ₁
And the alkylene group represented by B ₂ is methylene,
Examples include groups such as ethylene and trimethylene.

Examples of the substituent of the alkylene group represented by X, B ₁ or B ₂ include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group, etc.). m is 1
It represents an integer of 4, and is preferably 1 or 2.

Preferred specific examples of the compound represented by the above general formula [A-VII] are shown below, but the invention is not limited thereto.

[0143]

[Chemical formula 61]

[0144]

[Chemical formula 62]

[0145]

[Chemical formula 63]

Iron (III) aminopolycarboxylates of the present invention
As the complex salt, an iron (III) chelate of the following compound [A ′] group is also preferably used.

[Compound [A ′] Group] [A′-1] Ethylenediaminetetraacetic acid [A′-2] trans-1,2-cyclohexanediaminetetraacetic acid [A′-3] Dihydroxyethylglycine [A′-4 ] Ethylenediaminetetrakismethylenephosphonic acid [A′-5] Nitrilotrismethylenephosphonic acid [A′-6] Diethylenetriamine pentakismethylenephosphonic acid [A′-7] Diethylenetriaminepentaacetic acid [A′-8] Ethylenediaminedioltohydroxyphenylacetic acid [A′-9] Hydroxyethylethylenediaminetriacetic acid [A′-10] Ethylenediaminepropionic acid [A′-11] Ethylenediaminediacetic acid [A′-12] Hydroxyethyliminodiacetic acid [A′-13] Nitrilotriacetic acid [A '-14] Nitrilotripropionic acid [A'-15] triethyl Tetramine hexaacetic acid [A'-16] ethylenediamine tetrapropionic acid [A'-17] 1,3-propanediamine tetraacetic acid [A'-18] glycol ether diamine tetraacetic acid Particularly preferably [A'-1], [A '-7], [A'-
17] and [A'-18].

The iron (III) aminopolycarboxylic acid complex salt may be an anhydrous salt or a hydrated salt, but it is preferably a hydrated salt from the viewpoint of the effect of preventing scratches and chipping due to collision between tablets. preferable.

Particles containing an organic acid or a salt thereof and an aminopolycarboxylic acid iron (III) complex salt in the same particle according to the present invention (hereinafter, abbreviated as the particle of the present invention), an organic acid, the salt and an aminopolycarboxylic acid The content ratio of the iron (III) carboxylate complex salt can be any value as long as it contains at least both, but the total amount of the organic acid and the total salt of the aminopolycarboxylic acid iron (III) complex salt relative to the total number of moles (α) of the salt. The number of moles (β),
That is, the value represented by (β) / (α) is preferably 0.8 to 3.0, and particularly preferably 1.6 to 2.5.

These numerical values are ratios of the content ratios in the particles of the present invention. Furthermore, the average values in the particles of the present invention as a whole, that is, the pulverized product when the above-mentioned granulated product of the present invention is prepared. It is preferable to apply the numerical value represented by the mixing ratio of. Further, it is more preferable that the content of the organic acid and the aminopolycarboxylic acid iron (III) complex salt contained in the tablet is the above value.

Further, in addition to the particles of the present invention, a powder of an organic acid or a salt thereof, or a granule containing the same, or an aminopolycarboxylic acid iron (III) complex salt or a complex salt thereof is contained in the solid processing agent. Even when granules and the like are additionally contained, it is more preferable that the above values are obtained in all the treatment agents or one tablet contained in the same package.

A solid processing agent containing two or more kinds of the particles of the present invention can also be mentioned as one of the embodiments, but each particle of the present invention preferably has the above value.

The organic acid in the present invention means at least 1
The compound having two carboxyl groups, and the salt of an organic acid is preferably an alkali metal salt (sodium salt, potassium salt, lithium salt) or onium salt (ammonium salt) of the salt.

In the present invention, an organic acid or organic acid salt,
Alternatively, both can be used in combination. Further, two or more different compounds may be used in combination, and when an organic acid and the salt are used in combination, different salts of the free acid may be used.

The organic acid in the present invention is particularly preferably used from the compounds shown below among the compounds selected from the above general formula [II].

[0156]

[Chemical 64]

In the formula, X is --COOM, --OH, --SO ₃ M ₁ , --PO ₃
M ₂ M ₃ , and M, M ₁ , M ₂ and M ₃ may be the same or different and represent an alkali metal or hydrogen atom. Note that Xs may be the same or different from each other. r ₁ is an integer of ₁ to 4, Z is a linking group having 1 to 10 carbon atoms and is composed of n-valent carbon and hydrogen or carbon, hydrogen and oxygen atom, and k is 0 or 1.

A more preferred form is represented by the general formula [II-A] or [II-B].

[0159]

[Chemical 65]

Here, L ₈ and L ₉ are alkylene groups, and r ₂ ,
r ₃ is 0 or 1, r ₄ is an integer of 1 to 5, q is an integer of 0 to 4, and r ₄ + q ≦ 5. Or

[0161]

[Chemical formula 66]

Here, Y is

[0163]

[Chemical formula 67]

Is represented. L ₁₀ and L ₁₁ are alkylene groups, r ₅
~r ₈ is 0~1, A _10, A ₁₁ is -OH, -COOM, -SO ₃ M,
-PO ₃ M ₁ M _2, is _{-H, M, M 1, M} 2 is an alkali metal,
Or represents a hydrogen atom. L ₁₀ and L ₁₁ are divalent linking groups having 0 to 6 carbon atoms, and Y's may be the same or different from each other, and adjacent carbon atoms of Y are linked by a double bond. May be.

Further, a particularly preferred form of the compound represented by the general formula [II-B] is:

[0166]

[Chemical 68]

Or

[0168]

[Chemical 69]

It is

A particularly preferred X is -COOM. Further, preferable l ₆ is an integer of 0 to 6, and more preferably 2 to 4. Furthermore, l _7, l ₈ is an integer of 0 to 3, more preferably 0.

Specific examples of the organic acid of the present invention represented by the general formula [II] are shown below, but the invention is not limited thereto.

[0172]

[Chemical 70]

[0173]

[Chemical 71]

[0174]

[Chemical 72]

Among the above-exemplified compounds, particularly preferable are the exemplified compounds (II-1), (II-3), (II-4),
(II-5), (II-6), (II-10), (II-14),
(II-15), (II-21), (II-22), (II-23),
(II-26) and (II-27), and particularly preferable are (II-5), (II-6), (II-10) and (II-1).
5), (II-21), and (II-23). Examples of the acid salt include ammonium salt, lithium salt, sodium salt, potassium salt and the like, and sodium salt and potassium salt are particularly preferable from the viewpoint of storage stability. These organic acids or salts thereof can be used alone or in combination of two or more kinds.

Known rehalogenating agents according to the present invention include potassium chloride, sodium chloride, ammonium chloride, potassium bromide, sodium bromide, ammonium bromide, potassium iodide, sodium iodide and ammonium iodide. Although compounds can be used, bromide is preferable as a compound that further improves the effect of the present invention, and potassium bromide and ammonium bromide are more preferable.

The molar ratio of the rehalogenating agent to the aminopolycarboxylic acid iron (III) complex salt is 0.5 or more (particularly,
1.0 or more) is preferable, and 4.0 or less (particularly 3.5 or less (further 3.0 or less)) is preferable.

The saccharides as used in the present invention refer to monosaccharides and polysaccharides in which one or more monosaccharides are glycosidically linked to each other.

The monosaccharide means a single polyhydroxyaldehyde, polyhydroxyketone and their reduced derivatives,
It is a general term for a wide range of derivatives such as oxidized derivatives, deoxy derivatives, amino derivatives, and thio derivatives. Although many sugars are represented by the general formula C _n H _2n O _n , they are defined as monosaccharides in the present invention, including compounds derived from the sugar skeleton represented by this general formula. Among these monosaccharides, preferred are sugar alcohols obtained by reducing aldehyde groups and ketone groups of sugars to form primary and secondary alcohol groups, and particularly preferred is hexite having 6 carbon atoms.

The polysaccharides include celluloses, starches,
Glycogen and the like are included, and celluloses include derivatives such as cellulose ethers in which some or all of the hydroxyl groups are etherified, and starches are various decomposition products until they are hydrolyzed to maltose. Includes certain dextrins. Cellulose may be in the form of an alkali metal salt from the viewpoint of solubility. Those preferably used in these polysaccharides are celluloses and dextrins,
More preferred are dextrins.

Specific exemplified compounds of the monosaccharide of the present invention are shown below.

(C-1) Glycerin (C-2) D-trait (C-3) L-trait (C-4) meso-erythritol (C-5) D-arabit (C-6) L-arabit ( C-7) Adnit (C-8) Xylit (C-9) D-Sorbit (C-10) L-Sorbit (C-11) D-Mannit (C-12) L-Mannit (C-13) D-idit (C-14) L-idit (C-15) D-talit (C-16) L-talit (C-17) Zulcit (C-18) Allozulcit (C-19) L-erythrit (C- 20) D-erythritol Among these exemplified compounds, (C-
4) and (C-9) to (C-20).

Specific examples of the polysaccharide of the present invention are shown below.

(D-1) α-dextrin (D-2) β-dextrin (D-3) γ-dextrin (D-4) δ-dextrin (D-5) ε-dextrin (D-6) α- Limiting Dextrin (D-7) β-Limiting Dextrin (D-8) Phosphorylase Limiting Dextrin (D-9) Soluble Starch (D-10) Thin Nori Starch (D-11) White Dextrin (D-12) Yellow Dextrin (D) -13) British gum (D-14) Pine Flow (trade name, manufactured by Matsutani Chemical Co., Ltd.) (D-15) Paindex 100 (product name, manufactured by Matsutani Chemical Co., Ltd.) (D-16) Paindex 1 (Brand name, manufactured by Matsutani Chemical Co., Ltd.) (D-17) Paindex 2 (Brand name, manufactured by Matsutani Chemical Co., Ltd.) (D-18) Paindex 3 (Brand name, Matsutani Chemical Co., Ltd.) Company-made) (D-19) Pa-index 4 (trade name, manufactured by Matsutani Chemical Co., Ltd.) (D-20) Pa-index 6 (product name, manufactured by Matsutani Chemical Co., Ltd.) (D-21) Foodtex (product Name, manufactured by Matsutani Chemical Co., Ltd.) (D-22) Max 1000 (trade name, manufactured by Matsutani Chemical Co., Ltd.) (D-23) Glister P (product name, manufactured by Matsutani Chemical Co., Ltd.) (D-24) TK-16 (trade name, manufactured by Matsutani Chemical Co., Ltd.) (D-25) MPD (trade name, manufactured by Matsutani Chemical Co., Ltd.) (D-26) H-PDX (product name, manufactured by Matsutani Chemical Co., Ltd.) (D-27) Stacodex (trade name, manufactured by Matsutani Chemical Co., Ltd.) (D-28) Mabit (trade name, manufactured by Hayashibara Shoji Co., Ltd.) (D-29) Pullulan (trade name, manufactured by Hayashibara Shoji Co., Ltd.) (D-30) Methylcellulose (D-31) Dimethy Cellulose (D-32) Trimethyl cellulose (D-33) Ethyl cellulose (D-34) Diethyl cellulose (D-35) Triethyl cellulose (D-36) Carboxymethyl cellulose (D-37) Carboxyethyl cellulose (D-38) Aminoethyl cellulose (D-38) D-39) Hydroxymethylcellulose (D-40) Hydroxyethylmethylcellulose (D-41) Hydroxypropylcellulose (D-42) Hydroxypropylmethylcellulose (D-43) Hydroxypropylmethylcellulose acetate succinate (D-44) Carboxymethylhydroxyethylcellulose Among these exemplified compounds, those preferably used are
(D-1) to (D-28).

Saccharides are widespread in nature, and commercial products are easily available. Also, various derivatives can be easily synthesized by performing reduction, oxidation or dehydration reaction.

Next, the water-soluble polymer of the present invention will be described. Examples of these preferable compounds are given below.

Examples of the water-soluble polymer include polyalkylene glycol, polyvinyl alcohol, polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl acetate, aminoalkyl methacrylate copolymer, methacrylic acid-methacrylic acid ester copolymer, methacrylic acid. -Acrylic acid ester copolymers, methacrylic acid-based betaine-type polymers and the like can be mentioned. The polyalkylene glycol is preferably a compound represented by the following general formula [P].

The compound represented by the general formula [P] in the present invention will be specifically described.

[0189]

[Chemical formula 73]

In the formula, A ₁ , A ₂ and A ₃ represent linear or branched alkylene which may be substituted or unsubstituted, and these may be the same or different.

Preferably used are A ₁ , A ₂ , and A.
₃ are each unsubstituted. The most preferable forms of A ₁ , A ₂ and A ₃ are:

[0192]

[Chemical 74]

[0193]

L ₁ , l ₂ and l ₃ each represent an integer of 0 to 500.

However, l ₁ + l ₂ + l ₃ ≧ 5.

Of these, at least one of l ₁ , l ₂ and l ₃ is preferably 15 or more, more preferably 20 or more.

When the compound represented by the general formula [P] in the present invention is a copolymer type compound, it also includes those having the arrangements shown below.

-A-B-A-B-A-B-A-B-A-
B--A-A-B-A-B-B-A-A-A-B-A-A-
B-B-A--A-A-A-A-A-A-B-B-B-B-B-B-
AA-A-A-A- Among these, particularly preferred compounds include a block polymer of ethylene glycol and propylene glycol (Pluronic type nonionic) represented by the general formula [P '] and polyethylene glycol (hereinafter referred to as PEG). Sometimes abbreviated).

[0199]

[Chemical 75]

In the formula, l ₄ , l ₅ and l ₆ have the same meanings as l ₁ , l ₂ and l _{3 in the} general formula [P].

In the compound represented by the general formula [P '] in the present invention, the weight% of ethylene oxide in the total molecular weight is preferably 70% by weight or more, particularly preferably 80% by weight or more. The average molecular weight of glycol is preferably in the range of 1400 to 2100.

In the case of polyethylene glycol,
Those having an average molecular weight in the range of 600 to 20000 are preferable,
Particularly preferably, it is in the range of 1500 to 6000.

The average molecular weight in the present invention means the molecular weight calculated from the hydroxyl value.

The most preferred water-soluble polymer of the present invention is polyethylene glycol having an average molecular weight of 1500 to 6000.

In the present invention, the total addition amount of the saccharide and the water-soluble polymer is preferably 1 wt% or more of the solid processing agent, and 30 wt% or less (particularly 20 wt% or less).

The solid processing agent of the present invention can be used not only as a bleaching agent, but also as a bleach-fixing agent by using it together with a separately prepared fixing agent.

For example, the particles of the present invention and particles containing a fixing agent component (eg, granules) can be mixed, or the bleaching tablet of the present invention and a tablet containing a fixing component can be used together. is there. Further, it is advantageous in handling during use that the components of the bleaching agent and the components of the fixing agent are mixed in a predetermined amount and put in the same packaging material in advance.

A tablet obtained by tableting the mixture of the particles of the present invention and the fixing agent component can also be used.

When the bleaching agent of the present invention is used as a bleach-fixing agent in combination with a fixing agent, thiosulfate (ammonium salt, potassium salt, sodium salt) thiocyanate (ammonium salt, potassium salt, Sodium salt) is used. Further, it is preferable to use a preservative such as sulfite, hydrogen sulfite, metabisulfite, (ammonium salt, sodium salt, potassium salt).

[0210] Density (bulk density) of the apparent pressure compressed by solid processing agent obtained is preferably ^{1.0g / cm 3 ~2.0g / cm 3} , more preferably 1.1g / cm ³ ~1.5g / cm ^{Is 3} . When it is less than 1.0 g / cm ³ , the strength of the obtained solid is insufficient, and when it exceeds 2.0 g / cm ³ , the solubility of the obtained solid is deteriorated.

The use mode of the solid processing agent of the present invention is as follows:
For example, as described in JP-A-3-39739, a prescribed amount of solid processing agent can be dissolved in water to prepare a replenishing solution or a tank solution. Also, European Patent Publication EP-059
As described in 5312A publication, use the method of directly packaging the amount according to the pre-determined replenishment frequency and directly replenishing it to the processing tank according to the processing amount of the photosensitive material with the automatic developing machine. It is also possible and is not limited in any way.

[0212]

EXAMPLES The present invention will be described in detail below with reference to <Example 1> to <Example 10>.

<Example 1> (A) 1,3-Propanediamine tetrairon (III) acetate ammonium monohydrate 2500 g (B) Maleic acid 2000 g (C) Potassium bromide 1000 g (A), (B), Each of (C) was pulverized with a commercially available hammer mill to a particle size of 20 μm and used in the following experiments.

[Preparation of Sample (1-1)] Operation (1-1) The pulverized product (A) was stirred for 5 minutes in an agitation granulator for 5% of the powder weight.
While spraying water. Next, the granulated product was dried at a temperature of 50 to 65 ° C. by a fluidized bed dryer to almost completely remove the water content of the granulated product.

Operation (1-2) The crushed product (B) was also subjected to the same operation as the operation (1-2).

Operation (1-3) The granules obtained in the above operations (1-1) and (1-2) were
Sample (1-1) was prepared by mixing for 5 minutes with a cross rotary mixer.

[Preparation of Sample (1-2)] The pulverized product (A) and the pulverized product (B) were mixed in a stirring granulator for 3 minutes and then sprayed with 5% by weight of water of the powder weight. Granulation operation was performed for 5 minutes. Next, this granulated product is heated at 50 to 65 ° C. in a fluidized bed dryer.
The granules were dried at a temperature of 1 to almost completely remove the water content.

[Preparation of Samples (1-3) to (1-5)] The same granulation operation was performed using the combination of powders shown in Table 1 to prepare Samples (1-3) to (1-5). Created.

[Experiment] Each of the prepared samples was placed in a polyethylene resin container capable of being sealed and having a capacity of 2 L and having a rectangular parallelepiped shape.
A total of 2 g each were hermetically sealed. Next, the above container was set in a vibration tester BF-UA manufactured by IDEX, and a vibration test was performed. The first vibration was carried out immediately after the sample preparation, and the remaining one container was left at 25 ° C. for 24 hours after the sample preparation, and then the same vibration test was conducted. Vibration condition is 10-60
The period between H _Z was 40 minutes at a 200 sec cycle. Next, the above sample was sieved through a JIS standard sieve having an opening of 149 μm, and the weight ratio of particles dropped under the sieve was determined.
In this test, the smaller this value is, the less the generation of fine powder due to vibration and the better the handling.

The results are summarized in Table 1.

[0221]

[Table 1]

In the table, "granulation composition of granules" means, for example, [A, B] + [C] in sample (1-5) is (A).
A sample is shown in which the granulated product obtained by mixing the pulverized product of (1) and the pulverized product of (B) and the granulated product obtained by granulating the pulverized product of (C) are mixed. Furthermore, A, B and C are the same as the symbols described before for the materials in the above-mentioned prescription, and represent the following.

(A) Aminopolycarboxylic acid Fe (III) complex salt (B) Organic acid (C) Potassium bromide From the results shown in Table 1, the aminopolycarboxylic acid iron (III) complex salt and the ground product of the organic acid were mixed. In the granulated product of the present invention produced by granulation later, after 24 hours, the generation amount of fine powder was remarkably reduced by the vibration test, and the strength of the granule was increased by aging. Also, immediately after the preparation of the sample, it can be seen that the strength is stronger than that obtained by separately granulating the organic acid and the aminopolycarboxylic acid iron (III) complex.

<Example 2> In Example 2, a granule sample was prepared by the following procedure. That is, 1,3-propanediamine 4
Ferric acetate monoammonium monohydrate (PDTA-Fe-NH ₄ ) 1900g
And succinic acid (amount shown in Table 2), and potassium bromide 860
g in a commercial bantam mill until the average particle size was 20 μm, and then the fine powders were mixed in the ratios shown in Table 2,
2 kg of it in a commercial stirred granulator at room temperature for about 8 minutes,
Granulated by adding 150 ml of water. Next, the obtained granules are dried in a fluidized bed dryer at 60 ° C. for 2 hours to almost completely remove the water content of the granules to prepare granule samples (2-1) to (2-9). did.

Granule sample 800 prepared by the above method
g was stored in a thermo-hygrostat at 40 ° C. and 60% RH, the number of days until blocking was measured, and the generation rate of fine powder immediately after drying was also measured. The measurement method when fine powder is generated is a mesh opening 14
The particles were sieved through a JIS standard sieve of 9 μm, and the weight percentage of the particles dropped under the sieve was shown. The results are shown in Table 2 below.

[0226]

[Table 2]

From the results shown in Table 2 above, the sample of the present invention shows an effect of granule strength due to aging.
When the molar ratio of succinic acid to PDTA-Fe-NH ₄ is 0.8 to 3.0, even after the sample is prepared, the granular strength is higher than that outside the range of the above ratio. It was found that the generated amount was small and blocking was less likely to occur, and the handleability was excellent.

<Example 3> 1,3-Propanediamine 4 ferric ammonium acetate used in Example 1 was replaced by Japanese Patent Application No.
Example 2 using the ferric iron complex salt of Exemplified Compound AI-2 and the ferric ammonium complex salt of A-II-1, AV-1, and A'-1 described in JP-A-283032 Granule samples were prepared and storage experiments were conducted. The results are shown in Table 3. As shown in Table 3, the same results as in Example 2 were obtained.

[0229]

[Table 3]

<Example 4> The granule sample of Example 2 (2-
Table 4 shows the results of experiments conducted by the same operation as in Example 2 except that the compounds shown in Table 4 were added in the preparation of 5).

[0231]

[Table 4]

From Table 4 above, it can be seen that the generation of fine powder immediately after drying the water-soluble binder during granulation is further reduced, blocking does not occur during storage, and the effect of the present invention is better exhibited.

<Example 5> (A) 1,3-Propanediamine tetrairon (III) acetate ammonium monohydrate 2500 g (PDTA-Fe-NH ₄ ) (B) Succinic acid 2100 g (C) Potassium bromide 1000 g Each of (A), (B) and (C) was pulverized with a commercially available hammer mill to a particle size of 50 μm,
Created by the same operation as.

Granule samples N-lauroylsarcosine sodium (pulverized to a particle size of 100 μm or less) and 1.0 wt% of the granule weight were added to 2000 g of each and mixed for 3 minutes, and then the resulting mixture was mixed with Kikusui Seisakusho Ltd. Clean Press Collect 18K
With a tableting machine that has been modified, the filling amount per tablet is 2.0
g, and the compression pressure was set to 850 kg / cm ² , and 1500 tablet samples (5-1) to sample (5-5) each having a diameter of 17 mm were prepared. Immediately after tableting, and after leaving the tablet samples thus obtained for 24 hours in a closed container at 25 ° C for 24 hours after tableting, 20 tablets were randomly picked from each, and the speed checker NT-50 was used.
The hardness was measured using (Okada Seiko Co., Ltd.) and the average value was calculated. As the hardness measurement value, the maximum value of the load applied to the load cell (the load applied when the tablet breaks) is displayed. The results are shown in Table 5.

[0235]

[Table 5]

From the results shown in Table 5, the tablet of the present invention obtained by tableting the granulated product prepared by mixing the pulverized product of PDTA-Fe-NH ₄ and succinic acid was PDTA-Fe-NH ₄ . A surprising effect that hardness was increased by aging after tableting was observed, which was not found in tablets obtained by tableting a mixture of succinic acid granulated and mixed separately.

Example 6 10 g of N-lauroylsarcosine sodium was added to 1,000 g of each of the granule samples prepared in Example 2 and mixed for 3 minutes, and the obtained mixture was mixed with Kikusui Seisakusho Clean Press Collect. With a tableting machine modified from 18K, the filling amount per tablet is 2.0 g and the compression pressure is 850.
Tablet sample (6-1) with a diameter of 17 mm set to kg / cm ²
500 pieces of (6-9) were prepared. Take 20 tablet samples randomly obtained in this way and use the speed checker.
The hardness was measured using NT-50 (Okada Seiko Co., Ltd.) and the average value was calculated. Mold of raw material for tableting (tabletting machine)
The state of adhesion to the surface was observed. The results are shown in Table 6.
The values measured 24 hours after the same method as in Example 5 are shown.

[0238]

[Table 6]

<Example 7> (A) Aminopolycarboxylic acid iron (III) complex salt (described in Table 7) 5 mol (B) Succinic acid 1060 g (9 mol) Maleic acid 2Na / 1 monohydrate 270 g (1.5 mol) (C) 870 g of potassium bromide The above compounds were granulated and tableted in the same manner as in Example 5 to prepare tablet samples (7-1) to (7-30). In the same manner as in Example 5, the hardness of the tablets was measured immediately after tableting and after 24 hours.

The results are shown in Table 7.

[0241]

[Table 7]

From the results shown in Table 7 above, it was found that all the aminopolycarboxylic acid iron (III) complex salts of the present invention exhibited the same effects of the present invention as PDTA-Fe-NH ₄ .

<Example 8> (A) 1,3-Propanediamine tetrairon (III) acetate ammonium monohydrate 3 mol (B) Organic acid (described in Table 8) Total 7 mol (C) Ammonium bromide 350 g Granulation was performed in the same manner as in Example 5 and tableting was performed to prepare tablet-shaped samples (8-1) to (8-34). or,
These samples were evaluated in the same manner as in Example 5. The results are shown in Tables 8 and 9.

[0244]

[Table 8]

[0245]

[Table 9]

From the above results, a granule containing the organic acid of the present invention and an iron (III) complex salt of aminopolycarboxylic acid was obtained by tableting. As with succinic acid, the tablets were found to have the effect of increasing hardness due to aging. Further, by combining a plurality of organic acids and organic acid salts, a better effect can be obtained.

Example 9 (A) 1,3-Propanediamine tetrairon (III) acetate Ammonium monohydrate 4000 g (B) Succinic acid 1800 g Maleic acid 2Na · monohydrate 70 g Adipic acid 80 g (C) 1, 3-Propanediamine tetraacetic acid 20 g Exemplified compound (listed in Table 9) Potassium bromide 1600 g Each of the above compounds was pulverized to a particle size of 50 μm or less and mixed for 3 minutes with a stirring granulator, and then the powder weight was 5 The granulation operation was performed for 5 minutes while spraying% water. Next, this granulated product was dried at a temperature of 50 to 65 ° C. by a fluidized bed dryer to almost completely remove the water content of the granulated product.

To the granule sample obtained by the above operation, sodium N-lauroylsarcosine (pulverized to a particle size of 50 μm or less) was added in an amount of 1.0 wt% of the granule weight, and the mixture was mixed for 3 minutes. Tableting was performed by operation, and the hardness of the tablet was measured. However, the tablet diameter is 30 mm and the filling amount is
It was set to 11 g. Further, the variation in the weight of the tableted tablets was arbitrarily sampled, and 20 tablets were sampled to obtain the number 1.

[0249]

[Equation 1]

The results are shown in Table 10.

[0251]

[Table 10]

From the results shown in Table 10, an increase in hardness was recognized when the polyethylene glycols, saccharides and dextrins of the present invention were used. Further, among polyethylene glycols, those having a count of 1540 to 6000 have the effect of reducing not only the hardness but also the degree of variation in weight, and it can be inferred that the granules have good fluidity.

Further, when saccharides were added, a decrease in weight variation and a remarkable increase in hardness were observed, and it can be said that this is a better method for carrying out the present invention.

Also, it is understood that the addition amount is preferably 2% to 30%.

Example 10 (A) Aminopolycarboxylic acid iron (III) complex / ammonium salt, described in Table 11 5 mol (B) Succinic acid 1060 g (9 mol) Maleic acid 2Na / 1 monohydrate 270 g (1.5 mol) ( C) Potassium bromide 870 g The above compound was tested in the same manner as in Example 5. Tablet samples (10-1) to (10-10) were prepared. The hardness of the tablets was measured immediately after tableting and after 24 hours in the same manner as in Example 5. The results are shown in Table 11.

[0256]

[Table 11]

From the above results, the effect of similarly increasing the hardness by aging was obtained for the other chelating agents of the present invention.

From the above results, it can be seen that the tablet samples of the present invention all show an increase in hardness due to aging.
Molar ratio of succinic acid to TA-Fe-NH ₄ is greater hardness immediately after tableting when 0.8 to 3.0, also is good no deposits on the punch.

[0259]

As described above, the solid processing agent for bleaching silver halide color photographic light-sensitive material of the present invention has the following effects.

It becomes a processing agent that is easy to transport and handle. It does not require the resin bottle of the conventional processing agent container. It hardly generates fine powder. It hardly adheres to the tableting machine. It hardly causes blocking. The strength of processing is improved.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location // C07C 229/24 7537-4H

Claims (23)

[Claims] 1. A bleaching ability characterized by comprising at least particles containing at least one aminopolycarboxylic acid iron (III) complex salt and an organic acid and / or the salt all together in the same particle. Solid processing agent for silver halide color photographic light-sensitive materials. 2. The iron (III) complex salt of an aminopolycarboxylic acid is an iron (III) chelate compound of a compound represented by the following general formula [I] and / or a salt thereof. Solid processing agent for silver halide color photographic light-sensitive materials having the bleaching ability described above. [Chemical 1] 3. The iron (III) aminopolycarboxylic acid complex salt is represented by the following general formulas [AI], [A-II] and [A-II].
I], [A-IV], [A-V], [A-VI], [A-VI]
2. A silver halide color photographic light-sensitive material having a bleaching ability according to claim 1, which is an iron (III) chelate compound of a compound represented by the formula [I] or the following compound [A '] and / or a salt thereof. Solid processing agent. [Chemical 2] [In the formula, A _{1 to} A ₄ may be the same or different and each is a hydrogen atom, a hydroxy group, —COOM, —PO ₃ (M ₁ ) ₂ , or —CH ₂ COO.
M _2, represents a -CH ₂ OH or a lower alkyl group. However, A ₁ ~
At least one -COOM of _{A 4, -PO 3 (M 1} ) 2, -CH 2 COOM
_{Is 2} . M, M ₁ and M ₂ each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. ] [Chemical 3] [In the formula, A _{11 to} A ₁₄ may be the same or different,
CH ₂ OH, represents a -COOM ₃ or -PO ₃ (M _{4) 2.} M ₃ and M ₄ each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. X is an alkylene group having 2 to 6 carbon atoms _{- (B 1 O) n-} B 2 - represents a. n represents an integer of 1 to 8, and B ₁ and B ₂ may be the same or different and each represents an alkylene group having 1 to 5 carbon atoms. ] [Chemical 4] [In the formula, A _{21 to} A ₂₄ may be the same or different,
CH ₂ OH, represents a -COOM ₅ or -PO ₃ (M _{6) 2.} M ₅ and M ₆ each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. X ₁ represents a linear or branched alkylene group having 2 to 6 carbon atoms, a saturated or unsaturated organic group forming a ring, or — (B ₁₁ O) n ₅ —B ₁₂ —. n ₅ is 1
Represents an integer of 8, and B ₁₁ and B ₁₂ may be the same or different and each represents an alkylene group having 1 to 5 carbon atoms.
n _{1 to} n ₄ represent an integer of 1 or more, and may be the same or different. ] [Chemical 5] [In the formula, R ₁ and R ₂ each represent a hydrogen atom, an optionally substituted alkyl group or an aryl group. L is , Y _{1 to} Y ₃ each represent an alkylene group or an arylene group, X ₂ and X ₃ each represent an oxygen atom or a sulfur atom, and R _{3 to} R ₇ each represent a hydrogen atom, an alkyl group, Represents an aryl group. ] [Chemical 7] [In the formula, R _{1 to} R ₃ each represent a hydrogen atom, an optionally substituted alkyl group or an aryl group. L is a general formula [A
-IV] is synonymous with L. W represents a divalent linking group. ] [Chemical 8] [In the formula, R _{1 to} R ₃ and R _{6 to} R ₉ each represent a hydrogen atom, an optionally substituted alkyl group or an aryl group,
R ₄ and R ₅ are each a hydrogen atom, a halogen atom, a cyano group, a nitro group, an acyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, a sulfonyl group, a sulfinyl group, or an alkyl group which may be substituted. Alternatively, it represents an aryl group, and R ₄ and R ₅ may together form a 5-membered ring or a 6-membered ring. A represents a carboxy group, a phosphono group, a sulfo group, a hydroxy group, or an alkyl metal salt or ammonium salt thereof. Y represents an alkylene group or an arylene group and may have a substituent. t and u are 0 or 1 respectively
Represents ] [Chemical 9] Wherein, A ₁ to A ₄ is _{-COOM 1, -OH, -PO 3 M} 1 M 2, -CONH
_{2 and} may be the same or different.
M ₁ and M ₂ represent hydrogen ion, alkali metal ion or other cation. n _{1 to} n ₄ represent an integer of 0, 1 or 2. R _{1 to} R ₄ represent a hydrogen atom, a lower alkyl group or a hydroxy group (provided that when n ₁ + n ₂ = 1 and n ₃ + n ₄ = 1 R _{1 to} R ₄ do not become hydrogen atoms). X has 2 to 2 carbon atoms
6 substituted or unsubstituted alkylene group or - (B ₁ O) _m -
Represents B ₂ −. m represents an integer of 1 to 4, and 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. ] Compound [A '] group [A'-1] ethylenediaminetetraacetic acid [A'-2] trans-1,2-cyclohexanediaminetetraacetic acid [A'-3] dihydroxyethylglycine [A'-4] ethylenediaminetetrakismethylene Phosphonic acid [A'-5] Nitrilotrismethylenephosphonic acid [A'-6] Diethylenetriamine pentakismethylenephosphonic acid [A'-7] Diethylenetriaminepentaacetic acid [A'-8] Ethylenediaminedioltohydroxyphenylacetic acid [A'- 9] Hydroxyethyl ethylenediamine triacetic acid [A'-10] ethylenediaminepropionic acid [A'-11] ethylenediamine diacetic acid [A'-12] hydroxyethyliminodiacetic acid [A'-13] nitrilotriacetic acid [A'-14] Nitrilotripropionic acid [A'-15] triethylenetetramine hexa Acid [A'-16] ethylenediaminetetraacetic propionic acid [A'-17] 1,3-propanediamine tetraacetic acid [A'-18] glycol ether diaminetetraacetic acid 4. The iron (III) aminopolycarboxylic acid complex salt is selected from 1,3-propanediaminetetraacetic acid, ethylenediaminetetraacetic acid, ethylenediamine-N, N'-disuccinic acid or β-alanine-N, N-diacetic acid. The iron (I
II) A chelating compound, which is a solid processing agent for a silver halide color photographic light-sensitive material having a bleaching ability according to claim 1. 5. The solid processing agent for a silver halide color photographic light-sensitive material having a bleaching ability according to claim 1, wherein the solid processing agent is in a granular form. 6. Particles containing the at least one aminopolycarboxylic acid iron (III) complex salt and an organic acid and / or the salt together in the same particle are the organic acid and / or
Alternatively, the salt and the iron (III) aminopolycarboxylic acid complex salt are each a granulated product prepared by mixing the solid particles having a particle size of 150 μm or less, and the average particle size of the granulated product. Is 30
The solid processing agent for a silver halide color photographic light-sensitive material having a bleaching ability according to claim 5, which is 0 to 3000 μm. 7. The solid processing agent for bleaching silver halide color photographic light-sensitive materials according to claim 5, wherein the organic acid is a compound having at least one carboxyl group. 8. The solid processing agent for a silver halide color photographic light-sensitive material having a bleaching ability according to claim 7, wherein the organic acid is a compound represented by the following general formula [II]. [Chemical 10] 9. The organic acid is succinic acid, maleic acid,
A solid processing agent for a silver halide color photographic light-sensitive material having a bleaching ability according to claim 4 or 5, which is at least one compound selected from glycolic acid, adipic acid, citric acid and fumaric acid. 10. The granules are granulated so that the molar ratio of the total content of the organic acid and the salt to the content of the aminopolycarboxylic acid iron (III) complex salt is 0.8 to 3.0. A solid processing agent for a silver halide color photographic light-sensitive material having a bleaching ability according to any one of claims 5 to 9. 11. The solid treating agent is characterized in that the molar ratio of the total content of the organic acid and the salt with respect to the total content of the aminopolycarboxylic acid iron (III) complex salt is 0.8 to 3.0. The solid processing agent for silver halide color photographic light-sensitive materials according to any one of claims 5 to 10. 12. The silver halide color having a bleaching ability according to claim 5, wherein the solid processing agent contains at least one compound selected from the following compound group. Solid processing agent for photographic light-sensitive materials. (Group A) saccharides (Group B) water-soluble polymer (Group C) dextrins 13. The solid processing agent for a silver halide color photographic light-sensitive material having a bleaching ability according to claim 5, wherein the solid processing agent is a bleaching agent. 14. The solid processing agent for a silver halide color photographic light-sensitive material having a bleaching ability according to claim 1, wherein the solid processing agent is in the form of tablets. 15. A particle obtained by compression-molding particles containing the at least one aminopolycarboxylic acid iron (III) complex salt and an organic acid or an organic acid salt in the same particle all together. 14. A solid processing agent for a silver halide color photographic light-sensitive material as described in 14, which has a bleaching ability. 16. Particles containing the at least one aminopolycarboxylic acid iron (III) complex salt and an organic acid or the salt together in the same particle, wherein the organic acid and / or the salt and the amino Granules produced by mixing polycarboxylic acid iron (III) complex salts each of which is a solid having a particle diameter of 150 μm or less, and having an average particle diameter of 300 to 300.
16. The solid processing agent for a silver halide color photographic light-sensitive material having a bleaching ability according to claim 14, which is 0 μm. 17. A silver halide color photographic light-sensitive material having bleaching ability according to claim 14, wherein the organic acid is a compound having at least one carboxyl group. Solid processing agent. 18. The solid processing agent for a silver halide color photographic light-sensitive material having a bleaching ability according to claim 17, wherein the organic acid is a compound represented by the following general formula [II]. [Chemical 11] 19. The organic acid according to claim 14, wherein the organic acid is at least one compound selected from succinic acid, maleic acid, glycolic acid, adipic acid, citric acid, and fumaric acid. 2. A solid processing agent for a silver halide color photographic light-sensitive material as described in item 1, which has a bleaching ability. 20. The granulation is performed so that the molar ratio of the total content of the organic acid and the salt to the content of the particles and the iron (III) aminopolycarboxylic acid complex salt is 0.8 to 3.0. 20. A solid processing agent for a silver halide color photographic light-sensitive material having a bleaching ability according to any one of claims 14 to 19. 21. In the tablet-shaped solid processing agent, iron (III) aminopolycarboxylate in the total amount of the solid processing agent.
The molar ratio of the total content of the organic acid and the salt to the total content of the complex salt is 0.8 to 3.0, 14 to
21. A solid processing agent for a silver halide color photographic light-sensitive material according to any one of 20. 22. The halogen having a bleaching ability according to any one of claims 14 to 21, wherein the tablet-like solid processing agent contains at least one compound selected from the following compound group. Solid processing agent for silver halide color photographic light-sensitive materials. (Group A) saccharides (Group B) water-soluble polymer (Group C) dextrins 23. The solid processing agent for a silver halide color photographic light-sensitive material according to claim 14, wherein the solid processing agent is a bleaching agent.