JP2003344980A - Solid processing agent for color development for silver halide photographic sensitive material, and processing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid processing agent for a silver halide photographic sensitive material capable of improving abnormality in putting operation due to fine powder generated during transport of the solid processing agent and in putting and to provide a processing method for the same. <P>SOLUTION: In the solid processing agent for color development for a silver halide photographic sensitive material, (1) ≥50 mol% of a p-phenylenediamine color developing agent contained in the solid processing agent is a free body, (2) all of the p-phenylenediamine color developing agent is a free body or (3) an alkali metal hydroxide is not substantially contained in the solid processing agent. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a color developing solid processing agent and processing method for silver halide photographic light-sensitive materials,
More specifically, it relates to a solid processing agent for a silver halide photographic light-sensitive material and a processing method thereof, which is capable of remarkably improving charging operation abnormality due to fine powder generated during transportation or charging of the solid processing agent.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter, also referred to as a light-sensitive material or a light-sensitive material) is processed by processes such as development, desilvering, washing and stabilization after exposure. The processing is
Usually, a method of replenishing a replenisher so as to keep the activity of the processing solution constant is generally used in an automatic processor. The replenishment of the replenisher is intended to dilute the eluate from the light-sensitive material and replenish the consumed amount. Such a replenisher is usually manufactured, transported and stored in the form of a concentrated solution, and when used, it is diluted with a certain amount of water and used as a replenisher.

The form of this concentrated solution has several parts in order to increase the degree of concentration and reduce the load on transportation and storage, and to improve storage stability. In the case of a concentrated solution for color development, Usually has a three-part structure. recent years,
Attempts have been made to reduce the number of melting steps by converting this multi-part configuration into a single part (US Pat. No. 9,132,200).

However, since there is no change in preparing the replenishing solution, it is necessary to prepare a certain amount of water for the dissolving work when preparing the replenishing solution. Therefore, the complexity of the dissolution work does not change significantly even if the structure of the parts is reduced, and the inconvenience of the fixed amount of dissolved water has been a problem.

As a method for solving this problem, a method has been proposed in which the melting operation is made free and the replenisher is directly charged into the processing tank (US Pat. No. 5,557,614). This technique introduces a method of directly replenishing a concentrated solution with a concentrated solution. In this method, the number of pumps required for replenishment increases in the case of a color developer having multiple parts,
In addition, maintainability is poor because the concentrated solution must be replenished accurately.

Therefore, a method of directly introducing the solid processing agent into the processing tank has been introduced (Japanese Patent Laid-Open Nos. 6-208215 and 7-92623). Since this method replenishes the replenisher and the dissolved water separately, there is no load on the replenishing pump for the dissolved water and is considered to be an effective means. However, according to the research conducted by the present inventor, it has been found that a trouble occurs in a device for automatically adding a new solid processing agent. That is, the powder filling generated by the contact between the solid processing agent and the charging member or the solid processing agents during the solid processing agent manufacturing process, the transportation process, and the charging operation process enters the details of the automatic charging device and solidifies to cause an abnormal charging operation. May occur and affect the processing characteristics. Conventionally, the development has been attempted focusing on how to prevent the generation of this powder (Japanese Patent Laid-Open No. 8-22071).
5).

According to the research conducted by the present inventor, it is difficult to prepare a solid processing agent that does not generate powder at all, and even if the generation of powder can be suppressed to a minute level, a complete solution can be obtained even if there is a delaying effect. I came to the conclusion that it should not. As mentioned above,
It has been a proposition of a replenishment method using a solid processing agent to solve the charging operation failure due to the generated powder.

[0008]

In view of the above situation, an object of the present invention is to provide a solid processing agent for color development,
It is an object of the present invention to provide a solid processing composition and a processing method thereof, which can stably maintain processability without causing malfunction of a charging device caused by solidification of fine powder generated from the solid processing agent.

[0009]

The present invention for solving the above-mentioned problems has the following constitution. 1. A color developing solid processing agent for silver halide photographic light-sensitive materials, characterized in that 50 mol% or more of the p-phenylenediamine type color developing agent contained in the solid processing agent is a free form.

2. The above 1-characterized in that all of the p-phenylenediamine type color developing agents are in a free form.
A solid development agent for color development for the described silver halide photographic light-sensitive material.

3. 3. The solid developing agent for color development for silver halide photographic light-sensitive materials as described in 1 or 2 above, wherein the solid processing agent contains substantially no alkali metal hydroxide salt.

4. 4. The color development for silver halide photographic light-sensitive material as described in 1, 2, or 3, wherein the solid processing agent contains at least one compound represented by the following general formula (1) or (2). Solid processing agent.

[0013]

[Chemical 2]

[In the formula, R ₁ represents an alkyl group, R ₂ represents an alkyl group or a hydrogen atom, R ₃ represents an alkylene group, M represents a hydrogen atom, a sodium atom, a potassium atom,
Represents a lithium atom or triethanol ammonium. ]

General formula (2) R-O _n SO ₃ M [In the formula, R represents an aliphatic group, n represents 0 or 1, and M represents a cation. ]

5. Of the p-phenylenediamine color developing agents contained, 50 mol% or more of the color developing solid processing agent for silver halide photographic light-sensitive materials, in which 50 mol% or more is free, is divided as necessary and directly charged into the processing tank of the automatic processor. A method of processing a silver halide photographic light-sensitive material, characterized by:

6. 5. The above-mentioned p-phenylenediamine-based color developing agent is all free.
The method for processing a silver halide photographic light-sensitive material described in 1.

7. 7. The method for processing a silver halide photographic light-sensitive material as described in 5 or 6 above, wherein the solid processing agent does not substantially contain an alkali metal hydroxide salt.

8. 8. The method for processing a silver halide photographic light-sensitive material described in 5, 6 or 7, wherein the solid processing agent contains at least one compound represented by the general formula (1) or (2). .

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The p-phenylenediamine color developing agent used in the present invention is a p-phenylenediamine derivative, and representative examples thereof are shown below, but the invention is not limited thereto.

[Exemplified Compounds] 1: N, N-diethyl-p-phenylenediamine 2: 2-amino-5-diethylaminotoluene 3: 2-amino-5- (N-ethyl-N-laurylamino) toluene 4: 4- (N-ethyl-N- (β-hydroxyethyl)
Amino) aniline 5: 2-methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline 6: 4-amino-3-methyl-N-ethyl-N- (β-
(Methanesulfonamide) ethyl) aniline 7: N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide 8: N, N-dimethyl-p-phenylenediamine 9: 4-amino-3-methyl-N- Ethyl-N-methoxyethylaniline 10: 4-amino-3-methyl-N-ethyl-N-β-
Ethoxyethylaniline 11: 4-amino-3-methyl-N-ethyl-N-β-
Ethoxyethylaniline

Of these p-phenylenediamine derivatives, the compound particularly preferably used in the present invention is 4-amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline (exemplified compound). 6) and 2-methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline (Exemplified compound 5).

It is necessary to add 50 mol% or more of these p-phenylenediamine color developing agents in the form of a free salt, preferably 100% free salt. When used in combination, a sulfate, a hydrochloride, a sulfite, a p-toluenesulfonate, or the like is used.

The free salt of the p-phenylenediamine color developing agent has a low solubility in water, and it is troublesome to handle since it requires the addition of a solvent to stably supply it in a solution system such as a concentration kit. . In the case of a solid processing agent, it is possible to supply it as a solid, so no solvent is required, and by adding it directly to the processing tank without creating a replenisher, it dissolves under the conditions of sufficient stirring at a constant temperature, so the solubility is It doesn't matter. By using this free salt as a solid processing agent,
In addition to the advantages of handling as described above, it was a surprising effect that the generated fine powder is less likely to solidify and does not affect the charging operation.

The free salt may be produced by desalting from a commercially available color developing agent (CD-3 or CD-4) and, in that case, in order to improve the storage stability as a solid. Sulfite and hydroxylamine derivative compounds may be added.

Considering that the p-phenylenediamine color developing agent is a solid processing agent, the addition amount is 3% of the total weight.
-30% is preferable.

It is more preferable that the solid processing agent of the present invention does not contain an alkali metal hydroxide salt. The alkali metal hydroxide refers to a hydroxide salt of an element (lithium, sodium, potassium, rubidium, cesium, francium) which is classified in Group I of the periodic table. The absence of the alkali metal salt can further prevent solidification of the fine powder under high humidity conditions.

General formula (1) preferably used in the present invention
The compound represented by will be described.

In the general formula (1), R ₁ represents a linear or branched, optionally substituted, saturated or unsaturated alkyl group having 1 to 40 carbon atoms, preferably 3 to 30 carbon atoms. R ₂ represents a hydrogen atom or a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group. Group and amyl group are mentioned, and a methyl group is particularly preferable. R ₃ represents a linear or branched saturated or unsaturated alkylene group having 1 to 10 carbon atoms which may be substituted, and the substituent is a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a carboxybutyl group. And a carboxyamyl group. Preferred examples of R ₃ include methylene group, ethylene group, butylene group, propylene group, carboxymethylmethylene group, carboxyethylmethylene group, carboxymethylethylene group and carboxyethylethylene group, and particularly preferred is ethylene group. .

M represents a hydrogen atom, a sodium atom, a potassium atom, a lithium atom, or triethanolammonium.

Typical examples of the compounds represented by the general formula (1) are shown below, but the present invention is not limited to these compounds.

[0032]

[Chemical 3]

[0033]

[Chemical 4]

[0034]

[Chemical 5]

[0035]

[Chemical 6]

[0036]

[Chemical 7]

[0037]

[Chemical 8]

[0038]

[Chemical 9]

[0039]

[Chemical 10]

[0040]

[Chemical 11]

[0041]

[Chemical 12]

Of these exemplified compounds, those preferably used are (1) -4, (1) -7, (1) -10,
(1) -13, (1) -16, (1) -37, (1)-
40, (1) -43, (1) -46, (1) -49,
(1) -70, (1) -73, (1) -76, (1)-
79, (1) -82, and particularly preferably (1)-
10, (1) -13, (1) -16, (1) -40,
(1) -43 and (1) -49 are preferable.

In the present invention, the addition amount of the compound represented by the general formula (1) is per unit weight (as% by weight) of the solid developing agent for color development, preferably 0.1% (W / W).
~ 5% (W / W).

General formula (2) preferably used in the present invention
The compound represented by will be described.

In the general formula (2), R has 4 to 4 carbon atoms.
20 is preferable and C6-10 is the most preferable. Although the aliphatic group may be branched, it is preferably linear. Alternatively, it may contain an unsaturated group, but it is preferably a saturated group. Particularly preferably, the aliphatic group is an n-hexyl group or an n-octyl group.

M represents a cation, preferably an alkali metal, alkaline earth metal or ammonium group. Particularly preferred are sodium ion, potassium ion and lithium ion.

Specific examples of the compound represented by the general formula (2) are shown below, but the invention is not limited thereto. _{(2) -1 C 2 H 5} SO 3 Na (2) -2 CH 3 (CH 2) 5 SO 3 Na (2) -3 CH 3 (CH 2) 6 SO 3 Na (2) -4 CH 3 ( _{CH 2) 7 SO 3 Na (} 2) -5 CH 3 (CH 2) 6 OSO 3 Na (2) -6 CH 3 (CH 2) 7 OSO 3 Na (2) -7 CH 3 O (CH 2) 2 SO ₃ Na

[0048]

[Chemical 13]

(2) -9 CH ₃ CH ₂ CH ₂ CH = C
_{HCH 2 CH 2 CH 2 SO 3} Na (2) -10 CH 3 (CH 2) 5 SO 3 K (2) -11 CH 3 (CH 2) 6SO 3 Li (2) -12 CH 3 (CH 2) 7 _{SO 3 Li (2) -13 CH} 3 (CH 2) 7 SO 3 K

In the present invention, the addition amount of the compound represented by the general formula (2) is preferably 0.1% (w / w) per unit weight (as% by weight) of the solid developing agent for color development.
~ 5% (W / W).

In the present invention, an alkaline agent having a pH of 9 to 1 is used.
It is preferable to contain a buffering agent having a buffering capacity between 4 and 4. Particularly preferred are alkali metal carbonates, phosphates, salicylates, sulfosalicylates and the like, and most preferred are alkali metal carbonates.

The present invention preferably contains a compound represented by the general formula (3).

Formula (3) H- (OC ₂ H ₄ ) _m —OH [In the formula, m represents an integer of 1 to 500. ]

Among the compounds represented by the general formula (3), a polyethylene glycol compound having an average molecular weight of 200 or more is preferable, more preferably an average molecular weight of 1,000 to
It is 10000 polyethylene glycol compounds.

In the present invention, the glycol compound,
The amount of the other compound represented by the general formula (3) added is 1 g / L to 100 g as the amount when used as a color development processing solution.
/ L is preferable, and more preferably 5 g / L to 50 g / L.
Is the range.

In the present invention, as the antioxidant, sulfite,
Either a hydroxylamine salt or a compound represented by the general formula (4) may be contained.

[0057]

[Chemical 14]

(In the formula, L represents an alkylene group, and A ₀₁
Represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, an amino group, an ammonio group, a carbamoyl group or a sulfamoyl group, and R represents a hydrogen atom or an alkyl group. Each of L, A ₀₁ , and R includes a straight chain and a branched chain, and may be unsubstituted or substituted. L and R may combine to form a ring. )

The compound represented by formula (4) will be described in more detail. In the formula, L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. Specifically, groups such as methylene, ethylene, trimethylene, and propylene are mentioned as preferable examples. As the substituent, a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group,
It represents an ammonio group which may be alkyl-substituted, and preferred examples thereof include a carboxyl group, a sulfo group, a phosphono group, and a hydroxyl group. A ₀₁ represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, or an alkyl-substituted amino group, an ammonio group, a carbamoyl group or a sulfamoyl group, and a carboxyl group, a sulfo group, a hydroxyl group, Preferred examples include a phosphono group and a carbamoyl group which may be alkyl-substituted.

Preferred examples of -LA- ₀₁ include carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group and hydroxyethyl group. Of these, a carboxymethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group can be mentioned as particularly preferable examples.

R represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and has 1 carbon atom.
-5 are preferable. The substituent represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, or an amino group which may be substituted with an alkyl group, an ammonio group, a carbamoyl group or a sulfamoyl group. There may be two or more substituents. R as a hydrogen atom, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group,
Sulfobutyl group, phosphonomethyl group, phosphonoethyl group, hydroxyethyl group can be mentioned as a preferred example, hydrogen atom, carboxymethyl group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group, phosphonoethyl group is mentioned as a particularly preferred example. be able to. L and R may combine to form a ring.

Typical examples of the compounds represented by the general formula (4) are shown below, but the invention is not limited to these compounds.

[0063]

[Chemical 15]

[0064]

[Chemical 16]

[0065]

[Chemical 17]

[0066]

[Chemical 18]

In the compounds represented by the general formula (4), when A ₀₁ represents an ammonio group, a sulfate ion, p-toluenesulfonate ion, chlorine ion, sulfite ion or the like is used as a counter ion of the ammonio group. May be accompanied. Further, L and A ₀₁ are a carboxyl group, a sulfo group,
When accompanied by a substituent having an acid radical such as a phosphono group, a phosphinic acid residue, or a hydroxyl group, the hydrogen of the acid radical is
It may be replaced with an alkali metal atom or an ammonium atom group.

The amount of the compound represented by the general formula (4) added is preferably 0.05 mol / L to 5 mol / L, more preferably 0.1 mol, when the color developing solution is used. / L to 1 mol / L.

A triazinyl stilbene type optical brightening agent may be used in the solid processing agent of the present invention. As the triazinyl stilbene-based optical brightening agent, known ones can be used without particular limitation.

The solid processing agent of the present invention may contain a saccharide compound. Known saccharide compounds can be used without particular limitation. The solid processing agent of the present invention may contain a chelating agent. Any known chelating agent can be used without particular limitation.

Among the color-developing solid processing agents of the present invention, granules or tablets are preferably used because of high replenishment accuracy and easy handling.

To solidify the photographic processing agent, a concentrated liquid or fine powder or particles photographic processing agent and a water-soluble binder are kneaded and molded, or the surface of the temporarily molded photographic processing agent is mixed with a water-soluble binder. Arbitrary means, such as forming a coating layer by spraying, 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 preferable tablet manufacturing method is a method in which a solid processing agent in powder form is granulated and then a tableting step is performed. There is an advantage that the solubility and storability are improved and the photographic performance becomes stable as compared with the solid type processing agent formed by the tableting process by simply mixing the solid processing agent components.

As the granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation and spray drying granulation are used. Can be done.
In order to form tablets, the average particle size of the obtained granules is 100 to 800 μm in that when the granules are mixed and compressed under pressure, nonuniformity of the components, so-called segregation does not easily occur.
It is preferable to use the above-mentioned one, and more preferably 200
˜700 μm. Furthermore, the particle size distribution is 60 for granulated particles.
% Or more is preferably within a deviation of ± 100 to 150 μm. The obtained granulated product is used as it is as granules. When compressing the obtained granulated product under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a briquetting machine can be used. The solid processing agent obtained by compression under pressure can have any shape, but from the viewpoint of productivity and handleability, or from the problem of dust when used on the user side, a cylindrical type, a so-called tablet is used. preferable.

More preferably, at the time of granulation, the above-mentioned effect becomes more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a bleaching agent, a preservative and the like.

The method for producing the tablet treating agent is described in, for example, JP-A Nos. 51-61837, 54-155038 and 52-52.
No. 88025, British Patent No. 1,213,808 and the like, and can be produced by a general method described in the specification. Further, as a granule treating agent, JP-A Nos. 2-109042 and 2-10904 can be used.
It can be produced by a general method described in the specifications such as No. 3, No. 3-39735 and No. 3-39739. Further, the powder treating agent is described in, for example, JP-A-54-133332,
It can be produced by a general method as described in the specifications of British Patents 725,892 and 729,862 and German Patent 3,733,861.

For processing light-sensitive materials with the color developing solid processing agents of the present invention, color developing an imagewise exposed silver halide photographic element to produce the desired developed image,
It is carried out under a suitable time and temperature condition in a suitable processing apparatus, in contact with the color developing processing solution prepared according to the present invention. Thereafter, one or more of a development stop step, a bleach step, a fixing step, a fixing step, in a particular desired order as is known in the art.
Additional processing can be performed using conventional procedures including, but not limited to, bleaching / fixing steps, washing (or rinsing) steps, stabilizing steps and drying steps. Useful processing steps of various processing protocols, including conventional Process C-41 processing for color negative films, Process RA-4 for processing color papers, and Process E-6 for processing color reversal films, and their useful conditions. And materials are well known.

The processing time and temperature for each processing step of the present invention are generally those used in the art. For example, color development generally involves 20-6.
It is carried out at a temperature of 0 ° C. The preferred time for color development is 15
~ 250 seconds. For color paper processing, it is desirable that the color development time is shorter (for example, 45 seconds or less). The color developing solid processing agent of the present invention can be mixed with an alkali-containing part, if necessary, and appropriately diluted to at least 4 times and up to 12 times to prepare a working concentration solution or a replenishing solution. The dilution ratio is preferably 4 to 10 times, and water is usually used as the diluting liquid. It can be diluted during or before treatment.

In one embodiment of the present invention, the color developing solid processing agent is a photographic bleaching composition, a photographic bleaching / fixing composition,
One pharmaceutical formulation of a photoprocessing chemical kit that may include one or more other photoprocessing compositions including, but not limited to, a photofix composition, a photo stabilizing or a final rinse composition. Such additional compositions can be formulated into solid processing agents or concentrates or working strength solutions.

An example of an automatic processor (hereinafter, simply referred to as an automatic processor) to which the solid processing agent according to the present invention can be applied will be described with reference to the drawings. FIG. 1 is a schematic diagram of a printer processor in which an automatic developing machine A and a photo printing machine B are integrally configured.

In FIG. 1, in the lower left part of the photographic printing apparatus B, a magazine M containing unexposed photosensitive material photographic paper in a roll is set. The photographic printing paper pulled out from the magazine is cut into a predetermined size via the feed roller R and the cutter section C to become a sheet-shaped printing paper. The sheet-shaped printing paper is conveyed by the belt conveying means B,
The image of the original image O is exposed in the exposure section E. The exposed sheet-shaped printing paper is further conveyed by a plurality of pairs of feed rollers R and introduced into the automatic developing machine A. In the automatic developing machine A, the sheet-shaped printing paper is processed in the color developing tank 1A, the bleach-fixing tank 1B, the stabilizing tanks 1C, 1D, 1E (substantially 3
(Container structure) is sequentially conveyed by roller conveying means (reference symbol None), and color development processing, bleach-fixing processing, and
Stabilization processing is performed. The sheet-shaped photographic paper that has been subjected to each of the above processes is dried in the drying unit 35 and discharged to the outside of the machine.

Incidentally, the alternate long and short dash line in the figure indicates the conveyance path of the photosensitive material. In the embodiment, the light-sensitive material is introduced into the automatic developing machine A in a cut state, but it may be introduced into the automatic developing machine in the form of a strip. In that case, if an accumulator for temporarily retaining the photosensitive material is provided between the automatic developing machine A and the photoprinting machine B, the processing efficiency is improved. Further, it goes without saying that the automatic developing machine according to the present invention may be configured integrally with the photo printing machine B or may be a single automatic developing machine. Further, it goes without saying that the photosensitive material processed by the automatic developing machine according to the present invention is not limited to the exposed printing paper, and may be an exposed negative film or the like. Further, the description of the present invention will be made on a developing machine of substantially three tanks including a color developing tank, a bleach-fixing tank, and a stabilizing tank, but the present invention is not limited to this, and the color developing tank, the bleaching tank, and the fixing tank can be used. The present invention can be applied to an automatic developing machine having substantially four tanks including a tank and a stabilizing tank.

The present invention can also be applied to an automatic developing machine having a developing tank, a bleaching tank, a bleach-fixing tank, and a stabilizing tank in the order of processing light-sensitive materials. The present invention can also be applied to an automatic developing machine having a developing tank and a fixing tank in the order of processing light-sensitive materials. Even in these cases, it goes without saying that each processing tank has the following structure.

In FIG. 2, reference numeral 912 denotes a processing tank corresponding to the color developing tank 1A shown in FIG. 1, and the pinching and conveying roller array is not shown. 913 is an overflow pipe, and the processing tank 912 is an individual or common waste liquid tank 935.
Have been contacted.

Reference numeral 914 is a solid processing agent replenishing section, and 915 is a processing solution preparation section. The solid processing agent replenishment unit 914 opens the partial door 916 provided on the machine frame top plate of the automatic developing machine main unit 2 which can be opened as indicated by the arrow A, and is openable as indicated by the arrow B. As a result, the solid processing agent container 917 is attached and detached as indicated by the one-dot chain line.

The solid processing agent container 917 is the processing agent replenishing section 91.
4 is swingably provided on the mounting base 918, and the mounting base 918 is rotated counterclockwise from the alternate long and short dash line position to the solid line position to open the delivery end door 917a of the solid processing agent container 917. At the same time, the delivery end is set by matching the receiving end of the separation delivery device 919. The information set in the solid processing agent container 917 is input to the control device 910 from the set detection means 920.

On the other hand, the processing amount information is input to the control device from the photosensitive material sensor provided in the photosensitive material feeding portion of the photosensitive material supply device. Therefore, the control device drives the supply motor based on the set information and the processing amount information to rotate the supply roller 919a of the separation / delivery device 919. Every time the supply roller 919a makes one rotation, one processing agent tablet J rolls into one processing agent receiving recess provided in the supplying roller 919a, and the tablet J passes through the chute 922 from the processing agent receiving recess. Dissolution unit 923 of treatment liquid preparation unit 915
To fall.

The solid processing agent container 917 accommodates the tablets J in a plurality of rows, and a plurality of processing agent receiving depressions of the supply roller 919a are provided corresponding to the plurality of rows.
A plurality of tablets J may be dropped at one rotation of the supply roller 919a at the same time or at a predetermined rotation angle, and may drop, or the supply roller 919a may have processing agent receiving depressions at a plurality of circumferential positions. It is also possible to have a plurality of treatment agents to drop with one rotation. Further, the processing agent may be a powder or a granular processing agent which is intermittently added in an appropriate amount according to the processing amount of the photosensitive material. However, in order to stably supply the treatment agent by a simple means, the treatment agent is preferably a tablet having a rolling shape as described above.

It is to be noted that while taking advantage of the compactness by supplementing the solid processing agent, the solid processing agent is prevented from absorbing moisture,
From the viewpoint that the treatment can be stabilized by stable replenishment, it is preferable that the storage chamber for storing the solid processing agent or the solid processing agent package and the solid processing agent feeding section are dehumidifying spaces.

Here, the dehumidifying space is a space in which the humidity is kept lower than that of the surrounding space by the action of the dehumidifying means, and when the dehumidifying means to be used has a high dehumidifying capacity, it is a completely sealed space. You don't have to.

When the space is completely sealed, it is possible to prevent moisture from entering from the outside, so that the load of the dehumidifying means is small, which is preferable. However, opening and closing when storing the solid processing agent and discharging the solid processing agent. Depending on the opening and closing in such a case, the humidity is introduced by communicating with the external space. Therefore, the capacity of the dehumidifying means is also set to a large value, and after the space is closed, the dehumidification proceeds promptly. The ability required for the dehumidifying means is not specified in the present invention because it is appropriately selected depending on the size of the space and the desired degree of dehumidification.

The above-mentioned solid processing agent charging unit is a whole of the solid processing agent charging means which stores a solid processing agent for replenishment and has a function of discharging a unit quantity of the solid processing agent in response to a command from the control means. I mean.

The dehumidifying means is installed in the space and uses a desiccant that absorbs moisture, a method that uses a membrane module that replenishes the moisture that tries to enter the space, and an air is introduced into the space. A method of press-fitting to increase the internal pressure so that a high-humidity atmosphere does not enter from the outside,
A known method is applied to mean a method of maintaining the space in a dry state, such as a method of blowing dry air into the space. The reason for applying the dehumidifying means in particular is that the solid processing agent charging unit is installed above or near the processing tank in order to have a simple structure that does not require a complicated transport mechanism. It is surrounded by a high-humidity atmosphere containing water that evaporates from the inside, and prevents the stored solid processing agent from absorbing moisture due to the high-humidity atmosphere. This is to prevent the surface of the solid processing agent during transportation from collapsing and adhering due to humidity, and also to prevent dew condensation and to support the stable introduction of the solid processing agent. .

FIG. 3A is a sectional view of the powdery solid processing agent supply device, and FIG. 3B is a perspective view of the package.
The supply device 50 includes a hopper or package 51 for storing the powdery solid processing agent and a measuring hole 5 for measuring the powdery solid processing agent.
3 and a rotary drum 52 for feeding a fixed amount. The rotary drum 52 has a moisture-proof function by shifting the positions of the measuring hole 53 and the discharging portion 56. Package 51
The seal was cut and placed on top of the feeder ,. At that time, fine powder flew and the workability was poor. A certain amount of the powdered chemical is measured in the measuring hole 53, and when the drum 52 is rotated by the command of the processing amount detecting means of the photosensitive material and is in communication with the discharging section 56, it stops and passes through the discharging section 56. Is supplied to the constant temperature section (filter tank) of the automatic processor. After the end of supply,
When the drum 52 rotates and the metering hole 53 and the supply unit 57 communicate with each other, the drum 52 is stopped and the measurement of the powdery chemical is started.

[0095]

EXAMPLES Examples of the present invention will be given below, but the embodiments of the present invention are not limited thereto. Example 1 A color developing composition of the present invention (color developing solid processing agent) was prepared according to the following procedure.

[0096] Color developing composition   Addition amount per group     800 g of the sodium salt of the general formula (4) -7 compound     Chino Pearl SFP 200g     Sodium paratoluene sulfonate 1500g     Sodium sulfite 30g     3000g potassium carbonate     Diethylenetriamine pentaacetic acid 5 sodium salt 500g     D-mannitol 500g     Diethylene glycol # 4000 500g     Lithium hydroxide 250g

[0097]   2 groups     Color developing agent (described in Table 1) Amount described in Table 1

Operation 1 One group was added to the Ledige mixer M-20 manufactured by Matsuzaka Giken Co., Ltd., and pre-mixing was performed for 3 minutes at a rotation speed of 3000 rpm.

Operation 2 While stirring at a rotation speed of 230 rpm, the temperature was raised using a heat jacket, and the stirring operation was continued for about 10 minutes until the temperature of the granules reached 55 ° C.

Operation 3 While stirring at 230 rpm, the granules were air-cooled and continued until the temperature became 35 ° C. or lower (about 30 minutes).

Operation 4 Two groups were added to the above-prepared granules and mixed for 1 minute at a rotation speed of 230 rpm.

The thus-prepared granules were put into a commercially available rotary.
1400 kg / cm using a tablet machine ^TwoTableting with compression pressure
did. The produced tablet sample weighs 10.2 g and has a diameter of 30 m.
and a cylindrical shape having a thickness of about 10 mm. Use this tablet
The following experiment was performed.

Experiment 1 Evaluation of Effect on Loading Operation by Adhering Fine Powder Generated by Vibration and Contact Friction 40 tablets were set in a cartridge for ECOJET chemical manufactured by Konica Corporation. After that, assuming the generation of powder during transportation, it was vibrated under the following conditions using a vibration tester vibration tester BF-UA manufactured by IDEX Corporation. LOW-Hz 5Hz UP-Hz 67Hz Sweep time 5min 12cycle

Then, a charging experiment was conducted using the charging device shown in FIG. The charging device was used by removing it from the main body of the automatic processing machine and modifying it so that a charging test could be performed independently. The tablets after loading were set again in the cartridge and the loading experiment was repeated. Repeat this operation 500 times
I went there. Then, this charging device was left in an environment of 35 ° C. and 60% RH for 2 weeks, and the rotational torque of the charging device after standing was measured.

The smaller the torque is, the lower the possibility of the closing operation failure is. In this case, 10k
If it is less than gf · cm, there is no problem at all and it is 10 to 15k.
There is no particular problem with gf · cm, but a problem may occur in the long term, and if it exceeds 15 kgf · cm, the device will be stopped or damaged.

Further, the powder generation amount of the tablets was calculated from the change in the tablet weight before and after the repeating operation of the vibration test 500 times. The results are shown in Table 1.

[0107]

[Table 1]

As is apparent from Table 1, it is understood that the combination of the present invention can provide the solid processing agent which can rotate at a low torque and does not hinder the charging operation. It is clear from the effect of the rotating torque that the content of the free material of the color developing agent must be 50 mol% or more, preferably 100%.

It is a surprising finding that the combination of the present invention can reduce the load on the charging device, although it is almost the same from the viewpoint of the amount of powder generation as compared with the conventional structure. there were.

Example 2 The granules produced in Example 1 were not tableted but remained as they are in FIG.
When a similar experiment was conducted using the charging device shown in FIG. 3, there was a difference in the numerical values of the rotational torque, but in the configurations of the present invention, all were less than 15 kgf · cm, which was good. Example 3 No. 1 of Example 1. 7, the amount of lithium hydroxide added was changed to the amount shown in Table 2, and the storage condition after the loading test was changed to 3
The same experiment was performed except that the temperature was changed to 5 ° C. and 80% RH.
The results are shown in Table 2.

[0111]

[Table 2]

As is clear from Table 2, the absence of the alkali hydroxide salt has the effect of improving the malfunction due to the increase of the input torque due to the sticking of the powder particularly in the high humidity.

Example 4 No. 1 of Example 1 7, the additives shown in Table 3 were added to 2 groups and the same experiment was conducted, and the number of loading tests was changed to 10
The same evaluation was performed except that the number was changed to 00 times. The results are shown in Table 3.

[0114]

[Table 3]

Example 1 Compound Benzalkonium Chloride Example 2 compound Magnesium stearate

As shown in Table 3, it is desirable to use the compounds represented by the general formula (1) or (2) together as a combination that makes the present invention more effective. The addition amount is preferably in the range of 0.05% (w / w) to 5% (w / w) from the viewpoint of suppressing solidification of fine powder.

Example 5 Partial modification was performed using an automatic processor NPS-878J manufactured by Konica Corp. equipped with a charging device shown in FIG. 2 and then a running process was performed under the following conditions.

[0118] Step processing time processing temperature Replenishment rate color developing 22 sec 39.8 ° C. The tablets turned Taiminku Bu 1 tablet /1.6M ² water supply 63 ml / ^{m 2} bleach-fixing 22 seconds 37.0 ℃ 200ml / ^{m 2} stable (3 tanks Cascade) 22 seconds x 3 35 ° C 248 ml / m ²

Composition Color-Development Replenisher Experiment No. 1 of Example 1 1 (Comparative Example) and Experiment No. 7 (invention) were used respectively. Solution to be used K-J1P1H-01 manufactured by Konica Corporation was dissolved in a usual method and used.

Bleach-fixing replenisher = working solution A solution prepared by dissolving K-28P2R-02 manufactured by Konica Corporation by a conventional method was used.

Stable replenisher = working solution K-P3R-01 manufactured by Konica Corp. was dissolved by an ordinary method and used.

For the running treatment, Konica Color QA Paper was treated for 20 m ² every day, and the treatment was continued for 6 months. In the meantime, when the charging operation troubles caused by the generation of the powder of the color developing agent are counted every month, the results shown in Table 4 are obtained.

[0123]

[Table 4]

As is clear from Table 4, in the treatment method using the tablet constitution of the present invention, the trouble of charging due to the generation of powder, which has been frequently occurring in the past, can be avoided, and the treatment method excellent in maintainability can be provided.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of a printer processor in which an automatic developing machine and a photo printing machine are integrally configured.

FIG. 2 is a cross-sectional view showing another method of introducing a solid processing agent.

FIG. 3 is a cross-sectional view of a powdery solid processing agent supply device and a perspective view of a package.

[Explanation of symbols]

1 processing tank 1A-1E processing tank 35 Drying part

Claims (8)

[Claims] 1. A color developing solid processing agent for a silver halide photographic light-sensitive material, characterized in that 50 mol% or more of a p-phenylenediamine type color developing agent contained in the solid processing agent is a free form. 2. The solid processing agent for color developing for silver halide photographic light-sensitive materials according to claim 1, wherein all of the p-phenylenediamine type color developing agents are free. 3. The color developing solid processing agent for silver halide photographic light-sensitive materials according to claim 1, wherein the solid processing agent does not substantially contain an alkali metal hydroxide salt. 4. The silver halide according to claim 1, 2 or 3, wherein the solid processing agent contains at least one compound represented by the following general formula (1) or (2). Color development solid processing agent for photographic light-sensitive materials. [Chemical 1] [In the formula, R ₁ represents an alkyl group, R ₂ represents an alkyl group or a hydrogen atom, R ₃ represents an alkylene group, and M represents a hydrogen atom, a sodium atom, a potassium atom, a lithium atom or triethanolammonium. . General formula _{(2) R-O} n _SO 3 M [wherein, R represents an aliphatic group, n represents 0 or 1, M represents a cation. ] 5. A color developing solid processing agent for a silver halide photographic light-sensitive material, in which 50 mol% or more of a contained p-phenylenediamine type color developing agent is a free form, is divided as necessary to an automatic processor. A method for processing a silver halide photographic light-sensitive material, which is characterized in that it is directly charged into a processing tank. 6. The method of processing a silver halide photographic light-sensitive material according to claim 5, wherein all of the p-phenylenediamine color developing agents are in a free form. 7. The method of processing a silver halide photographic light-sensitive material according to claim 5, wherein the solid processing agent contains substantially no alkali metal hydroxide salt. 8. The silver halide according to claim 5, 6 or 7, wherein the solid processing agent contains at least one compound represented by the general formula (1) or (2). Processing method of photographic light-sensitive material.