JPH06282044A - Solid processing agent package for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the accuracy of the replenishing amt. by previously dividedly weighing solid processing agents and packaging the outer side thereof with packaging materials having the specific coefft. of in-package static friction between the surfaces of the solid processing agents and the surfaces of the packaging materials. CONSTITUTION:A partial packaging section H-b which is disconnected in sealing parts on both upper and lower sides and is opened at the top and bottom is controlled in the cross relation of a first transporting means 8 and a second transporting means 9 and the remaining beam-shaped sealing parts are brought near to each other and, therefore, the blister of this partial packaging section H-b is intensified and since the holding of the solid processing agents T is released, the solid processing agents T fall. The amt. of the processing agents to be charged at one time is preferably 10 to 30g' in the case of bleaching and bleach-fixing at 0.5 to 50g' the aimonopolycarboxylic acid iron salt-contg. solid processing agents T of this range are packaged by the packaging materials for maintaining <=1.5 coefft. of in-package static friction in such a manner as to attain the replenishing unit of one time. The processing agents are then directly charged into a part of the processing tank of a small-sized developing machine and the photosensitive materials are processed while these agents are slowly dissolved.

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 package for a silver halide photographic light-sensitive material, and more particularly to a solid processing agent for a silver halide photographic light-sensitive material which provides stable photographic performance with improved replenishment accuracy. Regarding packaging.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials are
Processing is performed by steps such as development, desilvering, washing and stabilization.
Processing is usually carried out by an automatic processor, in which case a replenisher replenishing system is generally widely used and is controlled so as to keep the activity of the processing solution in the processing tank constant. In the case of the replenisher replenishment method, the purpose is to dilute the eluate from the sensitive material, correct the evaporation amount, and replenish the consumption component.
A large amount of overflow liquid is usually discharged.

On the other hand, in recent years, there has been a worldwide increase in regulations regarding the dumping of photographic waste liquids into the ocean and regulations regarding the disposal of plastic materials. A new system that eliminates photographic waste liquids and does not use bottles for liquefaction processing agents Development is required. In addition, safety regulations for packaging materials have been strengthened to ensure the safety of transportation of liquid hazardous materials, which has led to an increase in cost. In addition, the development of exposure control technology for printing has progressed in the minilab store, which has been increasing rapidly in recent years, and a system that allows anyone to print has been introduced. However, the work of dissolving the replenisher and the management of the treatment liquid are still difficult, and very serious mistakes such as mistakenly dissolving and replenishing the treatment agent are likely to occur. There have been many complaints about this conventional replenishment system.

Therefore, in the photographic industry, there is a strong demand for the development of a solid chemical replenishing system which produces almost no photographic waste liquid, uses no processing agent bottle, and does not require any dissolving work.

As a method to meet this demand, WO92 / 2001
Japanese Patent Publication No. 3 discloses a method in which almost all processing components are made into a solid processing agent and directly charged into a processing tank. However, in this method, since the solid processing agent is directly charged into the processing tank, the processing agent adheres to the photosensitive material to be processed, causing an accident, or absorbing the evaporated water from the processing tank or the water in the atmosphere,
The solid processing agents stick to each other so that the solid processing agents are not reliably added to the processing tank, or the solid processing agents are adhered to the packaging material and the loading accuracy and weighing accuracy are drastically reduced. , The problem that only incorrect replenishment can be done, and further, when aminopolycarboxylic acid iron salt is present in the solid treatment agent, regardless of the packaging state, the solid treatment agents block each other over time and may not be added at the time of replenishment. It was also found that there is a problem with storage that seriously affects photographic performance, such as partial dissolution and air oxidation to form sulfides.

Further, in Japanese Patent Laid-Open No. 4-237045, a method of setting powdery processing agents in a processing machine for each part, and weighing them into a processing tank while weighing each necessary amount, and a processing machine of this powder chemical A method for preventing moisture is disclosed.

However, in this method, after the powdery chemical is set in the hopper of the charging device, the density changes due to its own weight and each part is not designed in a predesigned amount and the replenishment of the replenisher is not constant. It turned out that performance changed. Even if the evaporation water from the upper part of the processing tank is prevented to some extent, the problem of sticking of the powdery processing agent at the inlet due to moisture absorption is inevitable, and the set powdery processing agent is left in the atmosphere. Therefore, the powdery treatment agent is blocked and adhered to the packaging material, so that it cannot be accurately weighed.

As described above, the biggest drawback is that the amount of preparative change changes with the passage of time.

Further, WO91-7332 discloses a method in which a powder, granule or liquid processing agent is put in a pressure through package (PTP) packaging material and directly put into an automatic developing machine. However, this method merely discloses a replenishment method in which a solid processing agent and a chemical which cannot be solidified are directly charged into a processing tank in order to promote low-concentration replenishment. Or moisture absorption over time when packaged separately, especially solid treatment agent containing aminopolycarboxylic acid iron salt is easy to adhere to the packaging material of the solid treatment agent to be weighed in advance in the packaging that remains in the packaging material There is no suggestion to solve the problem regarding the optimum amount.

Furthermore, since PTP itself opens the packaging material by pressure, the powder easily scatters, and there is a problem that tar and the like adhere to the wall of the processing tank, and the scattered powder jumps into other processing tanks. It was also found that it could cause contamination. It was also found that when opened by pressure, a piece of packaging material was thrown in together with the solid processing agent to induce clogging of the filter.

The present inventors have examined a replenishing device and a packaging material for imparting moisture resistance to these problems.
I couldn't find a real solution. However, as a result of diligent studies, it was found that the solid processing agent in one replenishment unit was divided and weighed in advance in one replenishment unit within a range of 0.5 to 50 g, and the packaging was performed using the aminopolycarboxylic acid iron salt. As long as the product is packaged in a packaging material that maintains the internal friction coefficient between the surface of the packaging material containing slag and the surface of the packaging material to be 1.5 or less, the solid processing agent will be stored in the humidity of 80% for about 2 years. No blocking and adhesion of the solid processing agent to the packaging material. Further, it was found that when the container is opened and dropped by gravity, it is completely replenished without any residue, so that stable photographic performance can be obtained with minimal fluctuation in the concentration of the used liquid.
In addition, it was found that the melting work is free, it is easy to set in the automatic processor, there is no erroneous melting, contamination is prevented, and various problems concerning replenishment are solved.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is, firstly, to provide a solid processing agent package for a silver halide photographic light-sensitive material, which has an accurate replenishment amount.

Secondly, solid processing for silver halide photographic light-sensitive materials has been made possible by eliminating liquid chemicals that pose dangers in transportation and handling, and making it possible to use solid chemicals without complicated operations for users. To provide an agent package.

Thirdly, a solid processing agent package for a silver halide photographic light-sensitive material is provided, which eliminates the manual mixing and dissolving work of the concentration kit with water by the user himself and completes the replenishing system of the fully automatic solid processing agent. To do.

Fourth, eliminate many built-in refill tanks,
An object of the present invention is to provide a solid processing agent package for a silver halide photographic light-sensitive material to be used in a compact automatic processor.

A fifth object is to provide a solid processing agent package for a silver halide photographic light-sensitive material, which eliminates the need for storing a liquid replenishing solution, improves processing stability and reduces the amount of chemical waste solution.

A sixth object of the present invention is to provide a solid processing agent package for a silver halide photographic light-sensitive material, which achieves a low pollution system by reducing the use of plastic packaging materials for liquids and reducing plastic packaging materials.

[0018]

In order to solve the above problems, the inventors of the present invention have found that the following constitution can be achieved.

1. In a solid processing agent package for a silver halide photographic light-sensitive material, the solid processing agent is added per unit replenishment supply amount.
The coefficient of static friction inside the package between the surface of the solid processing agent and the surface of the packaging material, which is preliminarily divided and weighed in the range of 0.5 to 50 g, contains at least an aminopolycarboxylic acid iron salt and is outside the solid processing agent.
It is achieved for the first time with a solid processing agent for silver halide photographic light-sensitive materials, which is packaged with a packaging material of 1.5 or less.

Granules and tablets are preferred embodiments of the solid processing agent in terms of the effects of the present invention.

[0021]

The present inventors have found an optimum solid processing agent replenishment amount to be added at one time in order to prevent the photographic performance of each processing solution from changing with regard to directly adding the solid processing agent to the processing tank. It was thought that this optimum replenishment amount depended on the size of the processing tank of the automatic processor, that is, the capacity of the processing liquid, but by making good use of the characteristic that the solid chemical is difficult to dissolve,
It has been found that the concentration does not rise sharply even if added all at once, and that replenishing water can be injected in tandem with dissolution, which has the advantage of creating extremely stable photographic performance.

The packaging material is affected by temperature and humidity with the passage of time, and not only the coefficient of friction in the package with the surface of the solid processing agent changes, but also wrinkles occur in the packaging material, and the powders, granules and tablets as the solid processing agent are caught. We have found that it is difficult for the treatment tank to fall naturally.

The amount of the processing agent added at one time is 0.5 to 50 g, and in the case of bleaching and bleach-fixing, it is preferably 10 to 30 g. It is not until the general processing of a small developing machine is completed that the solid processing agent containing the aminopolycarboxylic acid iron salt in this range is packed with a packaging material that maintains the coefficient of friction in the package of 1.5 or less so that it becomes one replenishment unit. It has been found that a stable photographic state can always be maintained when the solution is placed directly in a part of the tank and slowly dissolved.

It has been found that the solid treating agent is always added in a predesigned amount without being affected by the preservation over time.

The present invention will be specifically described below.

In the present invention, the term "per unit replenishing and supplying amount of the solid processing agent" means the total weight of the solid processing agent added at one time when a certain fixed amount of the silver halide photographic light-sensitive material is processed. That is, if too much unit replenishment and supply is added to the processing tank of the solid treatment agent, dissolution failure of the solid treatment agent tends to occur, and if the unit replenishment and supply amount is small, a certain amount of solid treatment agent is supplied. Since the number of times of charging of the container increases, the accuracy of charging and the durability of the supply means also become a problem.

The packaging material of the present invention has an internal packaging friction coefficient of 1.5 or less with the surface of the solid processing agent of the present invention, preferably 1.0.
It is the following. Here, the coefficient of friction in the package is a value obtained by the following method.

The solid processing agent is put in the packaging material, and the packaging material is sealed and hermetically sealed. At a temperature of 25 ° C and a relative humidity of 40%, the packaging materials a and b shown in Fig. 8 were cut to obtain "Static Frict" manufactured by HEIDON.
Using ionTester HEIDON-10, fix the packaging material together and measure tan θ at which 80% or more of the solid processing agent slips off the packaging material. This tan θ is called the in-packaging friction coefficient between the surface of the solid processing agent and the surface of the packaging material.

The coefficient of friction in the package varies depending on the surface property, components, size and shape of the solid processing agent, the material of the packaging material, the surface roughness, and the storage condition. The object of the present invention is achieved for the first time by the packaging material in which the coefficient of friction in the packaging between the materials achieves 1.5 or less at the time of packaging and the solid processing agent which is pre-divided and weighed in the range of 0.5 to 50 g per unit replenishment supply amount is packaged. can do.

Therefore, any packaging material may be used as long as the combination of the surface of the solid treatment agent and the surface of the packaging material achieves an internal friction coefficient of 1.5 or less. In the embodiment of the present invention, a synthetic resin is used. Materials are preferably used, specifically, polyethylene, polypropylene, polyvinyl chloride,
Examples thereof include polyvinyl acetate, nylon, polyvinylidene chloride, polystyrene, polycarbonate, vinylon, and polyethylene terephthalate. They may be a single film or laminated with two or more kinds of films, or aluminum foil between the films. May be used.

The packaging material of the present invention has a coefficient of friction in the packaging with the surface of the solid processing agent of 1.5 or less, and further has a moisture permeability of 50 g / m ^2.
The effect of the present invention becomes more remarkable when the time is 24 hours (40 ° C / 90% RH) or less. In other words, when the moisture permeability is high, the amount of water that passes through the packaging material increases, so that the solid processing agent that exhibits deliquescent partly deliquesces, causing an unfavorable reaction with other photographic components, and the coefficient of friction within the package. It is because it also affects. A packaging material having a moisture permeability of preferably 20 g / m ² · 24 hr (40 ° C. 90% RH) or less is preferably used in the embodiment of the present invention.

The film thickness of the packaging material is 1 to 500 μm from the viewpoints of usability, disposal property of the packaging material, friction and moisture permeability.
It is more preferably 10 to 150 μm.

As a method of packaging the solid processing agent, there are four-sided seal, three-sided seal, stick (pillow package, gusset package), PTP (blister package), cartridge, and the like.

When the peel-open method is used as the unsealing and charging means, a sealant agent can be laminated to impart the peel-open suitability.

As a method of supplying the solid processing agent to the processing tank, there is a method of opening the package and taking it out. When opening the package, a method of separating the adhesive surface (peel open), and making a cut in a part of the seal package A method of opening by pulling, a method of cutting by an external force of a cutter, a method of forcibly pushing out the solid processing agent, and the like are preferably used.
When the solid processing agent is a tablet, the dulma dropping method described in W092 / 200013 is also preferably used.

The solid processing agent in the present invention means tablets, granules and powders. Tablets and granules are preferred for the storage stability of the solid processing agent and the accuracy of one-time loading, in view of the residual rate in the packaging material.

The powder agent in the present invention refers to an aggregate of fine crystal grains.

The granules referred to in the present invention are obtained by adding a granulation step to powder, and mean a granular material having a particle size of 50 to 5000 μm.
It is preferably 500 to 1500 μm. If it is small, it tends to remain in the packaging material at the time of loading and is easily scattered, and if it is large, fine powder particles are likely to be formed during transportation.

The tablet referred to in the present invention means a powder or granule obtained by compression-molding a certain shape.

The solid processing agent having a bleaching ability of the present invention preferably contains the following ferric salt of a chelating agent.

[0041]

[Chemical 1]

[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 represents a -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. ]

[0043]

[Chemical 2]

[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. ]

[0045]

[Chemical 3]

[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. ]

[0047]

[Chemical 4]

[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

[0049]

[Chemical 5]

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. ]

[0051]

[Chemical 6]

[In the formula, R _{11 to} R ₁₃ are each a hydrogen atom,
It represents an alkyl group or an aryl group which may be substituted.
L has the same meaning as L in formula [A-IV]. W represents a divalent linking group. ]

[0053]

[Chemical 7]

[In the formula, R _{21 to} R ₂₃ and R _{26 to} R ₂₉ each represent a hydrogen atom or an optionally substituted alkyl group or aryl group, and R ₂₄ and R ₂₅ represent a hydrogen atom, a halogen atom or a cyano group, respectively. Group, nitro group, acyl group, sulfamoyl group, carbamoyl group, alkoxycarbonyl group, allyloxycarbonyl group, sulfonyl group, sulfinyl group,
Represents an optionally substituted alkyl group or aryl group, R
₂₄ and R ₂₅ 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. General formula _{(II) X 4 -A 32 -COOM} 2 [ wherein, X ₄ represents a halogen atom, an amino group, hydroxy group, methoxy group, a -COOM ₇ or -SO ₃ M _8. A ₃₂ represents an alkylene group or an arylene group which may form a saturated or unsaturated ring, and may have a substituent.
M ₇ and M ₈ represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. Firstly, the compound represented by the general formula [AI] is described in Japanese Patent Application No. 4-
What is described in paragraphs [0044] and [0045] of 283032 is used.

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

Of these, the following compounds are preferably used in the present invention.

[0057]

[Chemical 8]

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.

As the compound represented by the above general formula [A-II], compounds described in paragraphs [0051] and [0052] of Japanese Patent Application No. 4-283032 are used.

The compound represented by the above general formula [A-II] can be synthesized by a generally known method. Among these, particularly preferable compounds are the following compounds.

[0062]

[Chemical 9]

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

In the general formula [A-III], in-(B ₁₁ O) n ₅ -B ₁₂ representing X ₁ , the alkylene groups represented by B ₁₁ and B ₁₂ include methylene, ethylene, trimethylene and the like. 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.

Further, the compound represented by the general formula [A-III] can be obtained by the method described in Japanese Patent Application No. 4-283032, paragraphs [0058] [0059] [006.
0] [0061] [0062] [0063] [0064] [0065] can be used. Of these, the following compounds are preferably used in the present invention.

[0066]

[Chemical 10]

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

In the above general formula [A-IV], R ₁₁ , R
Examples of the alkyl group represented by ₁₂ include linear, branched and cyclic groups having 1 to 10 carbon atoms, and a methyl group and an ethyl group are particularly preferable. The aryl group represented by R ₁₁ and R ₁₂ is preferably a phenyl group. When R ₁₁ and R ₁₂ are alkyl groups or aryl groups, they may have a substituent. Examples of the substituent of R ₁₁ and R ₁₂ include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group and an 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, carbonamido group, sulfonamide group,
A nitro group and the like can be mentioned, but preferably,

[0069]

[Chemical 11]

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).

Among 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].

[0073]

[Chemical 12]

[In the formula, R ₃₁ and R ₃₂ each represent a hydrogen atom, an alkyl group, or an aryl group, and L ₁ and L ₂
Each represents an alkylene group or an arylene group, and M
₉ represents a hydrogen atom, an alkali metal, an ammonium group or an organic ammonium group. ]

[0075]

[Chemical 13]

[Wherein R _{41 to} R ₄₄ are each represented by the general formula [B
-I] has the same meanings as R ₃₁ and R ₃₂ , and L _{1 to} L ₃ and M ₁₀ also have the same meanings as those of the general formula [BI]. Specific examples of the compound represented by the general formula [A-IV] include those described in paragraphs [0077], [0078], [0079] and [0080] of Japanese Patent Application No. 4-283032. To be

Among these, particularly preferable compounds are as follows.

[0078]

[Chemical 14]

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

In the above general formula [A-V], R _{11 to} R ₁₃
Examples of the alkyl group and aryl group represented by are the same groups as R ₁ and R _{2 in} the general formula [A-IV], and the same applies to these substituents. In the general 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,

[0082]

[Chemical 15]

(B ₂₁ , B ₂₂ represent an alkylene group or an arylene group, and n ₆ represents 1 to 3),

[0084]

[Chemical 16]

(Z is a hydrogen atom, unsubstituted or --COOM ₁₁ ,
—SO ₃ M ₁₂ , an alkyl group substituted with —OH, or an aryl group, and M ₁₁ and M ₁₂ represent a hydrogen atom, an alkali metal, or an ammonium group), and a combination thereof may be used.

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

[0087]

[Chemical 17]

[Wherein R ₅₁ and R ₅₂ each represent a hydrogen atom, an alkyl group or an aryl group, L _{11 to} L ₁₄ each represent an alkylene group or an arylene group, and M ₁₃
And M ₁₄ each represent a hydrogen atom, an alkali metal, an ammonium group or an organic ammonium group. ]

[0089]

[Chemical 18]

[Wherein R _{61 to} R ₆₄ are each represented by the general formula [B
-III], has the same meaning as R ₅₁ and R ₅₂ of LIII to L _{21 to} L ₂₄ , and M ₁₅
And M ₁₆ have the same meanings as those in formula [B-IIII]. Specific examples of the compound represented by the above general formula [AV] are described below in Japanese Patent Application No. 4-283032, paragraphs [0094], [0095] and [00].
96] [0097] and [0098] may be mentioned.

Among these, particularly preferable compounds are as follows.

[0092]

[Chemical 19]

[0093]

[Chemical 20]

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

Specific examples of the compound represented by the above general formula [A-VI] are described in Japanese Patent Application No. 4-283032, paragraphs [0103] and [0104].
Examples thereof include those described in [0105].

Among these, particularly preferable compounds are the following compounds.

[0097]

[Chemical 21]

Next, the bleaching agent represented by the general formula [A-VII] is shown.

[0099]

[Chemical formula 22]

[Wherein A _{31 to} A ₃₄ are —COOM ₁₇ , —OH, −
PO ₃ M ₁₇ M _18, represents -CONH _2, may each be the same or different. M _17, M ₁₈ represents a hydrogen ion, an alkali metal ion or other cation. n _{7 to} n ₁₀ represent an integer of 0, 1 or 2. R _{71 to} R ₇₄ represent a hydrogen atom, a lower alkyl group or a hydroxy group (provided that n ₇ + n ₈
= 1 and R ₇₁ to R ₇₄ when n ₉ + n ₁₀ = 1 is not a hydrogen atom).

X ₅ represents a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms or — (B ₂₁ O) _m —B ₂₂ —. m is 1
B ₂₁ and B ₂₂ may be the same or different and each represents a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms. Hereinafter, the compound represented by the general formula [A-VII] will be described.

In the formula, A _{31 to} A ₃₄ may be the same or different, and --COOM ₁₇ , --OH, --PO ₃ M ₁₇ M ₁₈ , --CONH ₂
Represent M ₁₇ and M ₁₈ 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 _{7 to} n ₁₀ represent an integer of 0 to 2, and may be the same or different, preferably n ₇ = 0 and n ₈ = 0. R _{71 to} R ₇₄ 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, when n ₇ + n ₈ = 1 and n ₉ + n ₁₀ = 1 R _{71 to} R
₇₄ does not become a hydrogen atom.

X ₅ represents a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms or — (B ₂₁ O) _m —B ₂₂ —. Also, B ₂₁
And B ₂₂ may be the same or different and each represents a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms. The alkylene group represented by X ₅ is ethylene,
Each group such as trimethylene, tetramethylene and the like can be mentioned.
Examples of the alkylene group represented by B ₂₁ and B ₂₂ include methylene, ethylene and trimethylene groups.

Examples of the substituent of the alkylene group represented by X ₅ , B ₂₁ or B ₂₂ include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group). m
Represents an integer of 1 to 4, preferably 1 to 2.

Further, preferable specific examples of the compound represented by the above general formula [A-VII] are described in paragraph [01] of Japanese Patent Application No. 4-283032.
16], [0117] and [0118].

The above bleaching agent is 20 to 60 Wt in 1 g of the solid processing agent.
%, The effect of the present invention is better exhibited.

The rehalogenating agent is 30 to 30 g in 1 g of the solid processing agent.
The effect of the present invention is better achieved by containing 70 wt%.

In the present invention, as the bleaching agent, in addition to the iron complex salts of the compounds represented by the above general formulas [AI] to [A-VII], ferric iron complex salts of the following compounds can be used.

[A′-1] Ethylenediaminetetraacetic acid [A′-2] trans-1,2-cyclohexanediaminetetraacetic acid [A′-3] Dihydroxyethylglycine [A′-4] Ethylenediaminetetrakismethylenephosphonic acid [A ''-5] Nitrilotrismethylenephosphonic acid [A'-6] diethylenetriaminepentakismethylenephosphonic acid [A'-7] diethylenetriaminepentaacetic acid [A'-8] ethylenediaminedioltohydroxyphenylacetic acid [A'-9] hydroxyethyl Ethylenediaminetriacetic acid [A'-10] Ethylenediaminepropionic acid [A'-11] Ethylenediaminediacetic acid [A'-12] Hydroxyethyliminodiacetic acid [A'-13] Nitrilotriacetic acid [A'-14] Nitrilotripropionic acid [A'-15] triethylenetetramine hexaacetic acid [ '-16] Ethylenediaminetetrapropionic acid [A'-17] 1,3-Propylenediaminetetraacetic acid [A'-18] Glycol etherdiaminetetraacetic acid Further, examples described in JP-A-4-174432, pages 7 to 11 Compounds 1 to 71, ferric iron complex salts of Exemplified Compounds 1 to 36 described in No. 4-204533, pages 25 to 30, and the like can also be used.

In addition to the above, a halide such as ammonium bromide, potassium bromide or sodium bromide, various optical brighteners, antifoaming agents or surfactants may be contained.

The sulfite adduct used in the present invention is described in Japanese Patent Application No. 4-28.
The compounds described in paragraphs [0134] to [0141] of 3032 can be used.

Among them, from the viewpoint of the effect of the present invention, B-22
Glutaraldehyde bis sodium bisulfite is preferred.

The sulfinic acid used in the present invention is Japanese Patent Application No. 4-28.
The compounds described in Nos. 3032 to [0049] to [0062] can be used.

Among them, S-2 from the viewpoint of the effect of the present invention.
Sodium paratoluenesulfinate is preferred.

These preservatives may be used in combination,
It may be used alone. In view of the effects of the present invention, the above-mentioned B-22
Glutaraldehyde sodium bisulfite and sodium S-2 paratoluenesulfinate are preferred. These preservatives are preferably contained in the solid processing composition in an amount of 2% by weight or more and 15% by weight or less in view of the effect of the present invention.

A method for solidifying a photographic processing agent is disclosed in Japanese Patent Application No. 2-
No. 135887, No. 2-203165, No. 2-203166, No. 2-203167
No. 2-203168, No. 2-300409, etc. can be used.

As the granulation method for tablet formation, known methods such as rolling granulation, extrusion granulation, compression granulation and fluidized bed granulation can be used. % Is ± 100
It is preferable that the deviation falls within a range of up to 150 μm from the viewpoint of input accuracy.

A method for producing a tablet processing agent is described in JP-A-51-61837.
No. 54-155038, No. 52-88025, British Patent 1,213,808
Can be produced by a known method or the like, and granule treating agents are disclosed in JP-A Nos. 2-109042, 2-109043, 3-39735 and 3-397.
No. 39, etc.
54-133332, British Patents 725,892 and 729,862, and German Patent 3,733,861 can be manufactured by known methods.

Next, a preferred form of the automatic processor equipped with a charging device for using the solid processing agent of the present invention will be described.

FIG. 1 shows a cross section of an automatic developing machine equipped with a charging device. It should be noted that, in the figure, a transporting means for transporting the photosensitive material and the like are omitted for easy understanding of the configuration. In addition, in this example, a case where a tablet is used as a solid processing agent will be described.

The processing bath 1 for processing the light-sensitive material comprises a solid processing agent feeding section 4 for supplying a solid processing agent (tablet) integrally provided on the outside of a partition wall forming the processing tank 1, and a constant temperature bath 2.
Have. The processing bath 1 and the constant temperature bath 2 are partitioned by a partition wall 21 having a communication window formed therein, so that the processing liquid can flow. Since the enclosure 5 for receiving the solid processing agent is provided in the charging section 4 provided above the constant temperature tank 2, the solid processing agent does not move to the processing tank 1 in a solid state. It should be noted that the enclosure 5 has a mesh-like or filter-like shape that allows the treatment liquid to pass therethrough, but does not allow the solid treatment agent to pass until it is dissolved.

The cylindrical filter 22 is provided below the constant temperature bath 2 so as to be replaceable, and has a function of removing insoluble matters such as paper waste in the treatment liquid. Inside this filter 22,
It is connected to the suction side of the circulation pump 24 (circulation means) via a circulation pipe 23 provided through the lower wall of the constant temperature bath 2.

The circulation system is composed of the circulation pipe 23 forming the liquid circulation passage, the circulation pump 24, the processing tank 1 and the like. The other end of the circulation pipe 23, which communicates with the discharge side of the circulation pump 24, penetrates the lower wall of the processing tank 1 and communicates with the processing tank 1. With such a configuration, when the circulation pump 24 is operated, the processing liquid is sucked from the constant temperature tank 2 and discharged to the processing tank 1, and the processing liquid mixes with the processing liquid in the processing tank 1 and returns to the constant temperature tank 2 again. The cycle of entering will be repeated. The flow rate of the circulation flow is preferably 0.1 (rotation = circulation amount / tank volume) or more with respect to the tank volume per minute, and more preferably 0.5 to 2.0.
It is rotation. Further, the circulation direction of the processing liquid is not limited to the direction shown in FIG. 1 and may be the opposite direction.

The waste liquid pipe 31 is for overflowing the processing liquid in the processing tank 1 and keeps the liquid surface level constant, as well as components brought into the photosensitive material from other processing tanks and the photosensitive material. The component leaching from the material is stored,
Helps prevent the increase.

The rod-shaped heater 25 is arranged so as to penetrate the upper wall of the constant temperature bath 2 and be immersed in the treatment liquid in the constant temperature bath 2. The heater 25 heats the treatment liquid in the constant temperature bath 2 and the treatment bath 1, in other words, keeps the treatment liquid in the treatment bath 1 within a temperature range suitable for the treatment (for example, 20 to 55 ° C.). It is a temperature adjusting means.

The processing amount information detecting means 32 is provided at the entrance of the developing machine and is used for detecting the processing amount of the photosensitive material to be processed. The processing amount information detecting means 32 has a plurality of detecting members arranged in the left-right direction and functions as an element for detecting the width of the photosensitive material and for counting the detected time. Since the conveying speed of the photosensitive material is mechanically preset, the processing area of the photosensitive material can be calculated from the width information and the time information. The processing amount information detecting means 32 may be any one capable of detecting the width and the conveying time of the photosensitive material such as an infrared sensor, a micro switch, an ultrasonic sensor. Further, the detected information may be a value that is proportional to the processing amount of the processed, processed, or being processed photosensitive material, such as the concentration of the processing liquid stored in the processing tank or the change in the concentration. It may be.

In FIG. 1, 6 is a container for accommodating a solid processing agent package, 9 is a second conveying means for conveying the package, and 16 is a processing agent which receives a signal from the processing amount information detecting means 32. It is a control means for controlling the supply of the throughput.

FIG. 2 is a perspective view for explaining in detail the specific structure of the seal packaging material opening / closing device 3, and FIG. 3 is a perspective view in which the viewing angle is further changed, and is also a block diagram showing the configuration.

In FIG. 2, the container 6 for housing the solid processing agent package contains the solid processing agent package H with its belt portion meandering. , The roller 8-a, the roller 8-b and the first conveying means 8 including the driving means, or the lid 7 is opened to guide the roller 9-a, the roller 9-b and the driving means. The second transfer means 9 is provided, and the lid 7 is closed.
The second transporting means 8 and the second transporting means 9 are engaged with each other. The second
Cutting means (cutter) 10 before engaging with the conveying means 9 of
By this, the upper and lower seal parts are separated and guided in the direction of arrow A to be removed.

Next, as shown in FIG. 3, the packaging portion H-b in which the upper and lower openings are separated by separating the upper and lower seal portions,
Since the mutual relationship between the first transporting means 8 and the second transporting means 9 is controlled so that the remaining girder-shaped seal portions are brought close to each other, the bulge of the packaging portion H-b is emphasized as shown in the figure,
Since the sandwiching of the solid processing agent T is released, the solid processing agent T
Falls. In FIG. 2, the guide 12 guides the progress of the band-shaped solid processing agent package H and regulates the position where the processing agent falls due to the bulge, whereby the inlet 13 does not have to be huge.

In this embodiment, the cutting means (cutter) 10 is a disk-shaped rotary cutter, but the invention is not limited to this. For safety, the cutter blade is preferably configured to be replaced as a set as the cutter tip 11.

As shown in FIGS. 2 and 3, the rollers 8-b,
The roller 9-b is a notched roller by removing a part of each cylinder, and since the axial distance of each roller pair is fixed, rotation of the roller pair causes the notched portion to be the roller 8-. When facing a or the roller 9-a, the nip pressure between both rollers is lost and the nip pressure is reduced.
The sandwiched strip-shaped solid treatment agent package H can freely move in the plane direction, and can return to the center, for example, when it starts to meander.

The detecting means 14 in FIG. 3 detects the detected portion 15 for each packaging recorded on the side end of the solid processing agent package H, and sends a signal to the processing amount supply control means 16 to turn on the motor. It controls and drives the 1st conveyance means 8 and the 2nd conveyance means 9.
It also indicates that it is also used to display the remaining amount.

Next, referring to FIG.
A situation in which the feeding speed of the conveying means 9 is low and the belt-shaped solid processing agent package H is bulged due to the difference in the feeding speed will be described. In FIG. 5, the same gears are fixed to the roller shafts of the first conveying means 8 and the second conveying means 9, and common gears are used.
Since the shafts are driven at the same time by 18, the number of rotations of the shaft is the same, but the rollers 9-a and 9-b of the second conveying means 9 have a smaller diameter than the rollers of the first conveying means 8 and therefore have a peripheral speed. Becomes smaller and the feed rate is slow.

The timing chart shows that the first and second conveying means are simultaneously driven.

Next, in FIG. 5, the second conveying means 9 is
An embodiment in which the transport means 8 is driven simultaneously with the transport means 8 and is then temporarily reversed. In this embodiment, the feeding speeds of the first conveying means 8 and the second conveying means 9 are the same, but the rotation of the second conveying means 9 which is reversed after the stop causes the belt-shaped solid treatment agent package H to be removed. The slack that is returned and the portion that sandwiched the solid processing agent T swells, and the solid processing agent T is released.

Next, FIG. 6 shows an embodiment in which the operation phases of the first conveying means 8 and the second conveying means 9 are different. Since the first transfer means 8 is first driven by the movable drive source 19 and then the second transfer means 9 is driven, the strip-shaped solid processing in which the seal parts on both sides are separated by the first transfer means. The girder-shaped seal portion preceding the packaging portion of the agent package H is
The second transport means 9 is reached, but still the second transport means 9
Is stopped because it is not driven, and solid processing agent package H
The sagging occurs in the bag, and the packing portion is inflated to release the solid processing agent T.

FIG. 7 shows a control flowchart of the supply operation regarding the dropping of the solid processing agent. That is, the remaining amount of the processing agent is checked by the processing information signal, and if there is no remaining amount, a signal indicating no remaining amount is output. If there is a remaining amount, the supply operation is started and the motor is driven. Then, the completion of the supply operation for one time is checked, and if the supply operation is completed, the supply operation is stopped, but if not completed, the motor M is driven again and the supply operation is repeated.

[0140]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these embodiments.

Example 1 A solid processing agent for a color negative film was prepared as shown below, and four-sided sealed with the packaging materials shown in Tables 1, 2 and 3 below and packaged.

(1) Bleaching Replenishing Powder Treatment Agent for Color Negative Film 1,3-Propanediamine 4 Ferric Ammonium Ferric Acid Monohydrate
175g, 1,3-propanediamine tetraacetic acid 2g, succinic acid 133
g, ammonium bromide 200g, potassium sulphate 66.7g, potassium hydrogencarbonate 60g are ground in a commercial Van Dam mill to an average particle size of 10 μm, and these materials are mixed in a room where the humidity is controlled to 40% RH or less. Was uniformly mixed for 10 minutes, and this was divided into 80 equal parts to prepare a bleaching replenishing powder processing agent (1) for 80 color negative films. (Hereinafter referred to as solid processing agent (1)) (2) Bleach replenishing granules for color negative film Operation (K) 1,3-Propanediamine 4 ferric ammonium acetate monohydrate
175 g, 1,3-propanediamine tetraacetic acid 2 g, and pine flow (Matsuya Chemical Co., Ltd.) 17 g were pulverized in the same manner as in (1) of Example 1,
Mix and granulate with water added to 8 ml. After granulation,
The granulated product was dried at 60 ° C for 30 minutes to almost completely remove the water content of the granulated product to prepare granules (K).

(Average particle size 1000 μm Density 0.80 g / cm ³ ) Operation (L) 133 g succinic acid, 200 g ammonium bromide and pine flow 1
0.2 g is pulverized, mixed and granulated in the same manner as in (1) of Example 1. The amount of water added was 17 ml, and after granulation, the granulated product was dried at 70 ° C. for 60 minutes to almost completely remove the water content to prepare granules (L).

(Average particle size 1000 μm Density 0.80 g / cm ³ ) Operation (M) 66.7 g of potassium sulfate, 60 g of potassium hydrogencarbonate and 8 g of mannite are pulverized, mixed and granulated in the same manner as in (1) of Example 1. . The amount of water added was 13 ml, and after granulation, the granules (M) were prepared by drying at 60 ° C. for 60 minutes to almost completely remove the water content.

(Average particle size 1000 μm Density 0.80 g / cm ³ ) The above granules (K) to (M) were mixed, and this was divided into 80 equal parts to obtain granules (2) for bleaching color negative film for 80 pieces. .
(Hereinafter referred to as solid processing agent (2)) (3) Tablet for bleach replenishment for color negative (K ') 1,3-Propanediamine 4 ferric ammonium acetate monohydrate
175 g, 1,3-propanediamine tetraacetic acid 2 g, and pine flow (Matsuya Chemical Co., Ltd.) 17 g were pulverized in the same manner as in (1) of Example 1,
Mix and granulate with water added to 8 ml. After granulation,
The granulated product is dried at 60 ° C. for 30 minutes to almost completely remove the water content of the granulated product.

(Average particle size 1000 μm, density 0.80 g / cm ³ ) Operation (L ′) 133 g succinic acid, 200 g ammonium bromide and pine flow 1
0.2 g is pulverized, mixed and granulated in the same manner as in (1) of Example 1. The amount of water added was 17 ml, and after granulation, the granules were dried for 60 minutes at 70 ° C to almost completely remove water.

(Average particle size 1000 μm Density 0.80 g / cm ³ ) Operation (M ′) Potassium sulfate 66.7 g, potassium hydrogen carbonate 60 g and mannite 8 g were pulverized, mixed and granulated in the same manner as in Example 1 (1). To do. The amount of water added is 13 ml, and after granulation, the granules are dried at 60 ° C for 60 minutes to almost completely remove water.

(Average particle size 1000 μm Density 0.80 g / cm ³ ) Granules prepared by the above operations (K ′) to (M ′) were prepared at 25 ° C. and 40%.
Mix evenly for 10 minutes using a mixer in a room whose humidity is adjusted to below RH. Next, 6 g of sodium N-lauroyl sarcosine is added to this mixed granulated product, and the mixture is mixed for 3 minutes. Next, the mixture was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with a filling amount of 6.5 g per tablet to make 80 bleaching tablets for color negative bleaching. This was used as a bleaching replenishing tablet for color negative film (3). (Density 1.9 g / cm ² ) (hereinafter referred to as solid processing agent (3)) After packaging the solid processing agent prepared above with the packaging materials shown in Table 1, Table 2 and Table 3, the temperature is 40 ° C. and the relative humidity is 60. % (Condition 1) temperature 5 ° C. Relative temperature 20% (condition 2) were alternately repeated every 6 hours and stored for 7 days.

The coefficient of friction in the package was measured by the method described in the present specification. The results are summarized in the table below. Furthermore, the weight (%) of the solid processing agent which was charged by using the seal packaging material opening and charging apparatus shown in FIG. 3 and adhered and remained in the packaging material to the divided and weighed solid processing agent was determined.

[0150]

[Equation 1]

The results are shown below.

[0152]

[Table 1]

[0153]

[Table 2]

[0154]

[Table 3]

As is apparent from the above table, when the coefficient of friction in the package is smaller than 1.49, the residual rate of the solid processing agent in the package decreases. Further, it can be seen that the value of 1.00 or less is more preferable. In addition, it can be seen that the tablet, the granule, and the powder are placed in this order in good accuracy.

It was also found that when the coefficient of friction in the package was outside the range of the present invention, the granules and tablets were liable to disintegrate with tree oil to form fine powder.

In the above table, "not measurable" means that the coefficient of friction in the package exceeds 1.5. The sealing method is shown in FIG.

Even when (A) was changed to (B), (C), and (D), the residual rate of the solid processing agent was the same. In this seal / packaging material unsealing / charging device, the four-way sealing methods (A), (B), and (C) shown in FIG. 9 are preferable from the viewpoint of unsealing and transportability, and (A) is preferable from the viewpoint of packaging material cost.

Further, as a method for sealing and packing tablets and granules, there is a 4-way seal, 3-way seal stick (pillow package, gusset package) PTP cartridge.

The four-way seal, three-way seal, and stick (pillow, gusset) packaging are different in form, and the above materials are used. However, when used in the peel-open method, a sealant agent is laminated to provide peel-open suitability. .

The peel-open method generally includes a cohesive failure method, an interface peeling method, and an interlayer peeling method.

The cohesive failure method is an adhesive called hot melt, which is used as a sealant in a heat seal lacquer, and peels off due to internal cohesive failure of the sealant layer at the time of opening.

The interface peeling method is a method of peeling at the interface between the films, and the sealing film (sealant) and the adherend are not completely fused and can be peeled off with appropriate strength. The sealant is a film in which an adhesive resin is mixed, and polyethylene, polypropylene or a copolymer thereof, a polyester type, or the like can be selected depending on the material of the adherend.

Further, the delamination method is one in which the sealant is peeled between the layers of the laminate film by using a multilayer coextrusion film such as a laminate film.

In the peel-open method using the film of the present invention, the interlaminar peeling method or the interfacial peeling method is preferable.

FIG. 10 shows an example of a carton for storing a continuous package containing these solid processing agents. A, B,
C and D are solid processing agents.

FIG. 11 shows a preferred form of the solid processing composition of the present invention.

(A) shows a form in which the maximum diameter of tablets having the same composition is different in order to control the solubility with a tablet solid processing agent, and (B) shows a packaging material divided for each type of drug and added once. (A), (B) and (C) are sometimes packaged so that they may be put in once. (C) shows a package in which powder or granules or a mixture of powder and granules to be added at one time is packaged. D) shows a form in which one tablet treatment agent is added at one time. (E) shows a form in which three tablet treatment agents are added at one time. (F) shows once. The solid treatment agent of the powder or granules, or the mixture of powder and granules, which is added to the above, is packaged for each chemical, and is further divided into two because there is a large amount of agent A. (H) shows a form in which the solid processing agent of granules or a mixture of powder and granules is packaged in every 4 medicines. The solid processing agent of powder or granules or a mixture of powder and granules is divided into two parts, and each of them is packed in two packages. (I) shows the case where three tablets are thrown in at one time. (J) shows the form in the case where four tablets are thrown in at one time. (K) shows the form in the case where there are four tablets put in one time and there are two parts. ) Shows the morphology in the case where four tablets are thrown in at one time and is in one part (M) shows the morphology in the case where one tablet is thrown in at one time and is in one part (N) is , (2) shows the morphology in the case where two tablets are thrown in at one time and is in one part (O) shows the morphology in the case where three tablets are thrown in at once and is in one part (A) to (O ) Is a continuous package, which is preferable when using the seal packing material opening and charging device shown in FIG. (P)-(U)
Shows an example that is not continuous packaging.

Example 2 The solid treating agent (2) prepared in Example 1 was used in Example 1
Example No. 1-32 packaging material (stretched polypropylene +
Unstretched polypropylene + low density polyethylene)
As shown in Table 5, the filling amount per one packet of the bleach replenisher is changed,
A running test was carried out using the automatic processor of FIG. 1 and the seal packing material opening and charging device of FIG.

The test is Konica Color Film DD-100.
(Manufactured by Konica Corp.) was treated until the amount of replenishing water became twice as much as the tank liquid.

The processing steps are as follows.

[0172]

[Table 4]

Fixing is from 2 to 1, stability is from 3 to 2, 2
It was a counter current system from 1 to 1, and the bleaching tank was aerated with an air pump.

Evaporation correction is color development, bleaching, fixing-1, fixing-2, stable-1, stable-2, stable- during temperature control.
10ml, 6.5ml, 7ml, 7ml, 8.6ml, 8.6 in 3 tanks for 1 hour each
Evaporation correction was performed using a program that replenishes water with 9.1 ml and 9.3 ml. When not in operation, the time when not in operation was added up, and the above tanks were collectively replenished with water at the start of operation in the amounts of 7.5 ml, 5 ml, 6 ml, 6 ml, 5 ml, 5 ml and 5 ml per hour.

The tank liquid at the start was prepared by using a replenisher and a starter for the processing agent CNK-4-52 for Konica color negative film.

The amount of replenishment water and the amount of solid processing agent supplemented were as shown in Table 5.

[0177]

[Table 5]

Next, a treated tablet for color negative film used for running treatment was prepared according to the following procedure.

1) Color development replenishing tablet operation for color negative film (1) CD-4 [4-amino-3-methyl-N-ethyl-N-β-] as a developing agent
150 g of (hydroxy) ethylaniline sulfate] are pulverized in a commercially available bandam mill until the average particle size becomes 10 μm. This fine powder is placed in a commercially available stirrer for about 7 minutes at room temperature for 10 minutes.
After granulating by adding ml of water, the granulated product is dried in a fluidized bed dryer at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product. In this way, N-lauroylalanine sodium 0.3 g and polyethylene glycol 6000 1.9 g were added to the adjusted granules, and the mixture was mixed with a mixer in a room where the temperature was adjusted to 25 ° C and 40% RH or less. Mix evenly for a minute. Next, the mixture is made into a tough pressed collect 1527H manufactured by Kikusui Seisakusho KK
A tableting machine modified from U was used to perform compression tableting with a filling amount of 1.1 g per tablet, to prepare 126 color development replenishing tablet A agents for color negative film.

Operation (2) 69.4 g of hydroxylamine sulfate and 4 g of Pine Flow (manufactured by Matsutani Chemical Co., Ltd.) were pulverized in the same manner as in operation (1), and then mixed and granulated. The amount of water added is 3.5 ml, and after granulation, it is dried at 60 ° C. for 30 minutes to almost completely remove the water content of the granulated product. In this way, 0.3 g of sodium N-lauroylalanine is added to the adjusted granulated product, and mixed for 3 minutes using a mixer in a room where the humidity is adjusted to 25 ° C. and 40% RH or less. Further, in the same manner as in operation (1), compression tableting was carried out with a tableting machine at a filling amount of 0.56 g per tablet, to prepare 120 tablet B agents for color development replenishment for color negative film.

Operation (3) 1-Hydroxyethane-1,1-diphosphonate disodium 15
g, potassium sulphite 72.8g, potassium carbonate 375g, sodium hydrogen carbonate 3g, sodium bromide 3.7g and mannite 22g are crushed and mixed in the same manner as in step (1), and the amount of water added is 40 ml for granulation. . After the granulation, the granulated product is dried at 70 ° C. for 60 minutes to almost completely remove the water content of the granulated product. In this way, 2 g of sodium N-lauroylalanine is added to the prepared granulated product and mixed for 3 minutes using a mixer in a room whose humidity is controlled to 25 ° C. and 40% RH or less. Further, in the same manner as in the operation (1), compression filling was carried out using a tableting machine with the filling amount per tablet being 3.9 g, to prepare 120 color developing replenishing tablet C agents for color negative.

2) Bleaching Replenishing Tablet for Color Negative The one prepared in Example 1 was used.

3) Fixing replenishing tablet for color negative (4) Ammonium thiosulfate 2500 g, sodium sulfite 150 g,
Operate 150g of potassium carbonate, 20g of ethylenediamine tetraacetic acid disodium salt and 65g of Pine Flow (Matsuya Chemical) (1)
Grind, mix and granulate as in. The amount of water added was 50 ml, and after granulation, the granules were dried for 120 minutes to almost completely remove water.

Operation (5) The granules prepared in the above operations (4) and (5) and 13 g of N-lauroylsarcosine sodium were mixed in a room where the humidity was adjusted to 25 ° C. and 40% RH or less with a mixer. Mix for minutes. Next, the mixture was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. so that the filling amount per tablet was 9.3 g, and 280 color negative fixing replenishing tablets were prepared. .

4) Stable replenishment tablet for color negative (6) m-Hydroxybenzaldehyde 150 g, sodium lauryl sulfate 20 g, ethylenediamine tetrasodium acetate 60 g,
65 g of lithium hydroxide monohydrate and 10 g of pine flow are pulverized, mixed and granulated in the same manner as in the operation (1). The amount of water added is 10
After the granulation, the granulated product is dried at 50 ° C. for 2 hours to almost completely remove the water content of the granulated product.

Operation (7) The granules prepared in the above operation (6) were placed in a room whose humidity was adjusted to 25 ° C. and 40% RH or less by a tableting machine which was modified from Kikusui Seisakusho Co., Ltd.'s Tough Press To Correct 1527HU. Compressing tableting was carried out with the filling amount per tablet being 0.48 g, to prepare 280 stable supplement tablets for color negative.

Next, the above-mentioned tablets were used for color development replenishment tablets, 2 tablets, 1 tablet and 1 tablet each for A, B and C, 2 tablets for bleaching replenishment tablet, 3 tablets for fixing replenishment tablet,
The tablets for stable replenishment were packaged one by one, and each continuous 20-minute package was packaged by a four-sided sealing method.

The amount of residual silver in the maximum exposed area of the imagewise exposed film after the completion of running was measured as a measure of the solubility of the solid processing agent and the accuracy of the single supply amount. The results are summarized in Table 6.

[0189]

[Table 6]

As is clear from Table 6, when the unit supply amount of the solid processing agent is 0.5 g to 50 g, the solubility and desilvering property are excellent, and 5 to 30 g is particularly preferable. In addition, the solid processing agent did not remain in the packaging material, which was very good.

When the unit supply amount of the solid processing agent is too large, the solid processing agent is not completely dissolved, and then the next solid processing agent is charged and further charged. It does not dissolve in a certain degree, and in fact becomes insoluble.

On the contrary, if the unit supply amount of the solid processing agent is too small, the proportion of the solid processing agent adhering to the packaging material becomes large and the input amount decreases, resulting in fluctuation of photographic performance.

It also causes a high cost of the packaging material.

As another effect, a preferable solid processing agent feeding device of the present invention is obtained by continuously packaging each packaging (in the present invention, a packaging represents a packaging unit packaged at a unit replenishing and supplying amount of the solid processing agent). It has been found that once used, the solid processing agent can be automatically replenished with high accuracy and waste packaging materials can be stored together in one place. Furthermore, it was also found that even if the packaging material is lost during transportation and transportation, the damage can be minimized by the separate packaging.

Example 3 In the same manner as in Example 2, except that the weight (%) of 1,3-propanediaminetetraacetic acid ammonium ferric acetate monohydrate in the solid treating agent of Example 2 was changed as shown in Table 7. It carried out like Experiment No. 2-5.

[0196]

[Table 7]

As is clear from Table 7, if the content is less than 20%, the content of the rehalogenating agent becomes high, the solubility becomes poor, and the photographic performance is adversely affected as a result.

If the content exceeds 60%, fine powder is likely to be generated, the amount remaining in the packaging material increases, and the following solid processing agent is supplied before completely dissolving, resulting in photographic performance. It was found to affect.

Example 4 Replacing granules (2) for replenishing color negative film bleaching prepared in Example 1 with 1,3-propanediaminetetraacetic acid ammonium ferric acid monohydrate in the same mole as the compounds in Table 8 was carried out. The experiment was conducted in the same manner as Experiment No. 1-12 of Example 1. The results are summarized in Table 8.

[0200]

[Table 8]

As can be seen from Table 8, the solid treatment agent package of the present invention is superior to the comparison of Example 1 in comparison.

Example 5 The solid processing agent (2) was put in the packaging material of PTP (Pressure Through Package) in FIG. 12 (a) and stored in the same manner as in Example 1. The coefficient of friction in the package was 0.52.

FIG. 13 relates to an apparatus for feeding a PTP-packaged solid processing agent. (A) is a solid processing agent (single processing agent) packaged in PTP, and (B) is a solid processing agent 13 'similarly packaged in PTP. (Multiple processing agents of different types), (C) is a cross-sectional view of the processing agent supply device.

The solid processing agent 13 'packed in PTP is supplied from the side surface of the container, and when the photosensitive material is processed by a certain amount, the information of the processing amount detection means is sent to the processing agent supply control means.
PT by the turntable 130 connected to the solenoid motor
The P-packaged solid processing agent is extruded and the roughing device 34 breaks the lower part of the PTP package, whereby the solid processing agent 13 'is put into the processing tank. Then, the packaging material 120 is transported by the transport notch 128 provided on the rotary disk 130.

[0205] Further, the charging device Fig. 2 was replaced with the charging device shown in Fig. 13, and the charging amount was measured to determine the residual ratio (%) of the solid processing agent.
It was 0.4.

From this, it was found that the granule treating agent was likely to remain at the contact point 24 'between the upper packaging material and the lower packaging material of the PTP packaging material of FIG. 12 (b). Experiment of Example 1
This is the difference in residual rate from No. 1-23, and the four-sided seal is preferable. Further, since it is opened by pressure, when the solid treatment agent to be added is powder or granules, it is easy to scatter and a four-way seal is preferable.

When the aluminum foil 23 'was replaced with pullulan and the same experiment was conducted, the coefficient of friction in the package could not be measured, and the solid processing agent residual rate (%) was 25.8 (%).

From the above, it can be seen that the coefficient of friction in the package has an important meaning even in the case of PTP packaging.

Further, as in Example 2, the unit supply amount was changed once. The residual rate was slightly worse than the uniform 4-way seal, but the tendency for the amount was the same. That is, it can be seen that the present invention can be applied to PTP packaging.

Example 6 FIG. 17 is a diagram showing an example of a cartridge type packaging form.

[0211] After the storage test in the same manner as in Example 1 using the dharma dropping device shown in Fig. 14 described in WO92 / 20013, a running treatment was carried out using the solid processing agent (3). However, the packaging form is shown in Fig. 17 (the packaging material is paper (50μ)). There was a big problem in the accuracy of feeding the solid processing agent (3).

The causes were the following two points.

That is, in FIG. 14 (a) and FIG. 14 (b), (a) the loaded tablet 32 'was stuck in the cartridge and was not in the standby state. Therefore, the tablets 32 'were not actually charged, and therefore the accuracy of charging was poor.

(B) The tablets 31 'and 32' are adhered,
Even if the pushing claw 18 'pushed the tablet 32', the tablet 32 'was difficult to be loaded. After the charging operation many times, it was charged, but a part of the tablet 32 'adhered to the tablet 31', and eventually the amount charged was small,
Therefore, the input accuracy was poor.

[0215] The same experiment was carried out by double-wrapping the above packaging material paper (50μ) with silica-coated stretched polyethylene terephthalate (12μ) and performing the same experiment, the coefficient of friction inside the package was 0.42, and the above problem (a) was improved by 100%. It was (B) has been improved by 90%.

The effects of the present invention are better exhibited by the solid treatment agent packaged in the moisture-proof package as described above.

Example 7 A running test was carried out using the solid processing agent (2) with the screw feeder type charging device shown in FIG. 15 described in WO92 / 20013.

There was a big problem in the accuracy of the solid processing agent (2), and the causes were the following two points.

In FIGS. 15 (a) and 15 (b), (c) due to the adhesiveness of the solid processing agent (2) in the hopper.
There was a space at 34 and the screw couldn't move the correct amount when it was rotated. Therefore, the injection accuracy was poor.

(D) The solid processing agent (2) was adhered to the tip portion 33 of the screw, and it should not drop, but it did not drop, so that the charging accuracy was poor.

The table type feeder feeding device shown in FIG. 16 described in Japanese Patent Laid-Open No. 4-237045 has the same problem, and has a serious problem in the feeding accuracy.

[0222]

The solid processing agent for silver halide photographic light-sensitive materials according to the present invention has a high replenishing amount accuracy, has no danger in transportation and handling, has completed a completely automatic replenishment system, and has many built-in replenishing systems. It is possible to use a compact automatic processor without the replenishment tank.

Also, the need for storing liquid replenisher was eliminated, the processing stability was excellent, the amount of chemical waste liquid could be reduced, the use of liquid plastic bottles was eliminated, and the plastic packaging material was reduced. A pollution system can be achieved.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a processing agent charging section and a processing agent charging device of an automatic processor.

FIG. 2 is a perspective view showing an example of a seal packaging material opening and charging device.

FIG. 3 is a perspective view of the seal packing material opening and charging device seen from another angle.

FIG. 4 is an explanatory diagram of an example in which the feed rate is different.

FIG. 5 is an explanatory diagram of an embodiment including reverse rotation.

FIG. 6 is an explanatory diagram of an embodiment in which the phase is changed.

FIG. 7 is a flowchart of control.

FIG. 8 is a diagram showing an example of seal packaging and stick packaging.

FIG. 9 is a plan view showing a specific example of seal packaging.

FIG. 10 is a state diagram showing an example in which the solid processing agent sealed and packaged is contained in a container.

FIG. 11 is a plan view showing a specific example of continuous seal packaging.

FIG. 12 is a cross-sectional view showing a specific example of PTP packaging.

FIG. 13 is a cross-sectional view and a perspective view of a PTP packaging treatment agent supply device.

FIG. 14 is a cross-sectional view showing an example of a charging unit of the dharma dropping charging device.

FIG. 15 is a sectional view showing an example of a screw feeder type charging device.

FIG. 16 is a perspective view showing an example of a powdery processing agent supply device for each part.

FIG. 17 is a perspective view showing an example of a cartridge type packaging form.

[Explanation of symbols]

 1 Processing Tank 2 Constant Temperature Tank 3 Sealing Packing Material Opening Feeding Device 4 Feeding Part 5 Enclosure 6 Storage Container 7 Lid 8 First Transfer Means 9 Second Transfer Means 10 Cutter 11 Cutter Tip 12 Guide 13 Input Port 14 Detection Means 15 Covered Detector 16 Processing amount supply control means 18 Gear 19 Drive source H Processing agent package T Solid processing agent 13 'Tablet (solid processing agent) 17' Processing agent supply means 18 'Push claw 21' Tablet pressing spring 22 'PET 23' Aluminum foil 24 'Point of contact between upper packaging material and lower packaging material 31' Tablet (solid processing agent) 32 'Tablet (solid processing agent) 33 Screw tip 34 Space

Claims (2)

[Claims] 1. A solid processing agent package for a silver halide photographic light-sensitive material, wherein the solid processing agent is 0.
It is pre-divided and weighed in the range of 5 to 50 g, contains at least an aminopolycarboxylic acid iron salt, and the outside of the solid processing agent has an internal friction coefficient between the solid processing agent surface and the packaging material surface of 1.
A solid processing agent package for a silver halide photographic light-sensitive material, which is packaged with a packaging material of 5 or less. 2. The solid processing agent package for a silver halide photographic light-sensitive material according to claim 1, wherein the solid processing agent is a granule or a tablet.