JPH0554928B2 - - Google Patents

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to the treatment of photographic processing liquid waste, and more particularly to the treatment of photographic processing waste liquid discharged when processing silver halide photographic light-sensitive materials with an automatic processor.

[Conventional technology]

In general, photographic processing of silver halide photographic materials includes development, fixing, washing, etc. in the case of black and white materials, and color development, bleach-fixing, bleaching, fixing, washing, stabilization, etc. in the case of color materials. A combination of processes using a treatment liquid having one or more functions is performed. In photographic processing in which a large amount of light-sensitive material is processed, components consumed during processing are replenished, and on the other hand, components that are dissolved into the processing solution or concentrated by evaporation (for example, during development) are replenished. Measures are taken to maintain the performance of the processing solution at a constant level by removing bromide ions in the solution and silver complex salts in the fixing solution and keeping the processing solution components constant. A replenisher is added to the processing solution, and a portion of the processing solution is discarded in order to remove concentrated components in the photographic processing. In recent years, the system has been changing to a system in which the amount of replenishment fluid, including the washing water used as a replenishment fluid for washing, has been drastically reduced due to pollution and economic reasons. The liquid is led out through a drain pipe, diluted with waste water from washing water, cooling water from automatic processors, etc., and then disposed of in a sewer or the like. However, due to the recent tightening of pollution regulations under the Water Pollution Control Law and the ordinances of each prefecture, it is now possible to dispose of flush water and cooling water into sewers and rivers.
It has become virtually impossible to dispose of photographic processing solutions other than these (eg, developer, fixer, color developer, bleach-fixer, bleach, stabilizer, etc.). For this reason, each photo processing company pays a specialized waste liquid processing company to take the waste liquid home or installs pollution treatment equipment. However, the method of outsourcing to a waste liquid treatment company requires a considerable amount of space to store the waste liquid, is extremely expensive, and the initial investment (initial cost) for pollution treatment equipment is high. It has drawbacks such as being extremely large and requiring a fairly large space for installation. More specifically, the pollution treatment methods for reducing the pollution load of photographic waste liquid include activated sludge method (for example, Japanese Patent Publication No. 51-12943 and Japanese Patent Publication No. 51-7952, etc.), evaporation method (Japanese Unexamined Patent Publication No. 49-1972),
89347 and Japanese Patent Publication No. 56-33996, etc.), electrolytic oxidation method (Japanese Patent Publication No. 48-84462, Japanese Patent Publication No. 49-119458, Japanese Patent Publication No. 53-43478, Japanese Patent Publication No. 49-119457, etc.), ion Exchange Law (Special Publication No. 51-37704, Special Publication No. 53-383,
(Japanese Patent Publication No. 53-43271, etc.), reverse osmosis method (Japanese Patent Publication No. 1987-43271, etc.)
22463, etc.), chemical treatment methods (JP-A-49-64257,
Japanese Patent Publication No. 57-37396, Japanese Patent Publication No. 53-12152, Japanese Patent Publication No. 1987-12152
No. 49-58833, Japanese Patent Publication No. 53-63763, Special Publication No. 1987-
37395 etc.) are becoming known, but each
It has the following drawbacks. For example, activated sludge method requires extremely large equipment and a considerably large installation area, electrolytic oxidation method requires high equipment and electricity costs, and ion exchange method and reverse osmosis method require resin and The membrane suffers from severe fatigue and becomes unusable soon. Furthermore, chemical treatment methods have poor treatment efficiency and always use far more chemicals than necessary, which poses a problem of pollution caused by the excess chemicals left behind. It has drawbacks such as the possibility of causing fatigue. On the other hand, due to constraints from water resources, rising water supply and drainage costs, the simplicity of automatic processor equipment, and the work environment around automatic processors, in recent years stabilization treatment has been used instead of washing with water, and Photographic processing using automatic developing machines (waterless automatic developing machines) that do not require piping for water supply and drainage is becoming popular.
In such processing, it is desired that cooling water for keeping the temperature of the processing liquid is omitted. In such photographic processing that does not substantially use rinsing water or cooling water, the photographic waste liquid from the automatic processor is not diluted with water compared to the case where washing is performed, so the pollution load is extremely large. It is characterized by a small amount of waste liquid. Therefore, since the amount of waste liquid is small, piping outside the machine for supplying and draining liquid can be omitted, which is considered to be a drawback of conventional automatic developing machines. All disadvantages such as difficulty in moving after installation due to piping installation, narrow leg space, high cost for piping work during installation, and energy costs for hot water supply have all been eliminated, making it easier to use in offices. The extremely large advantage of achieving compactness and simplification to the point where it can be used as a machine is exhibited. However, on the other hand, the waste liquid has an extremely high pollution load, and is disposed of not only in rivers but also in sewers, making it completely impossible to dispose of it in accordance with pollution regulations. Furthermore, although the amount of waste liquid from such photographic processing (processing that does not substantially involve water washing) is small, even in relatively small-scale processing, for example, when processing In recent years, the processing of waste liquids has become an increasingly serious problem, with the processing of color photosensitive materials reaching 30 per day and approximately 50 per day for processing color photosensitive materials. As a means of dealing with the above-mentioned problem, a method is known in which persulfate and hydrogen peroxide are added to photographic waste liquid to reduce the pollution load value. −63763, JP-A-49-
64257, JP 57-37396 and JP 53-
It is disclosed in No. 12152, etc. However, in these conventional methods, the reaction efficiency is low, so it is necessary to add considerably excessive amounts of persulfate and hydrogen peroxide, and in order to add persulfate and hydrogen peroxide that correspond to the pollution load value of the waste liquid, it is necessary to add COD and BOD. The measurement operation was extremely complicated.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a photographic waste liquid treatment kit that makes it possible to dispose of photographic waste liquid that cannot be disposed of in the sewer system, etc. by reducing the COD (chemical oxygen demand) to substantially zero. The object of the present invention is to provide a photographic waste liquid treatment kit that is extremely advantageous in terms of cost and does not require post-treatment of chemicals (eg, peroxosulfate) for removing excess COD. Furthermore, another object of the present invention is to provide a photographic waste liquid treatment kit that does not require measurement of pollution load values such as COD and BOD. Still another object of the present invention is to provide a photographic waste liquid treatment kit for photographic waste liquid from automatic processors that does not substantially use washing water.

[Structure of the invention]

The object of the present invention is to reduce the amount of photographic waste liquid per unit amount of photographic waste liquid of a silver halide photographic light-sensitive material in the presence of a chelating agent having a stability constant for iron of 7 or more and/or a metal complex salt of the chelating agent. This is achieved by a photographic waste liquid treatment kit characterized in that the peroxosulfate necessary to reduce the COD (chemical oxygen demand) to substantially zero is prepared in advance. The present invention is preferably applied to automatic developing machines that do not use rinsing water, and furthermore to processing of photographic waste liquid in automatic developing machines that do not require water supply and drainage pipes. In the present invention, "reducing the COD of the photographic waste to substantially zero" means reducing the COD of the photographic waste to a concentration that allows it to be disposed of in rivers or sewers. By the way, COD based on discharge standards to general rivers is
Although there is no regulation standard based on COD under the Sewerage Law, the iodine consumption equivalent to COD is 220 ppm (for example in Tokyo). Next, the present invention will be explained in detail. The present invention provides a photographic waste liquid treatment kit containing peroxosulfate that is pre-prepared so that the COD is substantially zero for a unit amount of a specific photographic waste liquid, so that only the minimum amount of peroxosulfate is required. It is economically extremely advantageous, and since there is almost no surplus peroxosulfate, no post-processing is required, and it is also an extremely simple photographic waste liquid treatment method that does not require COD or BOD measurement operations. Significantly superior to conventional technology. The peroxosulfates of the present invention include, for example, ammonium persulfate, potassium persulfate, sodium persulfate and persulfate, sodium peroxo-sulfate, potassium peroxo-sulfate, potassium peroxo-sulfate/potassium sulfate (trade name: Oxone (manufactured by DuPont). )) etc. are mentioned as specific example compounds, and these peroxosulfates may be used in solid form or in liquid form by dissolving in water etc. However, from the point of view of unnecessary dissolution time of peroxosulfates, Preferably, it is in liquid form. When in liquid form, the concentration of the peroxosulfate in the kit of the present invention is preferably 2 g/~500 g/;
Particularly preferably, the amount is in the range of 5 g/ to 250 g/. The amount of peroxosulfate required to reduce the COD of photographic waste to substantially zero per unit amount of photographic waste is 0.05 per unit of photographic waste.
-8 mol is preferable, and 0.1-5 mol is more preferable. Further, the photographic waste liquid treatment kit of the present invention may contain a pH neutralizing agent such as an alkaline agent or an acid so that the pH after the waste liquid treatment is 5 to 9. Furthermore, when the photographic waste liquid is mixed with the photographic waste liquid treatment kit of the present invention in the presence of a chelating agent with a stability constant for iron of 7 or more and/or a metal complex salt of the chelating agent, the generation of sludge is suppressed, Furthermore, it is more preferably used because it has the surprising effect of reducing COD more efficiently. As the chelating agent, compounds represented by the following general formulas [] and [] are particularly preferably used. General formula [] A-COOM General formula [] B-PO ₃ M In _the formula, A and B each represent a monovalent group or atom, and may be an inorganic substance or an organic substance. M represents a hydrogen atom or an alkali metal atom. Further, among the chelating agents represented by the general formulas [] and [], particularly preferred chelating agents for the present invention are compounds represented by any of the following general formulas [] to []. General formula [] A ₁ −R ₁ −Z−R ₂ −COOM General formula [] In the formula, E is a substituted or unsubstituted alkylene group,
Cycloalkylene group, phenylene group, -R ₇ OR ₇
−, −R ₇ OR ₇ OR ₇ −, −R ₇ ZR ₇ −, Z represents >NR ₇ −A ₆ , >N−A ₆ , and R ₁ to R ₇ are substituted or unsubstituted. represents an alkylene group, A ₁ ~
A ₆ represents hydrogen, -OH, -COOM, -PO ₃ M ₂ ,
M represents hydrogen or an alkali metal atom. Also A ₂
At least one of ~A ₅ is -COOM or -PO ₃ M ₂ . General formula [] R ₈ N (CH ₂ PO ₃ M ₂ ) ₂ In the formula, R ₈ is a lower alkyl group, an aryl group,
Aralkyl group, nitrogen-containing 6-membered ring group [as a substituent -
OH, -OR, -COOM], where is a hydrogen atom,
Represents an alkali metal atom. General formula [] In the formula, R ₉ to _{R 11} are hydrogen atoms, -OH, lower alkyl (unsubstituted or as substituents -OH, -COOM,
PO ₃ M ₂ ), B ₁ to B ₃ are hydrogen atoms, -OH, -
COOM, −PO ₃ M ₂ , −Nj ₂ , where J is a hydrogen atom,
Represents lower alkyl, -C ₂ H ₄ OH, -PO ₃ M ₂ , M
represents a hydrogen atom or an alkali metal, and n and m represent 0 or 1. Specific examples of the chelating agents represented by the general formulas [] to [] include the following.

【table】 / \
HOOCCH ₂ CH ₂ COOH

[Table] ｜
_CH3
The chelating agent and/or the metal salt of the chelating agent is preferably used in an amount of 0.2 to 200 g per photographic waste liquid, more preferably 0.4 to 140 g/
is within the range of Further, from the viewpoint of ease of handling, the photographic waste liquid treatment kit is preferably one part, but may have two or more parts in some cases. In the present invention, when a developing agent is contained in the photographic waste solution, no sudden reaction occurs, which eliminates accidents such as bumping, which is advantageous. In particular, the developing agent is preferably a paraphenylenediamine-based developing agent having at least one water-soluble group (hydrophilic group) on the amino group.
Representative examples of these developing agents include the following compounds. A particularly effective color developing agent for the present invention has -( _CH2 )n- _CH2OH ,- as a substituent on the amino group.
( _CH2 )m- _NHSO2- ( _CH2 )n- _CH3 ,-( _CH2 )
m-O-( _CH2 )n- _CH3 ,- _{( CH2CH2O} )
It is a compound having each group of nCmH ₂ m ^- ₁ , and specific compounds include (1), (2), (3), (4) of the above specific examples,
(6) and (7) are mentioned. However, m and n are integers of 0 or more, preferably 0 to 5. In the present invention, when a thiosulfate is contained in the photographic waste liquid, generation of tar is suppressed during mixing, which is a more preferred embodiment of the present invention.
Examples of the thiosulfate include ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, triethanolammonium thiosulfate, and the like. Further, when the photographic waste liquid of the present invention contains 5 g/less or less of benzyl alcohol, it can be preferably used in the present invention because it is good in suppressing the generation of tar and reducing COD.
In particular, it is particularly preferably used when the amount is 1 g/or less. The surface tension of the photographic waste liquid of the present invention is 20 to 70dyne/
In the present invention, surfactants are preferably used because the speed at which the COD decreases is particularly remarkable when the amount of COD is 1 cm. The surface tension is determined by "Analysis and Testing Methods for Surfactants"
(Co-authored by Fumio Kitahara, Shigeo Hayano, and Ichiro Hara, published March 1, 1982, published by Kodansha Co., Ltd.). is the value of surface tension at . In the present invention, the surface tension of photographic waste liquid is
The method for achieving 70 dyne/cm is arbitrary and any method may be used, but surfactants are preferably used. These surfactants that increase the surface tension of processing liquids with bleaching ability from 20 to 70 dyne/cm may be added in advance to photographic waste liquids, or may be added to photographic waste liquid processing kits, or may be added to photographic waste liquid processing kits. It may be added as a separate part during mixing. Further, as a specific method for adding it to the photographic waste liquid, it may be added to a replenisher, or it may be contained in the photographic waste liquid by being eluted from the photographic material. Among the above-mentioned surfactants, compounds represented by the following general formulas [] to [] are preferably used from the viewpoint of the effects of the present invention. General formula [] In the formula, one of R ₂₀ and R ₂₁ represents a hydrogen atom, and the other represents a group represented by the formula -SO ₃ M (M represents a hydrogen atom or a monovalent cation). A ₂₀ represents an oxygen atom or a group represented by the formula -NR ₂₄ - (R ₂₄ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). R ₂₂ and R ₂₃ each have 4 to 16 carbon atoms.
represents an alkyl group. However, R ₂₂ , R ₂₃ or R ₂₄
The alkyl group represented by may be substituted with a fluorine atom. General formula [] A ₂₁ -O-(B)m-X ₁ In the formula, A ₂₁ is a monovalent organic group, for example, carbon number is 6
~20, preferably 6 to 12 alkyl groups (e.g.
hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), or an aryl group substituted with an alkyl group having 3 to 20 carbon atoms, and preferably has 3 to 20 carbon atoms as a substituent.
12 alkyl groups (e.g. propyl, butylpentyl, hexyl, heptyl, octyl, nonyl,
decyl, undecyl, dodecyl, etc.), and aryl groups include phenyl, tolyl,
Examples include groups such as xynyl, biphenyl, and naphthyl, with phenyl or tolyl being preferred. The position where the alkyl group is bonded to the aryl group may be any of the ortho, meta, and rose positions. B represents ethylene oxide or propylene oxide, and m represents an integer from 4 to 50. X ₁ represents a hydrogen atom, SO ₃ Y or PO ₃ Y ₂ , and Y represents a hydrogen atom, an alkali metal atom (such as Na, K or Li) or an ammonium ion. General formula [] In the formula, R ₂₅ , R ₂₆ , R ₂₇ and R ₂₈ each represent a hydrogen atom, an alkyl group, or a phenyl group, but R ₂₅ ,
The total number of carbon atoms in R ₂₆ , R ₂₇ and R ₂₈ is 3 to 50. X ₂ represents an anion such as a halogen atom, a hydroxyl group, a sulfuric acid group, a carbonic acid group, a nitric acid group, an acetic acid group, or a p-toluenesulfonic acid group. General formula [] In the formula, R ₂₉ , R ₃₀ , R ₃₁ and R ₃₂ each represent a hydrogen atom or an alkyl group, and M is the general formula []
is synonymous with n and p are each 0 or 1 to 4
represents an integer and satisfies 1≦n+p≦8. Specific examples of compounds represented by the general formulas [] to [] are listed below, but the compounds are not limited thereto.

[Table] ｜ ｜

SO ₃ NaC ₂ H ₅

[Table] ｜ ｜
SO ₃ Na C ₂ H ₅

【table】

【table】

[Table] ｜

○＋

_CH3

[Table] ｜

○＋

( _{CH2CH2O ) −2H}

【table】

【table】

[Table] The actual processing solution discharge amount ratio discharged from the automatic processor according to the present invention is [color developing solution discharge amount]: [bleach fixing solution discharge amount (or bleach solution discharge amount + fixer discharge amount)] : [Stable liquid discharge amount (or first stable liquid discharge amount +
2nd stable liquid discharge amount)] = [0.1 to 2.4]: [0.1 to 1.6]:
[1] is particularly preferably used in the present invention because it has the effect of minimizing the generation of sludge and tar. The COD of the waste liquid from the above-mentioned processing solution varies depending on the formulation, but is essentially 3,000 to 50,000 ppm for color developer, 40,000 to 100,000 ppm for fixer, 40,000 to 100,000 ppm for bleach, and 1,000 to 10,000 ppm for stabilizer. It is. When the total amount of photographic waste liquid discharged from the automatic processor according to the present invention is 50 or less per day,
The waste liquid treatment kit of the present invention is preferably used in the present invention because it acts more effectively on the objective effects of the present invention, and is particularly preferably used when the amount of waste liquid treatment is 30 or less per day. When the photographic waste solution of the present invention contains less than 2 g of silver, it is preferably used in the present invention because sludge generation is extremely good.
It is particularly preferably used in a range of 0.5 g/or less. The photographic waste liquid specified in the present invention includes a single photographic processing liquid waste liquid obtained when a known silver halide photographic light-sensitive material is processed with a known photographic processing liquid, and a mixture of any two or more types of waste liquid. The photographic processing solution includes the following. Color developer: A color developer with a pH of 7 or higher containing a developing agent, an alkaline agent, a preservative, and other additives as shown below. Color developing agents include aromatic primary amine color developing agents, and the main agents include aminophenol derivatives and p-phenylenediamine derivatives. These may be organic or inorganic acid salts, such as hydrochloride, sulfate, p-toluenesulfonate,
It may be a sulfite, an oxalate, a benzenesulfonate, etc., and the concentration of the color developing agent is from 0.1 to
May be in the range of 30g. Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene, 2-oxy-3-
Includes amino-1,4-dimethyl-benzene and the like. Examples of p-phenylenediamine derivatives include N,N'-dialkyl-p-phenylenediamine compounds such as N,N'-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine Hydrochloride, N,N'-dimethyl-p
-phenylenediamine hydrochloride, 2-amino-5-
(N-ethyl-N-dodecylamino)-toluene,
N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline hydrochloride, N
-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p −
Included are toluene sulfonate and the like. Examples of alkaline agents include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, lithium metaborate, and borax. Preservatives include hydroxylamine, sulfites, and the like. Other additives include benzyl alcohol, alkali metal halides such as potassium bromide and potassium chloride, development regulators such as citradinic acid, various antifoaming agents and surfactants, methanol, dimethylformamide, etc. Organic solvents such as dimethyl sulfoxide, and antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-
Examples include anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, bentose or hexose, pyrogallol-1,3-dimethyl ether, and the like. Activator liquid: An aqueous solution of the alkaline agent mentioned in the color developer. Bleaching agents: bleaching agents such as metal complex salts of organic acids such as polycarboxylic acids, aminopolycarboxylic acids (which may be alkali metal salts, ammonium salts or water-soluble amine salts), or organic acids such as oxalic acid and citric acid. Specific examples of aminopolycarboxylic acids that are included in bleaching solutions with a pH of 2.0 or higher containing those coordinated with metal ions such as iron, cobalt, and copper are listed below. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycincitric acid (or tartaric acid)

[9] Ethyl ether diamine tetraacetic acid [10] Glycol ether diamine tetraacetic acid [11] Ethyl diamine tetrapropionic acid [12] Phenyl diamine tetra acetic acid [13] Ethylene diamine tetra acetic acid disodium salt [14] Ethylene diamine tetra acetic acid tetra( trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid sodium salt [18] Propylene diamine tetraacetic acid sodium salt [19] Nitriloacetic acid sodium salt [20] Cyclohexane diamine tetraacetic acid sodium salt These bleaching agents are used in an amount of 5 to 450 g/, more preferably 20 to 250 g/. In addition to the above-mentioned bleaching agent, the bleaching solution may optionally contain a solution containing sulfite as a preservative. Alternatively, it may be a bleaching solution containing an ethylenediaminetetraacetate iron() complex salt bleaching agent and a large amount of a halide such as ammonium bromide. The halides may include, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can. The bleaching solution is disclosed in Japanese Patent Publication No. 46-280, Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 46-556, Belgian Patent No. 770910, Japanese Patent Publication No. 46-556,
It is also possible to add various bleaching accelerators described in JP-A Nos. 45-8836, 53-9854, JP-A-54-71634, and JP-A-49-42349. Fixer: A compound that reacts with silver halide to form a water-soluble complex salt, such as those used in conventional fixing processes as a fixer, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, and thiocyanogen. acid potassium,
Included are those containing 5 g or more of thiocyanhydrochloric acid, thiourea, thioether, etc., such as sodium thiocyanate and monoium thiocyanate, within a soluble range. In addition, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate,
Those containing various PH laxatives such as ammonium hydroxide alone or in combination of two or more,
Furthermore, those containing various optical brighteners, antifoaming agents, or surfactants, preservatives of bisulfite adducts of hydroxylamine, hydrazine, and aldehyde compounds, and organic chelating agents such as aminopolycarboxylic acids. Or nitro alcohol,
Included are fixing solutions with a pH of 3.0 or higher that contain stabilizers such as nitrates, organic solvents such as methanol, dimethylsulfamide, dimethylsulfoxide, and the like. Bleach-fix solution: A bleach-fix solution containing as a bleaching agent the metal complex salt of an organic acid in the bleaching solution at a concentration ranging from 0.1 to about 300 g/, and as a fixing agent containing the fixing agent in the previous fixing solution at a concentration up to saturation. Further, it includes those containing sulfite as a preservative, those containing a PH moderator in the bleaching agent, and bleach-fixing solutions with a pH of 4.0 or higher containing the bleaching agent in the bleaching agent. . Also,
A bleach-fix solution consisting of an ethylenediaminetetraacetic acid iron () complex salt bleach and a small amount of a halide such as ammonium bromide other than the silver halide fixing agent mentioned above, or conversely, a large amount of a halide such as ammonium bromide added. It also includes a special bleach-fixing solution having a composition consisting of a combination of an ethylenediaminetetraacetic acid iron() complex salt bleaching agent and a large amount of a halide such as ammonium bromide. In addition to ammonium bromide, the halides include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide,
Also included are potassium iodide and ammonium iodide. Stabilizing liquid: ammonium compounds such as ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, ammonium fluoride, acidic ammonium fluoride, ammonium fluoroborate, arsenic acid Ammonium, ammonium bicarbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, ammonium lauric tricarboxylate, ammonium benzoate, ammonium carbamate, citric acid Ammonium, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium hydrogen phthalate, ammonium hydrogen tartrate, ammonium thiosulfate, ammonium sulfite, ammonium ethylenediaminetetraacetate, ferric ammonium ethylenediaminetetraacetate, ammonium lactate , ammonium malate, ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,4,6 , -tritonitrophenol ammonium, etc. from 0.001 to 1.0 mol/chelating agent such as organic carboxylic acid chelating agent, organic phosphoric acid chelating agent, inorganic phosphoric acid chelating agent, polyhydroxy compound, etc. Specifically, ethylenediamine diorthohydroxyphenyl Acetate diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, transcyclohexane Diaminetetraacetic acid, ethylenediaminetetraacetic acid, 1,1'-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-
0.01 to 50 g of tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, etc. per stabilizer, and organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), PH regulators (phosphates, borates,
Hydrochloric acid, sulfuric acid, etc.) Antifungal agents (phenol derivatives,
Catechol derivatives, imidazole derivatives, triazole derivatives, thiabendazole derivatives,
Organic halogen compounds, other fungicides known as slime control agents in the paper-pulp industry), optical brighteners, surfactants, etc.
Preservative, Bi, Mg, Zn, Ni, Al, Sn, Ti, Zr
Stabilizing solutions containing effective amounts of metal salts such as, etc. are included. Black and white developer: 4,4'-dimethyl-1-phenyl-
3-pyrazolidone, 4-methyl-4'-hydroxymethyl-1-phenyl-3-pyrazolidone,
Developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, potassium carbonate, potassium bromide and 2-methyl Inorganic substances such as benzimidazole and methylbenzthiazole,
Alternatively, it contains an organic inhibitor, a water softener such as a polyphosphate, a surface overdevelopment inhibitor consisting of a small amount of iodide or a mercapto compound, and the like. Included are black and white developers commonly used for silver halide photosensitive materials. Among these waste liquids, those containing silver are
The waste liquid treatment kit of the present invention may be used after removing silver by a known silver recovery method such as a metal substitution method using steel wool or an electrolytic method, or the waste liquid treatment kit of the present invention may be used while containing silver. You may also do this. Methods for mixing the photographic waste liquid treatment kit of the present invention with a unit amount of a specific photographic waste liquid include a method of mixing in small batches many times depending on the overflow amount (waste liquid amount), a method of mixing a relatively large amount of Methods include a method in which a certain amount of photographic waste liquid is stored and then mixed at once (), and a method in which a unit amount of photographic waste liquid is initially added to an excess photographic waste liquid processing kit according to the processing and mixed (). , in the present invention, the above method () is most preferably used. Specifically, the photographic waste liquid treatment kit of the present invention is added in advance to a waste liquid container at the bottom of an automatic processor, and mixed with overflowing photographic waste liquid. (See Figure 1) When the photographic waste liquid treatment kit of the present invention is mixed with photographic waste liquid, it may be left at room temperature and then discarded, but it is better to perform a heating operation because the reaction time is shorter. It is more preferably used in the present invention. Further, in the present invention, it is more preferable to use stirring means such as a stirring bar, magnetic stirrer, ultrasonic stirring, stirring, and shaking during the mixing because the reaction efficiency increases. When the photographic waste liquids as described above are mixed with the photographic waste liquid treatment kit of the present invention, each type of waste liquid may be mixed separately, or two or more types may be mixed together. Next, preferred embodiments will be shown. (B) Color photography (Part 1) Process: color development → bleach-fixing → stabilization The waste solutions from color development and stabilization are combined and mixed with the photographic waste solution treatment kit of the present invention, and the waste solutions from bleach-fixing are separated using a conventional method. Collect it as is in a container,
After recovering the silver, it is mixed with another photographic waste liquid treatment kit of the present invention. (B) Color photographic processing (Part 2) Process: color development → bleaching → fixing → stabilization The waste solutions from color development, bleaching, and stabilization are combined and mixed with the color development waste solution treatment kit of the present invention, and the waste solution from fixing is processed using the conventional method. After collecting the silver in a separate container,
Mix with another photographic waste liquid treatment kit of the present invention. (c) Black and white photographic processing Steps: Phenomenon → Fixing → Washing The waste liquid from development is mixed with the photographic waste liquid treatment kit of the present invention, the waste liquid from fixing is collected in a separate container, and after silver recovery,
Mix with another photographic waste liquid treatment kit of the present invention. Next, an example of an apparatus for carrying out the present invention will be explained with reference to the drawings. FIG. 1 is a schematic sectional view of an automatic processor for silver halide color photographic materials (film and paper). In the figure, reference numeral 101 denotes a mounting portion for mounting a magazine 103 containing a roll of connected and wound color negative film or color paper that has been photographed, and is provided on the side wall of the main body 104 of the automatic processor. Color negative film or color paper 102 of the film magazine attached to the mounting part 101
enters the main body 104 from the main body entrance part 105,
Color developer tank 106, bleach-fix tank 107, stabilization tank 1
After being automatically developed through step 10, drying section 1
11 (having an openable and closable lid) and taken out from the main body outlet 112, the product is made into a product through cutting and other processes. Although not shown, there are a replenisher tank, piping, etc. for replenishing each of the processing tanks 106 to 110 with replenisher. 113 is a control system material chamber for adjusting the temperature of the processing liquid. 114A, 114B, and 11
Reference numeral 4C denotes a drain pipe for guiding the photographic waste liquid from each processing tank 106 to 110 to a container (waste liquid container) 115 for receiving the photographic waste liquid.

【Example】

Next, the present invention will be explained in detail by way of implementation.
The present invention is not limited to these Examples. Example 1 Using silver chlorobromide (silver chloride 28 mol%), color sensitization was carried out using a regular sensitizing dye, an ortho sensitizing dye, and a panchromatic sensitizing dye, and three types of couplers, yellow, magenta, and cyan, were produced. Photographic emulsions were prepared using each of these in accordance with conventional methods. This emulsion was applied to polyethylene coated paper to prepare a color paper sample. Using this color paper, it was exposed to light using a printer and then subjected to continuous replenishment processing using an automatic developing machine. The treatment steps and composition of the treatment liquid at this time are as follows. Standard processing steps [1] Color development 38°C 3 minutes 30 seconds [2] Bleach-fixing 33°C 1 minute 30 seconds [3] Stabilization 25°C to 30°C 3 minutes [4] Drying 75°C to 80°C approximately 2 minutes Processing liquid composition <Color developing tank liquid> Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 1.3g Potassium chloride 0.2g Potassium carbonate 30.0g 3-Methyl-4-amino-ethyl-N-(β-
Mematanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g Hydroxylamine sulfate 3.0g 1-hydroxyethylidene-1,1-diphosphonic acid 0.4g hydroxy Ethyliminodiacetic acid 2.5g Maglucium chloride hexahydrate 0.7g 1,2-dihydroxybenzene-3,5-disulfonic acid disodium salt 0.2g Add water to make 1, then add KOH and H ₂ SO ₄ to PH10.20
And so. <Color developer replenisher> Benzyl alcohol 20ml Ethylene glycol 20ml Potassium sulfite 3.0g Potassium carbonate 30.0g Hydroxylamine sulfate 4.0g 3-Methyl-4-amino-N-ethyl-N-
(β-methanesulfonamidoethyl)-aniline sulfate 7.5g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.5g 1-hydroxyethylidene-1,1-diphosphonic acid 0.5g hydroxyethyliminodiacetic acid 3.0g Magnesium chloride hexahydrate 0.8g 1,2-dihydroxybenzene-3,5-disulfonic acid disodium salt 0.3g Water was added to make 1, and the pH was adjusted to 10.70 with KOH. <Bleach-fix tank solution> Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust to PH7.1 with potassium carbonate or glacial acetic acid At the same time, water was added to bring the total volume to 1. <Bleach-fixing replenisher A> Ethylenediaminetetraacetic acid ferric ammonium dihydrate 260g Potassium carbonate 42g Add water to make 1. This solution is adjusted to pH 6.7±0.1 using acetic acid and/or ammonia. <Bleach-fix replenisher B> Ammonium thiosulfate (70% solution) 500ml Ammonium sulfite (40% solution) 250ml Ethylenediaminetetraacetic acid 17g Glacial acetic acid 85ml Add water to bring the total volume to 1. This solution is adjusted to pH 5.3±0.1 using acetic acid and/or ammonia. <Stabilizing solution and stable replenishing solution> 5-chloro-2-methyl-4-isothiazolin-3-one 0.02g Orthophenylphenol sodium salt 0.1g 2-methyl-4-isothiazolin-3-one
0.02g 2-octyl-4-isothiazolin-3-one
0.01g Polyethylene glycol (molecular weight 1540) 1.0g 1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.5g Ammonium sulfite (40% aqueous solution) 2.0g MgSO ₄・7H ₂ O 0.2g ZnSO ₄ 0.2g Ammonium Water (25% aqueous solution) 2.5g Nitrilotriacetic acid 1.2g Sodium hydroxide 1.0g Water was added to bring the total amount to 1, and the pH was adjusted to _7.0 with _H2SO4 . Fill an automatic processor with the color developer tank solution, bleach-fix tank solution, and stabilizing solution described above, and add the above-mentioned color developer replenisher and bleach-fix replenisher A and B to the stabilizer every 3 minutes while processing the color paper. A running test was conducted while replenishing a predetermined amount of replenisher.
The amount of replenishment is 2.0ml per ^100cm2 of color paper to the color development tank, and the amount of bleach-fixing replenisher A and B to be refilled to the bleach-fixing tank.
0.5ml each, 2.8 ml of stabilizing solution to replenish the stabilizing tank
ml was replenished. The stabilizing tank of the automatic developing machine has the first to second layers in the direction of the flow of the photosensitive material, and the final tank is replenished, and the overflow from the final tank is allowed to flow into the previous tank, and the first tank is refilled. The tank overflowed. Using an automatic processor as shown in Figure 1, 10 m ² of color paper was continuously processed. The photographic waste liquid treatment kit of the present invention (476 g of sodium persulfate) is contained in the waste liquid container (115) of the automatic processor.
Contains. After continuous treatment, COD and residual sodium persulfate in the waste liquid container were measured. A similar experiment was conducted without adding a waste liquid treatment kit. At the same time, the generation of tar was observed. The above results are summarized in Table 1 below.

[Example 2]

Color agent (3-methyl-4-amino-N-ethyl-(β-methanesulfonamidoethyl)-aniline sulfate) in the color developer used in Example 1
A similar experiment was conducted by changing 3-methyl-4-amino-N,N-diethylaminoaniline hydrochloride. As a result, COD reduction and tar generation were almost the same, but when the photographic waste liquid and the photographic waste liquid treatment kit were mixed, a rather rapid reaction was observed and heat was generated. [Example 3] The discharge amount ratio of the processing solution in Example 1 was as follows: [Color developing solution discharge amount (hereinafter abbreviated as CD)]: [Bleach-fix discharge amount (hereinafter abbreviated as BF)]: [Stable An experiment similar to Example 1 was conducted with the ratio of liquid discharge amount (hereinafter abbreviated as SS) = 0.71:0.36:1, but the values of CD and/or BF were each set to 0.1 or less. Furthermore, a similar experiment was conducted with the CD value set to 2.4 or higher and the BF value set to 1.6 or higher. As a result, [CD]: [BF]: [SS] = [0.1~2.4]: [0.1~
1.6]: Outside the range of [1], the generation of sludge and tar was significant. [Effects of the Invention] The present invention is particularly advantageous in solving the above-mentioned technical problems that occur when an automatic processor is not equipped with a water supply pipe, a cooling water supply pipe, and a drain pipe. However, it is effective not only for such an automatic processor, but also for photographic processing using an automatic processor, or for photographic processing not using an automatic processor, in which a part of the photographic waste liquid cannot be disposed of in a sewer or the like.

[Brief explanation of the drawing]

FIG. 1 is a schematic sectional view showing an example of an apparatus for carrying out the present invention. 101...Magazine attachment part, 102...Color negative film or color paper, 103...Magazine, 104...Automatic developer material body, 105...
Main body inlet section, 106...Color developer tank, 107...
Bleach-fix tank, 110... Stabilization tank, 111... Drying section, 112... Main body outlet, 113... Control system equipment room, 114A, 114B and 114C... Drain pipe, 115... Waste liquid container.

Claims (1)

[Claims] 1 In the presence of a chelating agent with a stability constant for iron of 7 or more and/or a metal complex salt of the chelating agent,
The peroxosulfate required to make at least the COD (chemical oxygen demand) of the photographic waste liquid substantially zero per unit amount of the photographic waste liquid of the silver halide photographic light-sensitive material is prepared by adjusting in advance. Photo waste liquid treatment kit.