JPH0554930B2 - - 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, as pollution treatment methods for reducing the pollution load of photographic waste liquid, activated sludge method (for example, Japanese Patent Publication No. 12934/1982 and Japanese Patent Publication No. 7952/1983, etc.), evaporation method (Japanese Patent Publication No. 49/1989),
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. 1983-43271, etc.)
22463 etc.), chemical treatment method (JP-A No. 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, the activated sludge method requires extremely large equipment and a fairly large installation area, the electrolytic oxidation method requires high equipment costs and high electricity costs, and the 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 when washing is performed, so the pollution load is extremely large. It is characterized by a small amount of waste liquid. Therefore, due to the small amount of waste liquid, it is possible to omit piping outside the machine for supplying and draining liquid, which makes it difficult to move after installation to install piping, which is considered a drawback of conventional automatic processors. This eliminates all of the disadvantages such as the small leg space, the high cost of piping work during installation, and the high cost of energy for hot water supply, and it has been made compact and simple enough to be used as an office machine. This provides an extremely large advantage in terms of 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 The amount is 30 times a day for material processing, and about 50 times a day for color photosensitive materials, and the treatment of waste liquid has become an increasingly big problem in recent years. 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. No. 53-63763, JP-A-49
−64257, Japanese Patent Publication No. 57-37396, and Japanese Patent Publication No. 1983-
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 is to provide a photographic waste liquid treatment kit which is extremely advantageous in terms of cost and does not require post-treatment of chemicals (for example, perhalogenates) to remove 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 described above is to reduce the amount of perhalogenate, halite, and hypohalite necessary to make at least the COD (chemical oxygen demand) of the photographic waste liquid substantially zero per unit amount of the photographic waste liquid. This is achieved by a photographic waste liquid treatment kit characterized in that at least one selected from acid salts and a chelating agent are prepared and mixed 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 at least one of perhalogenates, halous acids, and hypohalous acids and chelates prepared in advance so that COD is substantially zero for a unit amount of a specific photographic waste liquid. It is economically extremely advantageous because the photographic waste solution treatment kit containing the agent requires only the minimum amount of perhalogenates, and since there is almost no excess perhalogenates, no post-treatment is required. Moreover, it is significantly superior to conventional techniques in that it is an extremely simple photographic waste liquid treatment method that does not require COD or BOD measurement operations. The perhalogenates used in the present invention include potassium perchlorate, sodium perchlorate, potassium perbromate, strontium perchlorate, cesium perchlorate, sodium perbromate, potassium periodate,
Specific example compounds include sodium periodate, and examples of the halides of the present invention include potassium chlorite, sodium chlorite, sodium bromite, sodium bromite, potassium iodine, and sodium chlorite. Specific example compounds include sodium iodate, and examples of the hypohalite of the present invention include potassium hypochlorite, sodium hypochlorite, calcium hypochlorite, potassium hypobromite, and hypohalite. Specific examples include sodium bromate, potassium hypoiodite, and sodium hypoiodite. These perhalogenates, halides and hypohalites may be used alone or in combination in the present invention. These perhalogenates, halides, and hypohalites may be used in a fixed form or in a liquid form as the photographic waste liquid treatment kit of the present invention, but they are particularly suitable for the photographic waste liquid treatment kit of the present invention. In the present invention, a liquid form is more preferably used from the viewpoint of reacting smoothly and more completely with the kit. When in liquid form, the perhalates, halites and hypohalites are preferably used in a concentration range of 0.2% to 50%, and more preferably 1%.
It ranges from % to 35%. 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 photographic waste liquid is mixed with the photographic waste liquid treatment kit of the present invention 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, the generation of sludge is suppressed. The surprising effect is that COD reduction progresses 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 ₅ 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], M 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 , 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】 \
_CH2 COOH

[Table] ｜
_CH2 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),
(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.). This is the value of surface tension according to 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, _R22 , _R23 or _R24
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, dodecyl, etc.), or an aryl group substituted with an alkyl group having 3 to 20 carbon atoms, and the substituent preferably has 3 carbon atoms.
~12 alkyl groups (e.g. propyl, butylpentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl groups)
Examples of the aryl group include phenyl, tolyl, 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 of 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 Na

[Table] ｜ ｜
SO ₃ Na C ₂ H ₅

【table】

[Table] ｜

○＋

( _{CH2CH2O ) −2H}

【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. Predicted COD in treatment agents and treatment processes
For this purpose, the necessary and sufficient waste liquid treatment kit of the present invention is applied. The COD of the waste liquid from the above-mentioned processing solution varies depending on the formulation, but for practical purposes it is 3,000 to 50,000 ppm for color developing solution, 40,000 to 100,000 ppm for fixer, 40,000 to 100,000 ppm for bleaching solution,
The stabilizer is 1000 to 10,000 ppm. 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: PH containing a developing agent, alkaline agent, preservative, and other additives as shown below.
Contains seven or more color developers. 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 acid or inorganic salts,
For example, it may be a hydrochloride, a sulfate, a p-toluenesulfonate, a sulfite, an oxalate, a benzenesulfonate, etc., and the concentration of the color developing agent may range from 0.1 to 30 g. Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-oxy-toluene, 2-aminophenol, and p-aminophenol.
-oxy-3-amino-1,4-dimethyl-
Contains benzene, etc. 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 sulfate, N-ethyl-N-β-hydroxyethylaminoaniline , 4-amino-3-
Included are methyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate, and the like. Examples of alkaline agents include sodium hydroxide,
Potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, sand, and the like are included. Preservatives include hydroxylamine, sulfites, and the like. Other additives include benzyl alcohol, alkali metal halides, potassium bromide, potassium chloride, etc.
Alternatively, development regulators such as citradinic acid, various antifoaming agents and surfactants, organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, and antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, etc. 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, bentose or hexose, pyrogallol-
Examples include 1,3-dimethyl ether. Activator liquid: An aqueous solution of the alkaline agent mentioned in the color developer. Bleaching solution: A bleaching agent containing a metal complex salt of an organic acid such as a polycarboxylic acid, an aminopolycarboxylic acid (which may be an alkali metal salt, an ammonium salt or a water-soluble amine salt), or an organic acid such as oxalic acid or citric acid. Included are bleaching solutions with a pH of 2.0 or higher that contain coordinated metal ions such as iron, cobalt, and copper. Specific examples of aminopolycarboxylic acids 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. Included are those containing 5 g or more of thiocyanhydrochloric acid such as potassium thiocyanate, sodium thiocyanate, and monoium thiocyanate, thiourea, thioether, etc., in an amount within the range that can be dissolved.
Furthermore, various PH laxatives such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be used alone or in combination. Those containing in combination, those containing various optical brighteners, antifoaming agents, or surfactants, preservatives for bisulfite adducts of hydroxylamine, hydrazine, and aldehyde compounds, and aminopolycarboxylic acids. Examples include fixing solutions having a pH of 3.0 or higher and containing organic chelating agents such as nitroalcohols, 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 a metal complex salt of an organic acid in the bleaching solution at a concentration ranging from about 0.1 to about 300 g/, and as a fixing agent containing the fixing agent in the fixing solution in a concentration up to a saturation amount. Further, it includes those containing sulfite as a preservative, those containing a pH buffering agent in the fixing agent, and bleaching fixers containing a bleaching agent with a pH of 4.0 or higher in the bleaching agent. In addition, a bleach-fixing 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 may be used. It also includes a bleach-fix solution having a composition in which ethylenediaminetetraacetic acid iron() complex salt is added to a bleach-fix solution, and also a special bleach-fix solution having a composition consisting of a combination of an ethylenediaminetetraacetic acid iron() complex salt bleach 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,
ammonium arsenate, 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, ammonium citrate, 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, malate ammonium acid, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate,
Ammonium tartrate, ammonium thioglycolate, 2,4,6,-trinitrophenolammonium, etc. 0.001 to 1.0 mol/
Chelating agents such as organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds, etc. Specifically, ethylenediamine diorthohydroxyphenyl acetate diaminopropane tetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediamine triacetic acid Acetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, 1,1'-diphosphonoethane −
2-carboxylic acid, 2-phosphonobutane-1,
2,4-tricarboxylic acid, 1-hydroxy-
0.01 to 50 g of 1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, etc. per stabilizer, and an organic acid salt. (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), PH regulators (phosphates, borates, hydrochloric acid, sulfuric acid, etc.), mold inhibitors (phenol derivatives, catechol derivatives, imidazole derivatives, triazole derivatives) , thiabendazole derivatives, organic halogen compounds, other fungicides known as slime control agents in the pulp and paper industry), optical brighteners, surfactants, preservatives, Bi, Mg,
Stabilizers containing effective amounts of metal salts such as Zn, Ni, Al, Sn, Ti, Zr, etc. are included. Black and white developer: 4,4'-dimethyl-1-phenyl-
developing agents such as 3-pyrazolidone, 4-methyl-4'-hydroxymethyl-1-phenyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone, metol and hydroquinone;
Preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate, and inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, and methylbenzthiazole. , a water softener such as a polyphosphate, a surface overdevelopment inhibitor consisting of a small amount of iodide or a mercapto compound, etc., and a black and white developer 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 solution from bleach-fixing is separated using a conventional method. After collecting the silver, the silver is collected as is in a container and mixed with another photographic waste liquid treatment kit of the present invention. (B) Color photographic processing (Part 2) Process: color development → bleaching → fixing → stabilization Color development The waste solutions from 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, it is mixed with another photographic waste liquid treatment kit of the present invention. (c) Black-and-white photographic processing step: Development → Fixation → Water 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 another container, and after silver recovery, the waste liquid from the development is processed by another photographic waste liquid treatment according to the present invention. Mix with kittuto. 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 equipment room 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 solution composition (color developing tank solution) Benzyl alcohol 15ml Ethylene glycol 15ml Potassium chlorite 2.0g Potassium bromide 1.3g Potassium chloride 0.2g Potassium carbonate 30.0g 3-Methyl-4-amino-ethyl-N-(β-methanesulfone) (amidoethyl)-aniline sulfate
5.5g Optical brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g Hydroxylamine sulfate 3.0g 1-hydroxyethylidene-1,1-diphosphonic acid 0.4g Hydroxyethyliminodiacetic acid 2.5g Maglucium chloride 6 Water salt 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 Hydroxyamine sulfate 4.0g 3-Methyl-4-amino-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 liquid and stable replenishing liquid> 5-chloro-2-methyl-4-isothiazoline-
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 Ammonia 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 tanks of the automatic processor are the first tank to the second tank 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 FIG. 1, 10 cm ² of color paper was continuously processed. In the waste liquid container 115 of the automatic processor, there is a photographic waste liquid treatment kit (10% sodium hypochlorite) of the present invention.
1.5 and 10% of exemplary chelating agent 210.1). After continuous treatment, COD and residual sodium hypochlorite 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. In addition, in the waste liquid treatment kit in which only the chelating agent was removed, the COD after treatment remained at 45 ppm, and the presence of a slight amount of sludge 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 [color developer discharge amount (hereinafter abbreviated as CD)]: [bleach-fix discharge amount (hereinafter abbreviated as BF)]: [stable Liquid discharge amount (hereinafter referred to as
Abbreviated as SS. )] = 0.71:0.36:1, but an experiment similar to Example 1 was conducted with the values of CD and/or BF set to 0.1 or less, respectively. 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. [Example 4] Example. 10% sodium hypochlorite used in step 1
Example by replacing 1.5 with 10% sodium periodate 4.3 and 10% sodium chlorite 1.8.
When we conducted an experiment similar to 1, almost all results were obtained. 1
obtained similar results. [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 automatic processors, but also for photographic processing using automatic processors where a part of photographic waste liquid cannot be disposed of into sewers, etc., or for photographic processing that does not require automatic processors. The material is not limited to silver halide photographic materials as long as the material is of a type that is treated with a processing liquid and the waste liquid of the processing liquid has a COD load.

[Brief explanation of drawings]

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

Claims (1)

[Scope of Claims] 1. Perhalogenates, halides, and hypohalogens 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. A photographic waste liquid treatment kit characterized in that at least one selected from acid salts and a chelating agent are prepared and mixed in advance. 2. The photographic waste liquid treatment kit according to claim 1, wherein the photographic waste liquid is a photographic waste liquid from an automatic developing machine that does not use washing water. 3. The photographic waste liquid treatment kit according to claim 1 or 2, wherein the photographic waste liquid is a photographic waste liquid from an automatic developing machine that does not require a supply or drain pipe.