JPH0554932B2 - - 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 have been taken to maintain the performance of the processing solution at a constant level by removing the effects of bromide ions in the solution and silver complex salts in the fixing solution and keeping the processing solution components constant. Therefore, a replenisher is added to the processing solution, and a portion of the processing solution is discarded to remove the thickening 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. 12943/1983 and Japanese Patent Publication No. 7952/1982), 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 generated sludge method requires extremely large equipment and a fairly large installation area, the electrolytic oxidation method requires high equipment and 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 the case where 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 30 per day for processing materials, 1 per day for processing color photosensitive materials
The number of waste liquids is approximately 50 per day, and treatment of the waste liquid has become increasingly necessary in recent years. As a means to deal with the above problem,
64257 and Japanese Patent Publication No. 57-37395, etc., methods using sodium hypochlorite are disclosed. However, since these conventional methods use strong acids or mineral acids, a large amount of sulfur dioxide gas is generated from the photographic waste liquid, especially the photographic waste liquid containing thiosulfates and sulfites, which is extremely problematic in terms of occupational health. was the reality. [Object of the Invention] Therefore, the object of the present invention is to create a photographic waste liquid that cannot be disposed of into a sewer or the like due to the contents contained therein, and which can be disposed of by reducing the COD (chemical oxygen demand) to substantially zero. An object of the present invention is to provide a waste liquid treatment kit, a method for removing COD from photographic waste liquid, and a method for neutralizing PH. Furthermore, another object of the present invention is to provide a photographic waste liquid treatment kit for suppressing harmful substances in the photographic waste liquid of an automatic processor that does not substantially use washing water, and a method for removing COD and PH neutralizing the photographic waste liquid. It's about doing. Furthermore, another object of the present invention is to provide a kit for treating photographic waste liquid that does not generate harmful gases such as sulfur dioxide gas, and a method for removing COD and neutralizing the pH of the photographic waste liquid. Furthermore, another object of the present invention is to provide a photographic waste liquid treatment kit that generates less tar and a photographic waste liquid treatment kit that generates less tar.
The purpose of the present invention is to provide a COD treatment and PH neutralization method.

[Structure of the Invention] The object of the present invention described above is to provide peroxosulfate,
A photographic waste liquid treatment kit comprising a combination of at least one compound selected from hydrogen peroxide, a hydrogen peroxide releasing substance, a perhalogenate, a halide, and a hypohalite and a surfactant, and the photographic waste liquid. This is achieved by a COD and PH controlled treatment method using a treatment kit and adding a PH neutralizer after holding it for a certain period of time. The waste liquid treatment kit preferably contains an alkaline agent, and is preferably prepared in advance by adding the photographic waste liquid treatment kit to photographic waste liquid to control COD and PH. The holding time is preferably at least 1 hour, 3 hours or more, or 5 hours or more depending on the conditions, and the holding temperature is preferably 20° C. or more. 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. Furthermore, to substantially reduce the COD of the photographic waste to zero means to reduce the COD to such an extent that it can be discharged into the sewer. By the way, COD based on discharge standards to general rivers is
120ppm, PH5.8~8.6, and according to the Sewerage Law
There is no regulation standard based on COD, but the iodine consumption equivalent to COD is 220ppm, PH5.7 to 8.7 (specific industries)
(Example of Tokyo). Next, the present invention will be explained in detail. In the present invention, a photographic waste liquid treatment kit containing a specific oxidizing agent and an alkaline agent is added to the processing of photographic waste liquid, and after keeping the photographic waste liquid under specific conditions, a PH neutralizing agent is added to react with the photographic waste liquid and the oxidizing agent. It is possible to control the reaction rate to perform a mild and complete reaction, and by adding a PH neutralizing agent, it is possible to perform an even more complete reaction. Furthermore, it is possible to neutralize the PH at the same time, so it can be used as is in the sewer system. The present invention is superior to the conventional technology in that it is a photographic waste liquid treatment method that allows for disposal to other sources and is extremely simple to operate. The peroxosulfates of the present invention include, for example, ammonium persulfate, sodium persulfate, potassium persulfate, sodium peroxo-sulfate, potassium peroxo-sulfate, potassium peroxo-sulfate.
Potassium sulfate salt (trade name: Oxone)
Supplied by Co., Ltd. ), and hydrogen peroxide releasing compounds include sodium percarbonate,
Potassium percarbonate, ammonium percarbonate, sodium perborate, potassium perborate, magnesium perborate, ammonium perborate, etc., and perhalogenates include potassium perchlorate, sodium perchlorate, potassium perbromate, Specific example compounds include strontium perchlorate, cesium perchlorate, sodium perbromate, potassium periodate, and sodium periodate. Examples of halides include potassium chlorite and sodium chlorite. , potassium bromite, sodium bromite,
Specific example compounds include potassium iodine, sodium iodine, etc., and examples of hypohalites include potassium hypochlorite, sodium hypochlorite, calcium hypochlorite, and hypobromite. Specific examples include potassium, sodium hypobromite, potassium hypoiodite, and sodium hypoiodite. These peroxosulfates, hydrogen peroxide, hydrogen peroxide releasing compounds, perhalates, halites and hypohalites according to the present invention may be used alone or in combination. Furthermore, in the photographic waste liquid treatment kit of the present invention, these may be used in solid or liquid form. These peroxosulfates, hydrogen peroxide, hydrogen peroxide releasing compounds, perhalogenates, halites and hypohalites according to the present invention are preferably used in an amount of 0.05 to 8 mol per photographic waste solution, More preferably, it is in the range of 0.1 to 5 mol. Specific examples of the alkaline agent according to the present invention include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium metaborate, borax, sodium phosphate, calcium hydroxide, magnesium hydroxide, etc. Illustrated as. The amount of the alkaline agent to be applied varies depending on the oxidizing agent, so it is appropriately determined depending on the oxidizing agent used. Further, the oxidizing agent and the alkaline agent may be mixed and used as a single part, or may be used as separate parts. The PH neutralizing agent according to the present invention refers to the PH neutralizing agent as described above.
It neutralizes the pH of the photographic waste liquid after it has been maintained at a temperature of at least 5 hours above .degree. C., and makes the pH substantially neutral (more specifically, PH5 to 9). Any agent may be used as long as it neutralizes the pH of the photographic waste liquid, but a particularly preferably used pH neutralizing agent is an inorganic pH neutralizing agent. More specifically, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, boric acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium metaborate, borax, sodium phosphate, calcium hydroxide, water Magnesium oxide and the like are particularly preferred PH neutralizing agents of the present invention. 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. 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], 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 represents a hydrogen atom, lower alkyl, −C ₂ H ₄ OH, −PO ₃ M ₂ ;
M represents a hydrogen atom or an alkali metal, n and m are 0
Or represents 1. Specific examples of the chelating agents represented by the general formulas [] to [] include the following.

【table】

【table】

[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. Color developing agents particularly suitable for the present invention include -( _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 nCmH ₂ m- ₁ groups, and specific examples 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, a surfactant is used in combination 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
Any method can be used to obtain 70 dyne/cm, and any method may be used. 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, 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 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 C ₂ H ₅

[Table] ｜ ｜
SO ₃ Na C ₂ H ₅

【table】

【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. The COD of the waste liquid from the above-mentioned processing solution varies depending on the formulation, but in practice it is 3000 to 50000 ppm for color developing solution, 40,000 to 100,000 ppm for fixer, 40,000 to 100,000 ppm for bleaching solution, and 1000 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/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 salts of organic or inorganic acids, 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
It may be in the range of 30g. Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-oxy-toluene, 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 sulfate, 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, sodium metaborate, sand, and the like. 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 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. Specific examples of aminopolycarboxylic acids included in bleaching solutions of pH 2.0 or higher containing those coordinated with metal ions such as iron, cobalt, copper, etc. 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. A fixing solution with a pH of 3.0 or higher containing an organic chelating agent such as, a stabilizer such as nitro alcohol or a nitrate, an organic solvent such as methanol, dimethylsulfamide, or dimethylsulfoxide, etc. is included. 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 buffer in the fixing agent, and the bleach-fixing solution containing a bleaching agent with a pH of 4.0 or higher. 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 FIG. 1) Furthermore, 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 process: Development → Fixation → Washing The waste solution from development is mixed with the photographic waste solution treatment kit of the present invention, the waste solution 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 is 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/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 12ml Diethylene 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-methanesulfonamide) ethyl)-aniline sulfate
5.0g 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 Water was added to make 1, and the pH was adjusted to _10.20 with KOH and _H2SO4 . <Color developer replenisher> Benzyl alcohol 17ml Diethylene 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 6.9g 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 was mixed with acetic acid and/or ammonia.
Adjust to PH6.7±0.1. <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 0.01g 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 MgSO ₄・7H ₂ O 0.2g Nitrilotriacetic acid 1.2g Sodium hydroxide 1.0g Add water to total amount was set to 1, and the pH was set to 7.0 with H ₂ SO ₄ . 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 2.5ml per ^100cm2 of color paper to the color developing 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 Figure 1, 10 m ² of color paper was continuously processed. Overflow liquids (photographic waste liquid) from the color developing tank 106, bleach-fixing tank 107, and stabilizing tank 110 accumulated in the waste liquid container 115 of the automatic processor. The photographic waste liquid treatment kit of the present invention (part sodium persulfate 450 g, part potassium carbonate 60 g, part exemplified surfactant 3.75 g) was added to this photographic waste liquid, and the holding temperature and time were changed as shown in Table 1. The pH was then adjusted to 7 using sodium hydroxide. The COD in the photographic waste liquid was measured at that time, and the generation of tar was observed. The following results are summarized in Table 1 below.

[Example 2]

In place of the sodium persulfate in the photographic waste liquid treatment kit used in Example 1, the same mole of potassium permanganate and potassium dichromate were used as a comparative example, and the same procedure as in Experiment No. 6 of Example 1 was carried out. I conducted an experiment. Furthermore, a similar experiment was conducted using the same moles of hydrogen peroxide (30% solution), sodium percarbonate, and sodium hypochlorite in place of persulfuric acid in Example 1, respectively. The above results are summarized in Table 2.

[Example 3]

Example 1 In Experiment No. 5, the photographic waste liquid treatment kit of the present invention was added to the photographic waste liquid, and then divided into six equal parts.
PH2 and PH using hydrochloric acid and sodium hydroxide
4. Adjusted to PH5, PH7, PH9, and PH10. At this time, the residual COD was measured and the generation of tar was observed. The results are shown in Table 3 below.

〔Effect of the invention〕

The present invention is particularly advantageous in solving the above-mentioned technical problem that occurs when an automatic processor is not equipped with a water supply pipe, a cooling water supply pipe, and a drain pipe. It is effective not only for automatic processors, but also for photographic processing using automatic processors where part of the 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 light-sensitive materials, as long as it is of the type to be processed 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, 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. A combination of at least one compound selected from peroxosulfates, hydrogen peroxide, hydrogen peroxide releasing substances, perhalates, halites, and hypohalites and a surfactant. A photographic waste treatment kit that includes: 2. The photographic waste liquid treatment kit according to claim 1, characterized in that it contains an alkaline agent. 3 A photographic waste liquid treatment kit is added to the photographic waste liquid, and after the photographic waste liquid is held for a certain period of time, a PH neutralizing agent is added thereto to control COD and PH.Claim 1 of the claims is characterized in that the product is prepared in a pre-adjusted manner. Or the photographic waste liquid treatment kit described in item 2. 4. The photographic waste liquid treatment kit according to claim 1, 2, or 3, wherein the photographic waste liquid is a photographic waste liquid from an automatic processor that does not use washing water. 5. The photographic waste liquid treatment kit according to claim 1, 2, 3, or 4, wherein the photographic waste liquid is a photographic waste liquid from an automatic developing machine that does not require a water supply or drainage pipe. 6 Photographic waste liquid treatment kit containing a combination of at least one compound selected from peroxosulfates, hydrogen peroxide, hydrogen peroxide releasing substances, perhalates, halites, and hypohalites and a surfactant. A regulated treatment method for COD and PH of photographic waste liquid, in which a pH neutralizing agent is added after holding for a certain period of time. 7. The COD and PH control method for photographic waste liquid treatment according to claim 6, characterized in that the photographic waste liquid treatment kit contains an alkaline agent. 8. The COD according to claim 6 or 7, characterized in that a photographic waste liquid treatment kit is added to the photographic waste liquid, and after holding for a certain period of time, a PH neutralizing agent is added.
and PH regulatory treatment methods. 9. The COD and PH control method for photographic waste liquid according to claim 8, wherein the holding time is at least 1 hour. 10. The COD and PH control method for photographic waste liquid according to claim 8, wherein the holding time is at least 3 hours. 11. The method for controlling COD and PH of photographic waste liquid according to claim 8, wherein the holding time is at least 5 hours. 12. Claims 6, 7, 8, 9, 10 or 10, characterized in that the temperature at which the photographic waste liquid treatment kit is added and maintained is 20°C or higher. COD of photographic waste liquid described in Section 11 and
Regulatory treatment methods for PH. 13. Claims 6, 7, 8, 9, and 1, characterized in that the photographic waste liquid is photographic waste liquid from an automatic processor that does not use washing water.
of the photographic waste liquid described in Section 0, Section 11 or Section 12;
Regulatory treatment methods for COD and PH. 14. Claims 6, 7, 8, 9, and 10, characterized in that the photographic waste liquid is photographic waste liquid from an automatic developing machine that does not require a water supply or drainage pipe.
A method for regulating COD and PH of photographic waste liquid as described in Section 1, Section 11, Section 12 or Section 13.