JPS61235834A - Photographic waste liquor treating kit - Google Patents

Abstract

PURPOSE:To reduce a COD of the photographic waste liquor by preconditioning and compounding an amount of hydrogen peroxide necessary to make the COD (the chemical oxygen demand) of the photographic waste liquor to zero. CONSTITUTION:A concentration of hydrogen peroxide in the waste liquor treating kit is a range of 50-250g/l. The neutralization agent of pH such as an alkaline and an acid agents may be contained in the kit so as to be pH of the treated waste liquor to 5-9. When the agent is added to the kit in the presence of a chelating agent having >=7 stability constant for an iron and/or a metal complex of the chelating agent, a generation of a sludge is depressed, thereby reducing the COD of the waste liquor with a good efficiency. Therefore, the COD of the photographic waste liquor makes substantial zero, thereby enabling to discard the waste liquor.

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, etc. in the case of color materials.
A combination of processes using a treatment liquid having one or more functions such as stabilization is carried out. In photographic processing in which a large amount of light-sensitive material is processed, the components consumed during processing are replenished, while the components that are dissolved into the processing solution or concentrated by evaporation (
For example, methods are used to maintain the performance of the processing solution at a constant level by removing bromide ions in the developing 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, systems have been changing to systems 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 from the tank 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 possible to dispose of washing water and cooling water into sewers or rivers, but other photographic processing solutions (e.g., developing solutions, It has become virtually impossible to dispose of fixing solutions, color developing solutions, bleach-fixing solutions, bleaching solutions, stabilizers, etc.). For this reason, each photo processing company pays a specialist 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, and is also extremely expensive.Furthermore, the initial investment (initial cost) for pollution treatment equipment is extremely high. It has disadvantages such as being large and requiring a fairly large space for installation. Furthermore, communally,
As a pollution treatment method for reducing the pollution load of photographic waste liquid, activated sludge method (for example, Japanese Patent Publication No. 51-12943 and Japanese Patent Publication No. 51-7952, etc.),
9347 and Japanese Patent Publication No. 56-339969, etc.), fi electrolytic oxidation method #Kaimei 48-844629. Japanese Patent Publication No. 49-11
No. 9458, Japanese Patent Publication No. 43478 (1983), Japanese Patent Publication No. 49 (1977)
No. 119457, etc. L-In Exchange Method C Special Publication No. 1987-37
No. 704, VF Publication No. 53-383, Special Publication No. 53-43
271, etc.), reverse osmosis method (JP-A-50-22463, etc.), chemical treatment method (JP-A-49-64257, JP-A-57-37396, JP-A-53-12152, JP-A-Sho 53-12152, etc.) 49-58833, JP-A-53-63783, JP-A-57-37395, etc.), but each has the following drawbacks. For example, the activated sludge method requires The electrolytic oxidation method is extremely large and requires a fairly large installation area, and the electrolytic oxidation method requires high equipment and electricity costs.The ion exchange method and reverse osmosis method cause significant fatigue of the resin and membrane when dealing with concentrated photographic waste liquid, and the In addition, chemical treatment methods have poor processing efficiency, and they always use far more chemicals than necessary, which can lead to pollution problems from the remaining surplus chemicals. have. 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, which 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 its pollution load is extremely light, and on the other hand, the waste liquid is It has the characteristic of being small in quantity. Therefore, due to the small amount of waste liquid, the piping outside the machine for supplying and draining liquid can be omitted, which eliminates the difficulty of moving after installation to install piping, which is considered a drawback of conventional automatic processors. All of the disadvantages such as the narrow leg space, the high cost of piping work during installation, and the high cost of energy for supplying hot water have been eliminated, and the machine has been made compact and simple enough to be used as an office machine. This offers a huge advantage. However, on the other hand, the waste liquid has an extremely high pollution load, and is not only disposed of in rivers but also in sewers, making it completely impossible to dispose of it due to pollution regulations.
Furthermore, although the amount of waste liquid in such photographic processing (processing that does not substantially involve water washing) is small, even in relatively modest processing, for example, in the processing of X-ray photosensitive materials, ions,
The processing of photosensitive materials for printing plates requires 30 Q per day, and the processing of color photosensitive materials requires approximately 50 Q per day, and the treatment of waste liquid has become a rather big problem in recent years. As a means to deal 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.-63763, JP-A-49-64257
No., Special Publication No. 57-37396 and Japanese Patent Publication No. 1982-121
It is disclosed in No. 52, etc. However, these prior art methods have poor reaction efficiency, so it is necessary to add considerably excessive amounts of persulfate and hydrogen peroxide, and in order to add persulfate and hydrogen peroxide that match the pollution load value of the waste liquid, COD and BO
The measurement operation of D was required and 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 a sewer system or the like by substantially reducing the COD (chemical oxygen demand) to zero. is extremely cost-effective,
Another object of the present invention is to provide a photographic waste liquid treatment kit that does not require post-treatment of chemicals (for example, hydrogen peroxide) for removing excess COD. Furthermore, another object of the present invention is to provide a photographic waste liquid treatment kit that does not require measurement of pollution load values such as COD and BOD. Still another object of the present invention is to provide a photographic waste liquid treatment kit for photographic waste liquid from an automatic processor that does not substantially use rinsing water. −

[Structure of the invention]

The above object of the present invention is characterized in that the amount of hydrogen peroxide 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 is adjusted and blended in advance. This is achieved by a photographic waste liquid treatment kit. 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 photographic waste to substantially zero" means reducing the COD of the photographic waste to a concentration that allows it to be disposed of into rivers or sewers6. COD is 12 pp theory, and although there is no regulation standard based on COD under the Sewage Law, the iodine consumption equivalent to COD is 220 pp theory (for example in Tokyo). Next, the present invention will be explained in detail. According to the present invention, for a unit amount of specific photographic waste liquid, substantially C.
It is economically extremely advantageous because it requires only the minimum amount of hydrogen peroxide because it uses a photographic waste liquid treatment kit that contains hydrogen peroxide pre-mixed so that the OD is zero, and there is almost no surplus hydrogen peroxide. This method is clearly superior to the prior art in that it is an extremely simple photographic waste liquid treatment method that does not require post-processing for this purpose and also does not require COD or BOD measurement operations. The hydrogen peroxide used in the present invention may be used as a concentrated solution of 30% to 35%, or may be diluted to several %. The concentration of hydrogen peroxide in the kit of the present invention is 5g/11~
350g/Q is preferable, particularly preferably 50g/Q~
It is in the range of 250g/Q. Further, the photographic waste liquid treatment kit of the present invention may contain a pH neutralizing agent such as an alkaline agent or an acid so that the pH after the waste liquid treatment is 5 to 9. Furthermore, when the photographic waste liquid is mixed with the photographic waste liquid treatment kit of the present invention in the presence of a chelating agent with a stability constant for iron of 7 or more and/or a metal complex salt of the chelating agent, the generation of sludge is suppressed, Furthermore, it is more preferably used because it has the surprising effect of reducing COD more efficiently. The chelating agent has the following general formulas (I) and (II).
Compounds represented by are particularly preferably used. General formula (1) A-COOM General formula ([) B-PO,M2 In the formula, and B each represent a monovalent group or atom, and may be a Flu 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 (II), particularly preferred chelating agents for the present invention are compounds represented by any of the following general formulas (III) to (Vl). General formula (III) A, -R, -Z-R2-CO
OM general formula [■] In the formula, E is a substituted or unsubstituted fullkylene group, cycloalkylene group, phenylene group -RtORt-1R70Rt
OR7-1Rt Z Represents R7-, Z is >N-R
Fu A6. >NA, R1-R2 represents a substituted or unsubstituted fullkylene group, Al to A6 are hydrogen,
-OH, -COOM, -PO3M2; 11; M represents hydrogen or an alkali metal atom; Also, at least one of A2 to A is -COOM or -P O, M 2
It is. General formula (V) RsN (CH2P O3M 2)
In formula 2, R8 is a lower alkyl group, an aryl group, an aralkyl group, a nitrogen-containing hexacyclic group [-OH, -OR as a substituent]
, -COOM), and M represents a hydrogen atom or an alkali metal atom.・(G) General formula [■] In the formula, R9 to R are hydrogen atoms, -OH, lower alkyl (
-OH, unsubstituted or as a substituent. COOM = P OsM 2), 81~B,
is a hydrogen atom, OHg COOM @ P 03
M 2 *N j 2 is represented, and J is a hydrogen atom or lower alkyl. C2H40H--P Os M 2 is represented, M represents a hydrogen atom or an alkali metal, and 1sle represents 0 or 1. Specific examples of the chelating agents represented by the general formulas (1) to [■] include the following. [Exemplary chelating agent] (10) (HOC2H4)28CH2COOHC
H2COONa 03H2 HO-C-CH3 OOH CI(2COOH HOOC-C-PO3H2 NH2 ■ 0H2COOH CH3 ■ H20,P-C-PO3H□ ? 03H2 , rl-rnnll H H2O5P-CPO3H2 CH3 The above chelate agent and/or the chelating agent. The metal salt is preferably used in a range of 90.2 to 200 g/Q per photographic waste liquid IQ, more preferably in a range of 0.4 to 140 g/Q. Furthermore, from the viewpoint of ease of handling, the photographic waste liquid treatment kit is preferably one-part, but may be two-part or more 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. Particularly, as the developing agent, a para-phenylenediamine type developing agent having at least one water-soluble group (hydrophilic group) on the amino group 7 is preferable. 1) C2H,C,H
4NHSO2CH3NH2 (3) C,H5(:,H,OH NH2 (4) C2H5C2H,OCH3 (5) Ca11. C,H,SO,HNH. (6) CH3C2H,OH NH. N". Nll. Nl2 (10) HCH2C0OH Nl2 (13) C2H3(CH,C)120), C,H5
A particularly effective color developing agent for the present invention is -(CHz)n-CHtOH-(CH2)II as a substituent on the ami7 group.
l-NHSO2-(CH2)n-C11p-(C1lz
)m-0-(CH2)n-C1ls. ”(CH2CH20)nCmH2a+-+, and specific examples include (
1), (2L(3), (4)t(6), and (7)).However, the height and n are integers of 0 or more, preferably θ to 5.In the present invention, photographic waste liquid When a thiosulfate is contained in the thiosulfate, generation of tar is suppressed during mixing, which is a more preferred embodiment of the present invention.As the thiosulfate, for example, ammonium thiosulfate,
Examples include sodium thiosulfate, potassium thiosulfate, triethanolammonium thiosulfate, and the like. In addition, the photographic waste liquid of the present invention contains 5 g of benzyl alcohol/
When containing Q or less, it suppresses tar generation and COD
It can be preferably used in the present invention because it is good in terms of reducing the . In particular, it is particularly preferably used when the amount is 1 g/Q or less. The surface tension of the photographic waste liquid of the present invention is 20 to 70 dyne/
In the present invention, a surfactant is preferably used because the COD decreases at a particularly fast rate when it is 1 cm. The surface tension is described in "Analysis and Testing Methods for Surfactants" (Fumio Kitahara, Shigeo Hayano, co-authors Harabe, published March 1, 1982, published by II Dansha Co., Ltd.). It is measured by a certain common measuring method, and in the present invention, it is a surface tension value measured by a common measuring method at 20°C. In the present invention, the surface tension of photographic waste liquid is 20 to 70 d.
Any method can be used to make yne/am, and any method may be used, but surfactants are preferably used. The surface tension of these processing solutions with bleaching ability is 20 to 70.
The surfactant for dyne/am may be added in advance to the photographic waste liquid, added to the photographic waste liquid treatment kit, or 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 (X) are preferably used from the viewpoint of the effects of the present invention. General formula [■] R2゜-CH-C0A2゜R22 R2, -CH-C00R2s In the formula, one of R2゜ and R21 is a hydrogen atom, and the other is a formula -8O,M (M is a hydrogen atom or a -valent positive *A2o represents an oxygen atom or a group represented by the formula -NR24- (R24 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). R22 and R2 each represent a furkyl group having 4 to 16 carbon atoms. However, the alkyl group represented by R2, R, or R24 may be composed of 7 atoms. General formula [■] Az+-0(B)mX. In the formula, A2. is a -valent organic group, e.g. having 6 to 20 carbon atoms.
, preferably an alkyl group having 6 to 12 carbon atoms (for example, each group such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl), or an aryl group configured with an alkyl group having 3 to 20 carbon atoms, The substituent is preferably an alkyl group having 3 to 12 carbon atoms (for example, propyl, butylpentyl, hexyl, heptyl, octyl,
Examples of the aryl group include phenyl, tolyl, xynyl, biphenyl, and 7-tyl groups, 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 para positions. B represents ethylene oxide or propylene oxide, B represents an integer from 4 to 50, Xl is a hydrogen atom, 5
O3Y also represents 1*PO, Y2e, and Y li represents a hydrogen atom, an alkali metal atom (such as Na, K or Li), or an ammonium ion. In the general formula CI, R2S, R2? and (/R2g represents a hydrogen atom, an alkyl group, and a phenyl group, respectively, but R25%R
2 R2? and the total number of carbon atoms in R20 is 3 to 50. X2 represents a 7-ion 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-)luenesulfonic acid group. General formula (X) In the formula, R21, R1°, R31 and R32 each represent two water atoms or an alkyl group, and M has the same meaning as in general formula [■]. n and p each represent 0 or an integer of 1 to 4, and are values satisfying 1≦n+p≦8. Specific examples of compounds represented by the general formulas [■] to (X) are listed below, but the invention is not limited thereto. (Compound represented by general formula [■]) CHCOOCH,C1(C,H. (iii) (iv) CHzCONHCsH+ t (V) SO,Na CHCONHC,.H21 (vi) (vii) So,Na (vi ) CH2COOC8Fl C1hCOOC,5lLt SO,JN!L (ix) 2H5 CH2C00CaH+□CHCH. (X) C1hCOOCH2(CF2CF2)zt1CHCOO
CH2(CF2CF2)J (xi) CH2COOC8Fl t CHCOOCsF l 7 038a (xi) (Compound represented by general formula [■]) (i) Cl2H2SO(C21140)IoH(
vi) Cs111J(CJsO)+J(iii
) C, II, 5O(C2H,0), SO, Na
(!v) C1oHz, 0(CzH-0)+sP
OJa2(v) (vi) (vii) (ix) (X) (Xi) (xi) (Compound represented by general formula [■]) (i) (ii) (iii) (iv) (V) ■ ICI. (vi) CH. (vii) (vii) CI. C++FIzs-cOOCH2CH2NHCOOH2-
N<H:+CQOI CI. (ix) (x) (Compound represented by general formula CXj) (i) (ii) (iii) (iv) (V) SO,Na (vi) (vii) (vii) (i,) In the present invention The actual processing solution discharge amount ratio discharged from the related automatic processor is [color developing solution discharge amount]: [bleach-fixing solution discharge amount (or bleach-fixing solution discharge amount (or bleach-fixing solution discharge amount)): (stabilizing solution discharge amount ( or 1st stable liquid discharge amount 10 2nd stable liquid discharge amount)
)=(0゜1~2.4):(0゜1~1゜6〕:[1]
When this is the case, it 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 solution of the processing solution varies depending on the formulation, but in practical terms it is 3000 to 50000 pp+s for color developing solution, 40,000 to 100,000 ppm for fixer, 40,000 to 100,000 ppm for bleaching solution,
The stabilizer is 1,000 to 10,000 pp-. When the total amount of photographic waste liquid discharged from the automatic processing machine according to the present invention is 5011 or less per day, the waste liquid treatment kit of the present invention acts more effectively on the objective effects of the present invention. In the present invention, it is preferably used, and furthermore, it is particularly preferably used when the amount of water is 30 or less per day. When the photographic waste liquid of the present invention has silver of 2 g/Q or less, sludge generation is very good, so it is preferably used in the present invention, and it is particularly preferably used when the silver content is 0.5 g/Q or less. It will be done. The photographic waste liquid specified in the present invention includes a single photographic processing liquid waste liquid obtained when a known silver halide photographic light-sensitive material is processed with a known photographic processing liquid, and a mixture of any two or more types of waste liquid. The photographic processing solution includes the following. Color developer: A color developer with a pH of 7 or more containing a developing agent, an alkaline agent, a preservative, and other additives as shown below. Color developing agents include aromatic primary amine color developing agents, and the herbal medicines include aminophenol derivatives and 9-phenylenediamine derivatives. These may be salts of organic acids or inorganic acids, such as hydrochlorides, sulfates, 9-)luenesulfonates, sulfites, oxalates, benzenesulfonates, etc. Concentrations may range from 0.1 to 30g. The aminophenol developer mentioned above is, for example, 0-7
Minophenol, p-7minor7-el, 5-7minor-2-oquine-toluene, 2-7minor-3-oxy-toluene, 2-oxy-3-ami/-1,4-dimethyl-benzene, etc. is included. Further, as the I)-phenylenediamine derivative, N is used. N'-1furkyl-1)-phenylenecyamine compounds such as N,N'-tumethyl-11-7 22-diamine hydrochloride, N-methyl-13-phenylenediamine hydrochloride, N,N'-dimethyl-11 -7 enylenzoamine hydrochloride, 2-7 mino-5-(N-ethyl-N-t'tecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-7 minoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino/-3-methyl-N, N-noethylaniline, 4-7minor N-(2-nodoxyethyl)
-N-ethyl-3-methylaniline-p-)luenesulfonate and the like are included. 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 trimethyl sulfoxide, etc., and antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose or hexose, pyrogaroll- Examples include 1,3-dimethyl ether. Activator wX: an aqueous solution of the alkaline agent mentioned in the color developing solution. Bleaching solution: As a bleaching agent, use a metal complex salt of an organic acid such as polycarboxylic acid, aminopolycarboxylic acid (which may be an alkali metal salt, ammonium salt or water-soluble amine salt), or an organic acid such as oxalic acid or citric acid. Specific examples of amide/polycarboxylic acids that can be used in bleaching solutions having a pH of 2.0 or higher and containing coordinated metal ions such as iron, cobalt, copper, etc. are listed below. [1] Ethylenediaminetetraacetic acid [2] Ethylenetri7minebentaacetic acid (3) Ethylenediamine-N-(β-oxyethyl)-N, N', N
'-Triacetic acid [4] Propylenenoaminetitraacetic acid [5] Nitrirotriacetic acid [6] Cyclohexanecyaminetetraacetic acid [7] Imi7
Noacetic acid [8] dihydroxyethylglycincitric acid (or tartaric acid)

[9] Ethyl ether cyamine 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 tetraacetic acid Tetra(tri/tylammonium) acetate salt [15] Ethylenenoaminetitraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt (17) Ethylenediamine-N-(β-oxyethyl)
-N, N', N'-) Liloacetic acid sodium salt [18] Propylenediamine tetraacetic acid sodium salt (19) Di) Lyloacetic acid sodium salt [20] Cyclohexanediamine tetraacetic acid sodium salt Q, more preferably 2
Use at 0 to 250g/11. As mentioned above for the bleach solution! In addition to bleach, if necessary, a solution containing sulfite as a preservative may be used to give the product a golden color. or,
A bleaching solution containing an ethylenediaminetetraacetate iron(l[I) complex salt bleaching agent and a large amount of a halide such as ammonium bromide may be used. In addition to ammonium bromide, the halides include hydrochloric acid,
Hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be contained. The bleaching solution is disclosed in Japanese Patent Application Publication No. 46-280 and Japanese Patent Publication No. 45-8506.
Various bleaching methods described in Japanese Patent Publication No. 46-556, Belgian Patent No. 770,910, Japanese Patent Publication No. 45-8838, Japanese Patent Publication No. 53-9854, Japanese Patent Application Publication No. 71634-1987 and Japanese Patent Publication No. 49-42349, etc. A promoter may be added. Fixer: A compound that reacts with silver halide to form a water-soluble complex salt, such as potassium periosulfate, sodium periosulfate, etc., which is used as a fixer in normal fixing processing.
Included are those containing thiosulfate such as ammonium thiosulfate, thiocyanhydrochloric acid such as potassium thiocyanate, sodium thiocyanate, and monoium thiocyanate, thiourea, thioether, etc. in an amount of 5 g/stand or more within the range that can be dissolved. In addition, boric acid, borax, sodium hydroxide,
Potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, acetic acid) 17
Those containing various pH41 sanitizing agents such as ammonium, ammonium hydroxide, etc. alone or in combination of two or more, and those containing various fluorescent brighteners, antifoaming agents, or surfactants, and hydroxylamine, Hydrazine, preservatives for bisulfite adducts of aldehyde compounds, organic chelating agents such as amide/polycarboxylic acids, or stabilizers such as nitroalcohols and nitrates, methanol, dimethyl sulfo-7
Included are fixing solutions having a pH of 3.0 or higher and containing organic solvents such as chloride, dimethyl sulfoxide, and the like. Bleach-fix solution: Used as a bleaching agent in the above bleach solution! Included are bleach-fix solutions containing a metal complex salt of an acid at a concentration ranging from about 0.1 to about 300 g/Q, as a fixing agent up to a saturating amount of the fixing agent in the fixing solution, and further as a preservative. containing sulfite, p in the fixing agent
Those containing a H buffering agent, and those containing a bleaching agent in the above bleaching agent. Bleach-fix solutions of H4.0 or higher are included. In addition, a bleach-fix solution consisting of an ethylenediaminetetraacetate iron (1) complex salt bleach and a small amount of a halide such as ammonium bromide other than the above-mentioned silver halide fixing agent, or conversely, an ammonium bromide-like light halide may be used. In addition, there are also special bleach-fix solutions containing a combination of ethylenetuaminetetraacetate iron (1) complex salt bleach and a large amount of a halide such as ammonium bromide. included. The halides include, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like. Stabilizing liquid: ammonium compounds such as ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate,
Ammonium phosphite, ammonium heptadide, acidic ammonium heptatide, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium heptahydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate , ammonium acetate, ammonium 7cipate,
Ammonium lauric tricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium hydrogen heptalate, ammonium hydrogen tartrate, ammonium thiosulfate, ammonium sulfite , ammonium ethylenediaminetetraacetate, ferric ammonium ethylenediaminetetraacetate, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, ammonium heptalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate , ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,4,6. -) linitrophenol ammonium, etc. 0.001-1
．． 0 mol/Q chelating agents such as organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds, etc. Specifically, ethylenediamine diorthohydroxyphenylacetic acid diaminopropane tetraacetic acid, nitrilotriacetic acid, hydroxy Ethylethylenedi7minetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminenipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenecyaminetetraacetic acid , 1.1'-diphosphonoethane-2-carboxylic acid, 2
-phosphonobutane-1゜2.4-tricarboxylic acid, 1-
Hydroxy-1-phospho/propane-1,2,3-tricarboxylic acid. Catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, etc., were added at 0.01 to 50 g per stabilizer IQ, and organic acid salts (citric acid, acetic acid, fuhaku 醇 S7+6
(Zenzihe Puke Guo). Fukisoujuri / Ninth floor salts, borates, hydrochloric acid, sulfuric acid, etc.) Antifungal agents (phenol derivatives, catechol derivatives, imiguzol field conductors, triazole derivatives, thiabenguzol derivatives, organic halogen compounds, other paper-bulps) Antifungal agents known as industrial slime control agents), optical brighteners, surfactants, etc.
Preservative, B i9MgvZ ntN +, A Q 5S
Stabilizing solutions containing effective amounts of metal salts such as ntT LZ r are included. Black and white developer *4,47-dimethyl-1-phenyl-3-
Pyrazolidone, 4-methyl-4'-hydroxymethyl-
1-phenyl-3-pyrazolidone, 1-phenyl-3-
developing agents such as pyrazolidones, methol and hydroquinone, preservatives such as sulfites, sodium hydroxide,
Accelerators consisting of alkalis such as sodium carbonate and potassium carbonate, potassium bromide and 2-methylbenraimigsol,
H05/N containing inorganic or organic inhibitors such as methylbenzthiazole, water softeners such as bo-17+7 phosphate, surface overdevelopment inhibitors consisting of trace amounts of iodides and mercapto compounds, etc. Included are black and white developers commonly used for silver-oxide photosensitive materials. Among these waste liquids, those containing silver may be removed by a known silver recovery method such as a metal substitution method using steel wool or an electrolytic method, and then the waste liquid treatment kit of the present invention may be used. Alternatively, the treatment may be performed using the treatment kit of the present invention while containing silver. A method of mixing the photographic waste liquid treatment kit of the present invention with a unit amount of a specific photographic waste liquid is to mix it in small batches many times depending on the over 70-it (waste liquid amount).
), a method in which a relatively large amount of photographic waste liquid is stored and then mixed at once (II), 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. (I[[) etc., but in the present invention, the above method: A(III) is most preferably used. Specifically, the photographic waste liquid treatment kit of the present invention is added in advance to the waste liquid container at the bottom of the automatic processor, and the over 7
(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. In the present invention, it is more preferable to perform the following because the reaction time is shorter.The reaction efficiency is higher when the reaction is performed, so in the present invention,
More preferred. 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 bleaching and stabilization waste solutions are combined and mixed with the color development waste solution treatment kit of the present invention, and the fixing waste solution 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 → fixing → washing with water The waste liquid from development is mixed with the photographic waste liquid treatment kit of the present invention, the waste liquid from fixing is collected in a separate container, and after silver recovery, the waste liquid from the development is processed by another photographic waste liquid treatment according to the present invention. Mix with the kit. Next, an example of an apparatus for implementing 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 magzine 103 containing a roll of film or color paper that has been photographed and wound up, and is provided on the side wall of the main body 104 of the automatic processor. The color negative film or color paper 102 attached to the mounting part 101 is attached to the main body entrance part 1.
It enters the main body 104 from 05, passes through a color development tank 106, a bleach-fix tank 107, and a stabilization tank 110, is automatically developed, is dried in a drying section 111 (with a lid that can be opened and closed), and is dried at the main body exit 112. After being taken out, it goes through cutting and other processes to become a product. 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 P for adjusting the temperature of the processing liquid, 8! It is a storage room. Reference numerals 114A, 114B, and 114C are drain pipes for guiding the photographic waste liquid from each of the processing tanks 106 to 110 to a container (waste liquid container) 115 that receives the photographic waste liquid.

【Example】

Next, the present invention will be explained in detail based on examples, but 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 to produce three types of couplers: yellow, magenta, and cyan. A photographic emulsion was prepared using each of the following methods according to a conventional method. 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 the composition of the treatment liquid in the case of .; are as follows. Standard processing step [1] Development -38℃ 3 minutes 30 seconds [2]
Bleach fixing 33℃ 1 minute 30 seconds [3] Stabilization treatment 25℃~30℃ 3 minutes [4] Drying
75°C to 80°C for about 2 minutes Processing liquid composition Color developing tank liquid> Benzyl alcohol 15. Ethylene glycol 15d Potassium chlorite 2.0g Potassium bromide
1.3g potassium chloride
0.2g potassium carbonate
30,0g3-methyl-4-amino-ethyl-N-
(β-notanesulfonamidoethyl)-aniline sulfate 5.5 g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0° hydroxylamine sulfate 3.0 g 1-hydroxyethylidene-1,1 -Diphosphonic acid 0.4g Hydroxyethyliminonoacetic acid 2.5g Maglucium chloride hexahydrate 0.7g 1.2-dihydroxybenzene-3,5-nosulfonic acid disodium salt 0.2g Add water to make IQ, K
The pH was adjusted to 10.20 with Oll and H2SO. <Color development replenisher> Benzyl alcohol 20WIQ Ethylene glycol 20Wl (l Potassium sulfite 3.0 amount a Potassium carbonate
30. O,ll Hydroxylamine sulfate 4.0-3-methyl-4-ami/-
N-ethyl-N-(β-notanesulfonamidoethyl)
-Aniline sulfate 7
．． 5g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.5g1
-Hydroxyethylidene-1,1-diphosphonic acid
0.
5g hydroxyethylimino vinegar ill 3,
0g chloride magnezi, rum hexahydrate salt 0.8g
1.2-Dihydroxybenzene-3,5-disulfonic acid disodium salt 0.3g Water was added to make IQ, and the pH was adjusted to 10.70 with KOH. Bleach-fix tank solution> Ethylenediaminetetraacetic acid ferric ammonium dihydrate eog ethylenediaminetetraacetic acid 3゜ammonium thiosulfate (7
0% solution) 1ooTnH ammonium sulfite (
40% solution) Adjust the pH to 7.1 with 27.5tQ potassium carbonate or glacial acetic acid and add water to bring the total volume to I
I named it Q. Bleach-fix replenisher A> Ethylenediaminetetraacetate ferric ammonium dihydrate 260FI potassium carbonate 42° Add water to make ill. The pH of this solution is 6.7±0.1. <Bleach-fix replenisher B> Ammonium 1000 sulfate (70% dissolved) 500.
Q Ammonium sulfite (40% dissolved) 250
d Ethylenediaminetetraacetic acid 17g Glacial acetic acid 85ml Add water to make the total volume IQ. The pH of this dissolution is 5.3±0.1. Stabilizing solution and stable replenishing solution> 5-chloro-2-methyl-4-isothiazolin-3-one 0.02g orthophenylphenol sodium salt 0.1g 2-methyl-4
-Isothiazolin-3-one 0.02g 2-octyl-4-isothiazolin-3-one 0.01
g Polyethylene glycol (molecular weight 1540) 1,0
g1-hydroxyethylidene-1,1-nophosphonic acid (
60% aqueous solution) 1.5g ammonium sulfite (40% aqueous solution) 2゜0gMg5○
,・7HpOO,2g ZnS O4,0,2g Ammonia water (25% aqueous solution) 2.5g
Nitrilotriacetic acid 1.2 g Sodium hydroxide 1.0 g Water was added to bring the total amount to a single level, and the pH was adjusted to 7.0 with 112 sO. Fill an automatic developing machine with the above color developing tank liquid, bleach-fixing tank liquid and stabilizing liquid, and add the above color developing replenishing liquid, bleach-fixing replenishing liquid A and B to the stabilizer every 3 minutes while processing the color vapor. A running test was conducted while replenishing a predetermined amount of replenisher. The amount of replenishment is 2゜TIIQ per 100 cm' of color paper to the color developing tank, and 0 to each of bleach-fixing replenishers A and B as the amount to be refilled to the bleach-fixing tank.
, 5d, add 2.8ml of stabilizing solution to the stabilizing tank.
Replenished. Note that the stabilizing tanks of the automatic developing machine are the first tank to the second WI in the direction of the flow of the photosensitive material, replenishment is performed from the final tank, and over 70- is allowed to flow from the final tank into the previous stage tank. It overflowed from the front tank. Using an automatic developing machine as shown in Figure 1, color paper 1
01112 was continuously processed. The waste solution container (115) of the automatic processor contains the photographic waste solution treatment killer of the present invention (300 mQ of 20% hydrogen peroxide). After continuous treatment, COD and residual sodium persulfate in the waste liquid container were measured. A similar experiment was conducted without adding the waste liquid treatment kit. At the same time, the generation of tar was observed. The above results are summarized in Table 1 below. Table 1 Also, by the method shown in Japanese Patent Application Laid-Open No. 53-63763,
When photographic waste liquid that had not been used in the photographic waste liquid kit was treated, the COD was reduced to only about 60 ppm, and furthermore, tar generation was severe. However, as shown in the above table, when using the waste liquid treatment kit of the present invention, the COD reduction is extremely good, and the residual hydrogen peroxide is also minimal (no post-treatment is required for this purpose, and It can be seen that the generation of tar is extremely low. [Example 2] The coloring agent (3-methyl-4-amino-N-ethyl-(β-methanesulfonamidoethyl)) in the color developer used in Example 1 -aniline sulfate), 3-methyl-4-
A similar experiment was conducted using 7minor N,N-diethylami7aniline hydrochloride instead. As a result, COD reduction and tar generation were almost the same, but when the photographic waste liquid and the photographic waste liquid treatment kit were mixed, a rather rapid reaction was observed and heat was generated. [Example 3] The discharge amount ratio of the processing solution in Example 1 was as follows: [Color developer discharge amount (hereinafter abbreviated as CD)]: [Bleach-fix discharge amount (hereinafter abbreviated as BF)]: [Stable Liquid discharge amount (hereinafter abbreviated as SS) = 0.71:0.38
:1, but the value of CD and/or BF is 0.
An experiment similar to that in Example 1 was conducted so that the value was 1 or less. Furthermore, a similar experiment was conducted with the CD value set to 2.4 or higher and the BF value set to 1°6 or higher. As a result, (C
D):(BFI:(SS)=(0,1~2.4):(0
, 1 to 1.6): Outside the range of (1), sludge and tar were likely to be generated. [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 or non-automatic processors in which a portion of the photographic waste liquid cannot be disposed of in sewers, etc.
The photographic material is not limited to silver halide photographic materials as long as it is of the type that is processed with a processing liquid and the waste liquid of the processing liquid has a COD load.

[Brief explanation of drawings]

#IJ1 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 filter A111...Drying part or color paper 103...Magazine 112...Main body outlet 104...Automatic developer material body 113 ... Control system equipment room 105 ... Main body entrance section 114^, 114
B and 114C... Drain pipe 106... Color developing tank
115...Waste liquid container 10F...Bleach-fix tank Applicant: Konishiroku Photo Industry Co., Ltd. Procedural amendment May 22, 1985 1゜Indication of the incident 1985 Patent application No. 77836 2゜Name of the invention Photographic waste liquid treatment kit 3, relationship with the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo 1-5 Sakura-cho, Hino-shi, Tokyo 191 Object of amendment ``Details of the invention "Explanation" Column 6, Contents of Amendment (1) Page 55, Line 1 of the Specification: [The pH of this solution is 6°7±0°1. "Adjust this solution to pH 6.7±0.1 using acetic acid and/or ammonia."
Correct. (2) “(70% dissolved)” on page 55, line 3 of the specification is replaced with “
(70% solution)”. (3) Change “(40% dissolution)” to “(40% dissolution)” on page 55, line 4 of the specification.
(40% solution)”. (4) Page 55, line 8 of the specification: “The pH of this dissolution is 5.
It is 3±0.1. ” [This solution is adjusted to pH 5.3 ± 0.1 using acetic acid and/or ammonia. ”
Correct.

Claims (3)

[Claims] (1) A photographic waste liquid characterized in that the amount of hydrogen peroxide required to make the COD (chemical oxygen demand) of the photographic waste liquid substantially zero per unit amount of the photographic waste liquid is prepared by adjusting in advance. processing kit. (2) Claim 1, characterized in that the photographic waste liquid is photographic waste liquid from an automatic developing machine that does not use washing water.
Photographic waste liquid treatment kit described in section. (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.