JPS6114508B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention uses a photographic developer as a styrene-divinylbenzene copolymer (hereinafter abbreviated as styrene-DVB copolymer) resin or (and) a monohydric or polyhydric alcohol methacrylic acid monoester-polyhydric alcohol methacrylic acid polyester copolymer. It relates to a method of selectively separating a developing agent in the liquid by bringing it into contact with a copolymer (hereinafter abbreviated as methacrylate copolymer) resin, and then purifying the liquid. When forming images using silver halide photographic materials, various processing solutions such as developer, stop solution, fixer, bleach solution, bleach-fix solution, hardening solution, neutralization solution, alkaline pre-bath solution, and stabilizing solution are used. is used. A photographic developer contains various compounds including a developing agent, but it is sometimes necessary to dissolve some or all of these compounds and then remove or separate specific compounds from the solution. It happens often. For example, liquid that is no longer needed after the development process, liquid that is partially or completely unnecessary after it has been mixed, or so-called waste liquid such as the liquid that overflows from the developer tank when being refilled during the development process. In this method, the developing agent is removed and separated and recovered. Photographic processing solutions generally have biochemical oxygen demand (hereinafter referred to as BOD) and chemical oxygen demand (hereinafter referred to as COD).
It is abbreviated as ) contains many organic compounds,
Directly discharging unnecessary liquid into sewage or rivers has a strong possibility of causing environmental pollution. Therefore, when disposing of photographic processing liquid,
It is necessary to remove pollutants from the environment, render them harmless, recover any remaining active ingredients, or take a combination of these measures before disposal. The developing agents and benzyl alcohol color development accelerators in photographic developers have large BOD and COD values. Therefore, if these substances are removed from the treatment liquid, waste liquid treatment becomes easier. In particular, developing agents and the like are expensive, and it is not preferable to simply disassemble and process them, and it is preferable from an economical point of view to recover them by some method and reuse them. Conventionally, various methods have been proposed for separating specific compounds from photographic processing solutions. For example, as described in Japanese Patent Publication No. 48-33698, a method in which a salt such as sodium sulfate is added to a developer to perform salting out to recover the developing agent, etc., and US Pat.
Examples include an extraction method using an organic solvent as described in US Pat. No. 3,253,920, and a method of recovering the dissociated developing agent using an ion exchange resin as described in US Pat. No. 3,253,920. A method of separating and removing these specific compounds by bringing activated carbon into contact with a photographic processing solution has also been considered. However, none of these methods is considered to be economically satisfactory. The salting-out method requires a large amount of salt, which imposes a large economic burden, and in order to precipitate all poorly soluble compounds without distinction, the process of refining the developing agent, etc. separated from the salt solution into individual compounds is complicated. Have difficulty. Also before adding salt
PH adjustment is also difficult to operate and is extremely difficult to carry out at a commercial laboratory. Furthermore, in the case of organic solvent extraction, a large amount of solvent is used, which not only makes the cost of the solvent expensive, but also requires sufficient consideration in terms of disaster prevention and health and safety, resulting in high equipment costs. Furthermore, since the organic solvent for extraction dissolves into the processing solution, it is difficult to reduce the BOD.COD in the processing solution to a certain value or less. A method using an ion exchange resin has extremely poor recovery efficiency if the compound to be recovered is not dissociated. Therefore, recovery of developed main images such as paraphenylene diamines and 3-pyrazolidones is substantially difficult. Although the adsorption removal method using activated carbon has excellent operability and ability to separate organic substances from aqueous solutions, it adsorbs most organic substances and the adsorption is strong. Therefore, elution and purification of adsorbed substances are complicated and recovery costs are high. Furthermore, once used activated carbon is difficult to regenerate, which increases the cost of activated carbon. Furthermore, it is difficult to dispose of activated carbon once it has been used, and since activated carbon has relatively weak physical strength, it becomes fine during use and scatters as powder or flows into the liquid. It was difficult to handle. Accordingly, a first object of the present invention is to provide a novel, relatively simple and easy-to-operate method for selectively separating relatively expensive developing agents from photographic developer waste solutions. A second object of the present invention is to provide a method for recovering a developing agent from a photographic developer waste solution, purifying it, and then reusing it in the same way as a newly synthesized product. A third object of the present invention is to provide a new method for removing developing agents from photographic developer waste and preventing contamination of sewage or rivers with BOD, COD, and the like. As a result of various studies, the present inventors have discovered that the first and third objects described above can be achieved by bringing photographic development waste into contact with a styrene-DVB copolymer resin or (and) a methacrylate copolymer resin. I found it. Styrene used in the present invention -
DVB copolymer resin or (and) methacrylate copolymer resin is much easier to elute adsorbed substances than activated carbon, and once used, styrene-DVB copolymer resin or (and) methacrylate copolymer resin It is extremely advantageous economically as it can be used repeatedly without deterioration of performance by contacting it with an appropriate solvent.
It is also easy to handle and operate. Styrene-DVB copolymer resin or (and) that can be used in the present invention
Methacrylate copolymer resin is characterized by being porous, and such porous copolymers have a pore volume of about 0.1 to 3 ml/g and a specific surface area of about 1.
A range of 2000 m ² /g is preferred. Porous styrene-DVB that can be used in the present invention
The copolymer resin and/or methacrylate copolymer resin may be manufactured by any method. In general, porous copolymers can be synthesized in a system in which a diluent that does not participate in polymerization is present, in a system in which a polymer compound that does not participate in polymerization is present, or in a system in which a polymer compound and a diluent are present. A method is employed in which polymerization is carried out in a system in which both are present at the same time. A method of polymerizing in the presence of a diluent that does not participate in polymerization involves polymerizing a non-solvent that does not participate in polymerization and is a good solvent for the monomer but has no or little ability to swell the resulting polymer or copolymer. This is a method of adding it to the system and copolymerizing it to form a porous structure. In the case of styrene-DBV copolymer resin, the diluent is t-amyl alcohol, sec
-Alcohols such as butyl alcohol, aliphatic hydrocarbons such as hexane and isooctane, or aromatic hydrocarbons such as toluene, ethylbenzene and diethylbenzene are used, and are used in an amount of 20-50% by volume based on the system involved in copolymerization. Ru. The ratio of each monomer of styrene and divinylbenzene, the reaction temperature,
Regardless of time etc., any suitable diluent can be used as the diluent applied above. In the method carried out in the presence of a polymer compound that does not participate in polymerization, ethyl maleate-vinyl acetate copolymer, ethyl maleate-methyl methacrylate copolymer, ethyl maleate-acrylonitrile copolymer, polyethylene glycol (molecular weight approx.
20,000) or polystyrene (molecular weight approximately 50,000~
A method of obtaining a porous copolymer by adding a linear polymer compound such as 100,000) to a monomer system as a kind of filler, polymerizing it, and eluting out the linear polymer compound that does not participate in the polymerization after the polymerization is completed. It is. In addition to styrene and divinylbenzene, other ethylenic monomers may be present as a third component in the polymerization.
Also, instead of styrene, 2-vinylpyridine, 4-
Vinylpyridine, etc. can also be used. Methacrylate copolymer resin is also styrene.
It is produced in the same manner as the DVB copolymer resin, but the most commonly used methacrylate esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate. Ethylene glycol dimethacrylate is most often used as the polyhydric alcohol methacrylic acid polyester of the crosslinking monomer, but polyethylene glycols (n=
1-10) Dimethacrylates are also preferably used.
Furthermore, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, etc. can also be used. As a porous methacrylate copolymer, monohydric or polyhydric alcohol/methacrylic acid monoester 10
-90% by weight and polyhydric alcohol/methacrylic acid polyester 90-10% by weight. Among these, those containing 50% or less of polyhydric alcohol methacrylic acid polyester are preferred. The method of polymerization in a system where a polymer compound and a diluent are present at the same time uses a linear polymer compound used in the method of polymerizing in a system where a polymer compound is present in combination with an aromatic hydrocarbon such as dichloroethane, xylene, or toluene. This is a method to obtain a copolymer with a porous structure. According to the method of the present invention, it can be used regardless of the porous copolymer synthesis method, but among the various physical properties of the synthesized copolymer, the specific surface area is approximately 100 to 700 m ² /
A copolymer having a pore volume of about 0.2 to 1.5 ml/g and a pore radius of about 30 to 2000 Å are particularly preferred in terms of adsorption capacity and elubility of the adsorbed substance. Specifically, styrene-DVB copolymer resins such as High Porous Polymer manufactured by Mitsubishi Kasei Corporation and Amberlite XAD-2 and -4 manufactured by Rohm and Haas Co., Ltd. exhibit such physical properties and are therefore preferred. Examples of methacrylate copolymer resins include loam,
Amberlight XAD− manufactured by And Haas
7, -8, -9, etc. are preferable because they exhibit such physical properties. Developing agents which can be separated by the method of the invention are, for example, polyhydroxybenzenes which are generally well known in the art (e.g. hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3- dichlorohydroquinone, 2,5-dimethylhydroquinone, pyrogallol, catechol, etc.), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone,
1-phenyl-4-methyl-3-pyrazolidone,
1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-4-hydroxymethyl-3
-pyrazolidone, 1-phenyl-5-methyl-3
-pyrazolidone, etc.), aminophenols (o
-aminophenol, p-aminophenol, N
-Methyl-θ-aminophenol, N-methyl-
p-aminophenol, 4-N-benzylaminophenol, 2,4-diaminophenol, etc.), ascorbic acid, 1-aryl-3-aminopyrazolines (e.g. 1-(p-hydroxyphenyl)-3- aminopyrozoline, 1-(p-aminophenyl)-3-aminopyrazoline, etc.), hydroxylamines (e.g., hydroxylamine, N-N-diethylhydroxylamine,
N-hydroxymorpholine or British patent
No. 1327032, No. 1327033, No. 1327034, No. 1327032, No. 1327033, No. 1327034, No.
1327035 etc.), p-phenylenediamines (e.g. N/N-
Diethyl-p-phenylenediamine, N.N-diethyl-3-methyl-p-phenylenediamine,
4-amino-3-methyl-N-ethyl-N-methanesulfamide ethylaniline, 4-amino-3
-Methyl-N-ethyl-N-hydroxyethylaniline, N-ethyl-N-hydroxyethyl-p
-Phenylene diamine or US Patent 2193015
No. 2592364, JP-A-48-64933, etc.), and salts thereof (e.g., hydrochloride,
sulfates, nitrates, p-toluenesulfonates, etc.). Furthermore, various embodiments are conceivable for carrying out the simple method for separating developing agents of the present invention. For example, the polymer may be present in a photographic processing bath, or the liquid overflowing from the bath may be collected and the polymer may be present therein. But that's fine. A specific method of bringing the treatment liquid into contact with the polymer is, for example, by filling a cylindrical container with the polymer to form a polymer layer, and then flowing the treatment liquid from top to bottom or from bottom to top. A so-called column method is used. In some cases, a polymer may be added to the treatment liquid, stirred to precipitate the polymer, and then filtered. In addition, the polymer is packed in a container made of a material that allows the processing solution to freely pass through.
Alternatively, this container may be placed in a treatment liquid tank, and the treatment liquid components may be adsorbed onto the polymer while stirring the liquid in the tank. Among these methods, the first column method is preferred because it requires simple equipment and operation and can be processed continuously. The method of the present invention can be used for processing silver halide photosensitive materials, regardless of black and white, color, as long as the photographic processing solution contains the above-mentioned developing agents, negative/positive reversal, autopositive type photosensitive materials, lithium type photosensitive materials, etc. It can be applied to processing solutions for all photosensitive materials such as autoradiographic photosensitive materials. Of course, developing agents and other chemicals such as color development accelerators, bromide ions,
The method of the present invention can be applied even if buffers and the like coexist. Furthermore, the developing agent is not only contained in the developing solution, but also mixed into the bath or washing water that follows the development. Therefore, the method of the present invention can be applied not only to developing solutions but also to any processing solution containing the above-mentioned substances. The developing method in the method of the present invention includes an automatic developing method using a hanger type automatic developing machine, a roller conveyance type automatic developing machine, a belt conveying type automatic developing machine, etc., and a manual processing method such as a dish phenomenon or a tank phenomenon. It can be applied to processing solutions obtained by any development processing method known in the art. According to the method of the present invention, it is possible not only to remove the developing agent from the photographic processing solution, but also to separate the developing agent at a high concentration by using inexpensive sulfuric acid, etc., and subsequent processing is also easy to perform. Next, a method for purifying and recovering the developing agent separated from the developer by the method of the present invention will be outlined. (1) Styrene-DVB copolymer resin or (and)
The developing agent in the developer solution adsorbed by contact with the methacrylate copolymer resin is desorbed from these resins by treatment with an aqueous solution of a suitable acid. The acid used here is preferably at least one of sulfuric acid, hydrochloric acid, nitric acid, nitrous acid, phosphoric acid, and the like. (2) In order to create a phase that can be separated from the aqueous phase from the aqueous solution of the acid mentioned above, organic solvent-soluble components other than the developing agent such as benzyl alcohol are removed by solvent extraction using an organic solvent. Solvents used here include ethyl acetate and ethyl acetate derivatives (for example, ethyl dichloroacetate, ethyl diazoacetate, ethyl cyanoacetate, etc.), butyl acetate, propyl acetate,
Benzyl acetate, pentyl acetate, butyl formate, isopentyl formate, ethyl butyrate, butyl butyrate, ethyl valerate, methyl salicylate, benzene, toluene, xylene, methyl butyl ketone, salicylaldehyde, diallyl ether, cyclohexane, cyclopentane, cyclopentanone,
Dichloroethane, dichloropropanol, etc. are preferred, and at least one of these is used. This step may be omitted if there is no need to remove organic solvent-soluble components other than the developing agent. (3) After removing the solvent phase, adjust the remaining aqueous phase to pH 8-9 with an alkaline agent. The alkaline agents used here are potassium hydroxide, sodium hydroxide,
At least one kind of alkali is used among ammonium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, and the like. (4) When the same organic solvent as in (2) is added to this weakly alkaline aqueous solution, the developing agent is transferred to the organic solvent system. (5) This organic solvent system is washed with the same alkaline aqueous solution as in (3) to remove alkali-soluble components. If there are no components to be removed in the organic solvent system, this step may be omitted. (6) Next, crystallize with lower alcohol.
As the lower alcohol used here, a single solvent or a mixed solvent such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol is preferably used. In the above method, when the recovered liquid in (1) contains almost no substance other than the developing agent, use a crystallization solvent (lower alcohol: methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol) after concentrating the recovered liquid. It is also possible to crystallize the developing agent by directly adding . Examples are shown below to explain the present invention in more detail. Example 1 A developer 40 having the following composition was prepared.

[Table] Add water to bring the total amount to 1.
100 m ² of color paper was processed with this color developer. Divide this solution into 2 parts, first 20 styrene-DVB
The copolymer (spherical with an average diameter of about 1 mm, specific surface area 700 m ² /g, pore area 1 ml/g) was passed through a jacketed column filled with 2.5 g of resin for 45 minutes. Next, hot water at 75°C was passed through the jacket to warm the column, and 1.5% of 1N sulfuric acid was passed through the column over a period of 30 minutes. This aqueous sulfuric acid solution was placed in a flask and heated to 70°C in a constant temperature bath while the pressure was reduced using a vacuum pump, and water vapor was condensed using a Liebig condenser. This operation produces a sulfuric acid aqueous solution.
It was concentrated to 0.3. Ethyl acetate-soluble components such as benzyl alcohol contained in the sulfuric acid aqueous solution were extracted and removed from this solution with 150 ml of ethyl acetate under acidic conditions (pH 2 or lower). Next, this acidic solution was neutralized with sodium hydroxide and sodium hydrogen carbonate, and the pH was 8 to 9.
It was prepared as follows. Furthermore, 400 ml of ethyl acetate was added to this solution, and a color developing agent (4-amino-3-methyl-N-
Ethyl-N-(β-methanesulfonamidoethyl)aniline sesquisulfate monohydrate) was extracted. The ethyl acetate solvent used at this time contained components eluted from the treated color paper and sodium sulfate produced during neutralization, which prevented efficient crystallization. Therefore, eluted components and sodium sulfate from these light-sensitive materials were back-extracted using a saturated aqueous solution of sodium hydrogen carbonate. Add 200ml of metal alcohol, 200ml of isopropyl alcohol, 17.5ml of concentrated sulfuric acid, and 17.5ml of water to the remaining ethyl acetate solution.
ml of 4-amino-3-methyl-N was added one by one and slowly stirred while cooling with ice water. After about 2 hours, 4-amino-3-methyl-N
-Ethyl-N-(β-methanesulfonamidoethyl)aniline sesquisulfate monohydrate crystals were precipitated. The yield of the crystals after filtration, separation, and drying was 66 g. 33 g of crystals of 4-amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sesquisulfate monohydrate thus obtained were dissolved in 10 ml of 60°C warm water, Added in 150ml of isopropyl alcohol. When the mixture was slowly stirred while being cooled with ice water for about 2 hours, white crystals were precipitated. The crystals were separated by filtration, dried, and weighed to give a yield of 29.5 g. Before recrystallization, it was colored somewhat brown,
After recrystallization, it turned into white crystals. Example 2 A blue-sensitive layer containing a yellow coupler and a silver chlorobromide photographic emulsion was coated on a polyethylene-coated support, and a green-sensitive layer containing a magenta coupler and a silver chlorobromide photographic emulsion was coated on top of the blue-sensitive layer. A color paper coated with a red-sensitive layer containing a cyan coupler and a silver chlorobromide photographic emulsion was developed at 31°C using the color developing solution shown in Example 1.
Treated for 3.5 minutes. However, there are three kinds of developing agents: one newly synthesized, a crude crystal product recovered according to the method of Example 1 of the present invention, and a recrystallized product recovered according to the method of Example 1 of the present invention. Next, ethylenediaminetetraacetic acid/iron salt 40g/,
The sample was treated with a bleach-fix solution containing 100 g of ammonium thiosulfate at pH 7.0 (25° C.) for 2 minutes, and then washed with water for 2 minutes. Image stability experiments conducted under the photographic and ANSI PH1.42-1969 conditions for the three methods showed similar behavior, as is clear from the table below. Concentration difference between sample density 1.5, 0.5 and fog density

[Table] Concentration difference between samples under each severe storage condition Upper left: Alignal concentration 1.0 area Lower right: Fog density area

[Table] Example 3 A developer 60 having the following composition was prepared.

[Table] Add water to bring the total volume to 1.
60 m ² of color negatives were processed with this color developer. The used developer solution was passed through a jacketed column filled with 30 to 2.5 parts of styrene-DVB copolymer resin for 45 minutes, starting after 2 minutes. Next, hot water at 75°C was passed through the jacket to warm the column, and 1.5% of 0.4N sulfuric acid was passed through it over a period of 30 minutes. This aqueous sulfuric acid solution was placed in a flask, heated to 70°C in a constant temperature bath, reduced pressure with a vacuum pump, and water vapor was condensed using a Liebig condenser. By this operation, the sulfuric acid aqueous solution was concentrated to about 0.2. This flask was heated to 70°C in a constant temperature bath, 0.6% of ethanol was added to this liquid, and by stirring slowly, N-ethyl-N-β-hydroxyethyl-2-methyl-p-ethylenediamine mono Sulfate crystallized. When this was separated by filtration and dried, 115 g of white crystals were recovered. Example 4 A red-sensitive layer containing a cyan coupler and a silver iodobromide photographic emulsion was coated on a film support, a green-sensitive layer containing a magenta coupler and a silver iodobromide photographic emulsion was coated on top of the red-sensitive layer, and then a green-sensitive layer containing a magenta coupler and a silver iodobromide photographic emulsion was coated on top of the red-sensitive layer. Example 2 A color negative coated with a blue-sensitive layer containing a yellow coupler and a silver iodobromide photographic emulsion was prepared.
It was processed for 3 minutes and 15 seconds at 38°C using a color developing solution. However, as the developing agent N-ethyl-N-β-hydroxyethyl-2-methyl-p-ethylenediamine monosulfate, one recovered in Example 3 and one newly synthesized were used. The sample was then treated with a bleaching solution containing 100 g of iron salt of ethylenediaminetetraacetate and bromide ions for 4 minutes, and for 4 minutes with a fixing solution containing 150 g of ammonium thiosulfate. The photographic performance and image stability were compared using the same method as in Example 1, and they were found to be in good agreement. Example 5 In place of the styrene-DVB copolymer resin used in Example 1, a methacrylate copolymer resin XAD-7 manufactured by Rohm & Haas (spherical shape with an average diameter of about 1 m/m and a specific surface area of 450 ^m2) was used. /g, average pore size
As a result of carrying out the same operation as in Example 1 using 90 Å resin), a good regeneration effect was observed.

Claims (1)

[Claims] 1. Bringing photographic development waste into contact with at least one adsorbent selected from styrene-divinylbenzene porous copolymer resin and monohydric or polyhydric alcohol methacrylic acid monoester-polyhydric alcohol methacrylic acid polyester porous copolymer. A method for purifying and recovering a developing agent from a photographic development waste solution, characterized in that the developing agent is adsorbed onto the adsorbent, and then the developing agent is desorbed from the adsorbent by treatment with an acid.