JPS60254134A - Automatic developing machine for color photographic sensitive material - Google Patents

Abstract

PURPOSE:To perform high-temperature fast processing by providing a rinse stabilizing tank between the bleaching tank and fixing tank of the automatic developing machine which uses no washing tank, and using processing solutions with >=500ppm dissolved material concentrastion in all processing tanks. CONSTITUTION:The magazine 103 containing a roll whih is connected to and wound with a color negative film 102 after photography is fitted to a fitting part 102 provided to a side wall of the automatic developing machine 104. The film 102 enters the main frame 104 from an entrance part 105 and is developed automatically through a color developing tank 106, bleaching tank 107, rinse stabilizing tank 108, fixing tank 109, and the 1st and the 2nd stabilizing tanks 110A and 110B, and dried 111 and discharged 111A. A cooling chamber with a fan 113 is provided nearby the color developing tank 106. A control part 116 holds the liquid temperature at necessary temperatures by a large-capacity heater 117, small-capacity heater 118, and the fan 113 according to the detection result of a temperature sensor 115. Consequently, the high-temperature fast processing is performed without using any cooling water.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an automatic processor used for processing color photographic materials. More specifically, the present invention relates to an automatic developing machine for color photographic materials, which consists essentially of color development, bleaching, rinsing stabilization, fixing, and stabilization processing steps, and has virtually no washing tank.

[Prior Art] In photographic processing, when the photographic light-sensitive material to be processed is for color, for example, steps such as color development, bleaching, fixing 1, washing, and stabilization are automatically performed. Fixing may also be carried out by bleach-fixing processing in which both functions are provided in one bath.

In photographic processing, there is a method in which a processing tank such as a color developing tank contains a processing solution in an amount necessary for development, and a color photographic light-sensitive material is processed in a batch manner while being immersed in the processing solution in the tank. This method is generally called tank development or tank development. In this method, washing is carried out with standing water, but there is a drawback that the stability of the color dye is generally impaired, and the color developer becomes fatigued after two to three treatments, resulting in changes in color development characteristics. In order to compensate for this drawback, there is a method of processing while replenishing the consumed components due to fatigue, but it is difficult to stably process a large amount of color photographic materials using this batch processing. To this end, it is generally done to keep the finished photographic performance constant by continuously processing the photographic material and continuously replenishing the consumed components one after another to keep the processing liquid components constant.

On the other hand, just like these photographic properties, the long-lasting shelf life of color photographic pigments is also an extremely important property, and it is now extremely common to maintain this long-lasting shelf life by thoroughly washing with water. It has become common knowledge. Commercial continuous color photographic processing therefore requires large amounts of water;
In addition, the location required a large amount of drainage, allowing for the supply and drainage of a large amount of washing water.

However, recently, the price of municipal tap water has risen sharply due to rising water resource development costs, and sewerage drainage costs continue to rise as well. While this soaring price of water may be due to mere economic reasons, there are also situations in which supply cannot keep up with increasing demand in densely populated large cities. In this way, we have entered an age where water, which was said to be infinite, is now finite, and drought conditions that lead to water supply restrictions are actually occurring. In areas with such water supply restrictions, there is a shortage of drinking water and washing water, and it seems extremely difficult to secure washing water for photo processing. In large cities, a water-saving society is forming, and it is no longer acceptable to use large amounts of washing water for photographic processing.

Furthermore, automatic processors for color photographic materials use a large amount of water not only for washing water but also for adjusting the temperature of the processing solution.

In this case, the processing liquid filled in each processing tank must be subject to fairly strict temperature control, and this temperature control must also be carried out strictly in the case of the above-mentioned replenishment liquid replenishment method. Even a slight change in the liquid temperature will have a significant impact on photographic performance, and the commercial value of finished prints will be significantly impaired. Conventionally, temperature control in this type of automatic processor has been accomplished by extremely frequent intermittent operations between an electric heater in a heating section and a cooling action in a cooling section using cooling water. Even the supply of processing liquid cooling water for the developing machine is limited during times of drought, so the emergence of an automatic developing machine that uses as little water as possible for cooling the developing machine is eagerly awaited.

Generally, a desired size of work space is required around each of these automatic processors, in which operations such as adjusting the replenishment cock, correcting evaporation, replacing the processing solution, and dissolving the replenisher are performed. Having water pipes under the feet of these workers is dangerous and undesirable in terms of the working environment. Furthermore, when newly installing or relocating an automatic developing machine, water piping work is always required, and such work requires time and money.

[Problems to be Solved by the Invention] The present invention has been made against the background of the above-mentioned circumstances. Firstly, it is possible to perform the developing process in an automatic developing machine without using washing water. , To improve safety by removing piping that is dangerous to the working environment. 3rd, to eliminate the need for piping work and make new installation or relocation extremely easy. 4th, to eliminate flushing water and reduce waste liquid. The chemical and physical treatment of water is easy and can be recovered, resulting in less environmental pollution.Fifth, the use of cooling water can be omitted, contributing to water conservation, which is a social need. The technical challenge is to

[Means for Solving the Problem] The automatic developing machine for color photographic light-sensitive materials of the present invention for solving the above-mentioned technical problem is an automatic developing machine that does not substantially have a water washing tank, and has no bleaching tank. The present invention is characterized in that it has a rinsing stabilization tank between it and the fixing tank, and is treated with a processing solution whose dissolved substance concentration is at least 500 ppm in all the processing tanks.

In a preferred embodiment of the present invention, the processing tank consists of a color developing tank, a bleaching tank, a rinsing stabilizing tank, a fixing tank, and a stabilizing tank, which are arranged substantially sequentially in the direction in which the photosensitive material travels, and all the processing tanks include It is to be treated with a treatment liquid having a dissolved substance concentration of at least 500 ppm or more.

The present invention is particularly suitable for developing color photographic materials without water washing, and it is also possible to provide an automatic developing machine for color photographic materials in which a water pipe for washing is omitted. That is, instead of washing with water,
No. 834, JP-A-58-105145 and JP-A-58
A system using a stabilizing liquid or a rinsing stabilizing liquid, as described in each publication of No. 18631, is adopted. Furthermore, the color developing tank of the present invention is not equipped with a heat exchange type cooling device using tap water, and the processing temperature of the processing tanks other than the color developing tank of the present invention is 3°C higher than that of the color developing tank.
It is preferable that it is lower than that.

The processing steps in the automatic developing machine of the present invention consist of five steps: color development, bleaching, rinsing stabilization, fixing, and washing alternative stabilization processing, but each processing step (bath) does not necessarily have to be one tank. Not.

For the purpose of increasing processing speed, there may be one bath or two or more baths, each bath may be connected so that the liquid can freely flow in and out, or there may be a method called a countercurrent method in which the overflow flows backwards. It may also be a method in which they are tied together. Further, each processing liquid may be composed of a plurality of processing agents having different functions. For example, the first color developing tank and the second color developing tank may be filled with processing liquids made of different processing agents, and the consumed components may be replenished separately, and the tanks may also be separated from each other. Also, regarding the rinse stabilizing liquid, the chemical concentration is 500 ppm during continuous processing.
As long as it is above, the starting liquid may be simply water.

Furthermore, as a stabilizing liquid to replace washing with water, the first stabilizing liquid may contain an anti-piping agent as a main component, and the second stabilizing liquid may contain a surfactant as a main component. Of course, in this case as well, replenisher fluids are prepared separately and replenished separately.

In the present invention, the rinsing stabilizing tank used between the bleaching tank and the fixing tank may be a bath containing simple water or a bath containing an anti-piping agent or a chelating agent. Alternatively, a second stabilizing liquid may be used.

The present invention will be explained in more detail below.

Typical examples of the processing tank configuration in the present invention are shown in FIGS. 1 to 5, and in each figure, Cal is a color developing tank,
BL stands for the bleach tank, STR stands for the rinse stabilization tank, Fix stands for the fixing tank, and ST stands for the stabilization tank, and the numbers l, 2, and O added after each symbol indicate the type of nuclide. 1st
, 2nd, Φ, etc., indicating that the liquid is separated into two or more tanks with different liquid compositions, and (a), (
B) Letters such as ``work'' indicate tanks filled with processing solutions of the same composition.

In each figure, solid lines indicate that each species is effectively separated, dashed lines and one-way arrows indicate that adjacent vessels are connected in a countercurrent manner, and dashed lines and two-way arrows indicate that each species is effectively separated. indicates that adjacent tanks are connected in such a way that they can mix freely. Capital letters A, B, C, etc. indicate replenishment fluids for each type, and lowercase letters a, b, C@ken. indicate overflow fluids from each type.

The preferred arrangement of processing tanks is as shown in Figures 1 to 5 above. In particular, the examples shown in Figures 4 and 5 are for color negatives and are characterized by the use of two types of stabilizing solutions; An example is shown in which the stabilizer is divided into a first stabilizing liquid for the purpose of desalting, and a second stabilizing liquid for final drainage, exerting a bath-like effect and preventing uneven water droplets.

Regarding the first stabilizing liquid, although the compactness is lost in the case of two tanks compared to the case of one tank, the amount of replenishment to obtain the same desalting effect may be extremely small. This is because the countercurrent method provides extremely good desalination effects.

Furthermore, although the automatic developing machine of the present invention has a color developing tank, a bleaching tank, a fixing tank, and a stabilizing tank, all of these processing tanks are housed in a single automatic developing machine main body. For example, the fixing tank may be housed in one automatic developing machine body, and the stabilizing tank may be housed in another developing machine body.

A processing step outside the scope of the present invention is a bleach-fixing process in which bleaching and fixing are performed in one bath. Although this bleach-fixing process is excellent in terms of speed and simplicity, Since it also contains sulfites, the oxidation-reduction potential of the solution decreases and the bleaching blade for image silver becomes extremely weak. For this reason, for photographic photographic materials mainly composed of silver iodobromide, which has a relatively large amount of silver and has poor bleaching properties, it is actually faster to separate the bleaching and fixing processes rather than a single bath bleach-fix process.

Therefore, the automatic processor of the present invention is suitable for processing color photosensitive materials for photography.

The automatic processor of the present invention has the above tank configuration, and the various processing solutions have a dissolved substance concentration of at least 500 ppm or more. In this case, the degree of immersion of the dissolved substance may be a concentration that is maintained in the steady state of processing by carry-over from the previous solution.

Therefore, the processing liquid used in each processing tank will be explained below.

In the present invention, the color development processing step is a step of forming a color image, specifically a step of forming a color image by a coupling reaction between an oxidized product of a color developing agent and a color coupler.

Therefore, in the color development processing process, it is usually necessary to incorporate a color developing agent into the color developing solution, but it is necessary to incorporate the color developing agent into the color photographic material, and use a color developing solution or a color developing agent containing the color developing agent. It also includes treatment with an alkaline solution (activator solution).

The color developing agent contained in the color developing solution is an aromatic primary amine color developing agent, and includes aminophenol derivatives and P-phenylezine amine derivatives. These color developing agents can be used as salts of organic and inorganic acids, such as hydrochloride, sulfate, phosphate, p-)luenesulfonate, sulfite, oxalate, benzenedisulfonate, etc. Can be used.

These compounds are generally used in color developer 1! It is used at a concentration of about 0.1 g to about 30 g per L, more preferably about 1 g to 15 g per color developer. 0
．． If the amount added is less than 1 g, sufficient color density cannot be obtained.

Further, the temperature of the processing solution in the color developing tank is 10'C to 65C, more preferably 25C to 45C.

Examples of the aminophenol-based developer include 0-aminophenol, p-aminophenol, and 5-aminophenol.
Included are 2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like.

Particularly useful primary aromatic amine color developers include N, N-
A dialkyl-p-phenylenediamine compound,
Alkyl groups and phenyl groups may be substituted or unsubstituted. Among them, examples of particularly useful compounds include 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-amine aniline sulfate, N-ethyl-N-β-hydroxy Ethylaminoaniline, 4-amino-3-methyl-N, N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N
-ethyl-3-methylaniline-p-1 luenesulfonate and the like.

Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the color developing agent may be incorporated into the color photographic material. For example, a method of incorporating a color developing agent as a metal salt as in US Pat. No. 3,719,482, and US Pat. No. 3,342,55! I
T issue and Research Red Disclosure (Resear
ch [1isclosure) 1978 No.
15159, a method of incorporating a color developing agent into a Schiff salt, as shown in JP-A-58-1999. -65429 and No. 58-24137, etc., and the method of incorporating it as a dye precursor, as shown in U.S. Patent No. 3.34.
A method of incorporating the color developing agent as a precursor as shown in No. 2.597 can be used. In this case, it is also possible to process the silver halide color photographic light-sensitive material with an alkaline earth metal activator solution instead of a color developing solution, and the material is bleached immediately after the alkaline solution.

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. In addition, various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citrazic acid, and preservatives such as hydroxyamines or sulfites may be added. May be contained. Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained.

The pH of the color developing solution used in the present invention is usually 7 or more, preferably about 9-13.

In addition, the color developing solution used in the present invention may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose, or hexose, pyrogallol-1,
3-dimethyl ether and the like may also be contained.

Various chelating agents can be used in combination as metal ion sequestering agents in the color developing solution used in the present invention. For example, the chelating agent may be an amine polycarboxylic acid such as ethylenediaminetetraacetic acid or diethylenetriaminepentaacetic acid, an organic phosphonic acid such as 1-hydroxyethylidene-1,1'-disulfonic acid, or an aminopolycarboxylic acid such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphoric acid. Polyphosphonic acid, oxycarboxylic acid such as citric acid or gluconic acid, 2-phosphonobutane-1,2,4
- Phosphonocarboxylic acids such as tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, polyhydroxy compounds, and the like.

In the present invention, the bleaching step refers to a step of bleaching the developed silver image after the color development step with an oxidizing agent (bleaching agent).

As a bleaching agent, a metal complex salt of an organic acid is used, for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid, oxalic acid, citric acid, etc., coordinated with a metal ion such as iron, cobalt, copper, etc. is used. .

Among the above organic acids, the most preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts, or water-soluble amine salts.

Specific examples of these include the following.

[1] Ethylenediaminetetraacetic acid [21 diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N, N'
, N'-triacetic acid [43 Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycinecitric acid (or tartaric acid) [91 Ethyl ether diamine tetraacetic acid [10J] glycol ether diamine tetraacetic acid [11J ethylenediaminetetraprobionic acid [121 phenylenediaminetetraacetic acid [13] ethylenediaminetetraacetic acid disodium salt [14] ethylenediaminetetraacetic acid tetra(
trimethylammonium) #A [15] Ethylenediaminetetraacetic acid tetrasodium salt 118] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β-oxyethyl)
-N,N'',N-triacetic acid sodium salt [18]propylenediaminetetraacetic acid sodium salt C
131 Triacetic acid sodium salt [201 Cyclohexanediamine tetraacetic acid sodium salt These bleaching agents are used at 5 to 450 g/JL, more preferably 20 to 250 g/M.

In addition to the above bleaching agent, the bleaching solution may contain a sulfite as a preservative, if necessary. It also contains an ethylenediaminetetraacetate iron(III) complex salt bleaching agent, and a small amount of a halide such as ammonium bromide may be added.

Alternatively, it may be a bleaching solution containing a large amount of a halide such as ammonium bromide. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

In the present invention, the fixing step refers to a step of desilvering and fixing using a fixing solution containing a silver halide fixing agent. Silver halide fixing agents used in the fixing solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes. Typical examples include thiosulfates such as, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and the like. These fixing agents are used in an amount of 5 g/1 or more, within the range that can be dissolved, but are generally used in an amount of 70 g to 250 g. Note that a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank.

The bleaching solution and/or fixing solution may include boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. p
H buffering agents may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, and organic A solvent and the like can be contained as appropriate.

The bleaching solution used in the present invention includes JP-A No. 46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770,910, JP-A No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The pH of bleaching solution used is 2.0 or higher, but generally the pH is higher than 2.0.
Used at pH 4.0 or higher and pH 9.5 or lower, preferably p
It is used at a pH of 4.5 or more and 8.0 or less, and more specifically, the most preferred pH is 5.0 or more and 7.0 or less. The processing temperature is 80'O or less, which is 3°C or more, preferably 5°C or more lower than the processing solution temperature in the color developing tank, but preferably 55°C or less to prevent evaporation, etc. do.

The pH of the fixer is used at 3.0 or higher, but generally the pH is 3.0 or higher.
Used at pH 4.5 or higher and pH 10 or lower, preferably pH
It is used at a pH of 5 or more and 9 and 5 or less, and more specifically, the most preferable pH is 6 or more and 9 or less. The processing temperature is 80° C. or lower, which is 3° C. or more, preferably 5° C. or more lower than the temperature of the processing solution in the color developing tank, but preferably 55° C. or lower to prevent evaporation.

Further, in the fixing step, etc., silver may be recovered from the soluble silver salt in the fixing solution by a known method. For example, electrolysis method (described in Buddhist Patent No. 2,298,8177), precipitation method (described in JP-A-52-73037, Second Patent No. 2,331,
220 specification), ion exchange method (# Kaikai 51-1
7114, Sec. Patent No. 2,548,237), and metal substitution method (British Patent No. 1,353).
, No. 805) etc. can be effectively used. Furthermore, when recovering silver, the soluble silver salt may be used to collect the overflow solution of the processing solution and recover silver using the above method, and the remaining solution may be disposed of as waste solution, or a regenerating agent may be added and used as a replenisher or seed processing solution. May be used.

In the present invention, a rinsing stabilization tank is provided between the bleaching tank and the fixing tank for rinsing stabilization treatment using a stabilizing solution, which will be described later. When a rinsing stabilization tank is provided between the bleach tank and the fixing tank, mixing of bleaching solution components into the fixing solution is minimized and deterioration of the fixing solution components is prevented. It is also possible to prevent fading of the cyan dye due to bleach components changed in the fixing solution, such as ethylenediaminetetraacetate iron (bivalent), and it is possible to stabilize images after processing.

Rinse stabilizing liquid is effective because it fulfills this function.

The stabilizing liquid filled in the rinse stabilizing tank of the present invention exhibits the above effects even if it is simply water (tap water), but various anti-spill agents may be added to prevent the water from spoiling. preferable. However, it is preferable that the stabilizing solution has a low replenishment amount such that the total concentration of the bleach carry-on concentration and the stabilizer is 500 ppm. In addition, the same chelating agents that can be used in the bleaching agents described above can be used. The stabilizing solution filled in the rinsing stabilizing tank may be a stabilizing solution immediately after the fixing process. In this case, formalin or a surfactant may be included in addition to the above additives.

The pH value of the rinse stabilizing solution used in the present invention is 0.1
The pH is preferably adjusted to pH 10 to 10, preferably 2 to 8, more preferably 4 to 8.5.

The treatment temperature during the rinse stabilization treatment is 15°C to 6°C.
0℃ and 3℃ or higher than the color developing tank, preferably 5℃
The temperature is lower than ℃, more preferably 20℃ to 38℃
A range of C is good.

Note that a conditioning tank may be provided before the bleaching step, and the conditioning tank stops the development,
It is used to accelerate the bleaching reaction, and is useful for preventing the developer from being mixed into the bleaching solution and reducing its negative effects, and the conditioning tank contains, for example, a bleaching accelerator and a buffer agent. . As the bleaching accelerator, organic sulfur compounds are generally used, including mercapto compounds and thione compounds. Furthermore, acids and alkaline agents such as acetic acid, citric acid, succinic acid, sulfuric acid, and sodium hydroxide are used to adjust the pH of the conditioner. The amount of these bleaching accelerators and eight-fermenting agents added is in the range of 0.001 g to 100 g per conditioner ti.

In addition to the above additives, chelating agents and the like may also be added.

The stabilization treatment used in the present invention is an alternative treatment to water washing, and refers to the image stabilization treatment described in Japanese Patent Application No. 58-2709, etc. in addition to the above-mentioned Japanese Patent Application Laid-open No. 58-134636. This is to eliminate processing. Therefore, the name of the treatment bath does not necessarily have to be stabilization treatment.

Among the stabilizing liquids, there are also stabilizing liquids that have a function of stabilizing color images and a function of draining bath to prevent contamination such as uneven washing. These stabilizing liquids also include coloring adjustment liquids for coloring color images and antistatic liquids containing antistatic agents. When fixing components are brought into the stabilizing solution from the prebath, measures are taken to neutralize, desalt, and inactivate these components so as not to deteriorate the storage stability of the dye.

Among the components contained in such a stabilizing liquid, there is a chelating agent having a chelate stability constant of 6 or more with iron ions. These chelating agents include organic carboxylic acid chelating agents,
There are organic phosphoric acid chelating agents, polyhydroxy compounds, inorganic phosphoric acid chelating agents, etc. Among them, preferred chelating agents include ethylenediamine diorthohydroxyphenylacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and hydroxyethylimine diacetic acid. Acetic acid, diaminopropanoltetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, l-hydroxyethylidene-1,1'-diphosphonic acid, 1,1'-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane- 1
, 2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, atrium tetrapolyphosphate, and sodium hexametaphosphate. For the effects of the present invention, particularly preferred are diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, and salts thereof.

These compounds generally contain approximately 0.0
A concentration of 1 g to 10 g, more preferably about 0.5 g to 5 g per serving of stabilizing liquid is used.

Furthermore, desirable compounds to be added to the stabilizing solution of the present invention include pH adjusters such as acetic acid, sulfuric acid, hydrochloric acid, nitric acid, sulfanilic acid, potassium hydroxide, sodium hydroxide, and ammonium hydroxide, sodium benzoate, and hydroxyl. Butyl benzoate, antibiotics, tehydroacetic acid, potassium sorbate, thiabentazole, anti-inflammatory agents such as ortho-phenylphenol, 5-chloro-2-methyl-4-inthiazolin-3-one, 2-octyl-4 -Isothiazoline-
3-one, 1,2-pentzinthiazolin-3-one,
Preservatives such as water-soluble metal salts, dispersants such as ethylene glycol, polyethylene glycol, polyvinylpyrrolidone,
Examples include hardening agents such as formalin, optical brighteners, and the like.

Among these compounds, the most effective one is
It is an ammonia compound described in the specification of No. 8693. These maintain the pH in the image coating.

It works to adjust the acidity to the optimal weak acidity for the body.

The pH value of the stabilizing liquid used in the present invention is preferably adjusted to 0.1 to 10, preferably 2 to 9, and more preferably 4 to 8.5.

The processing temperature during the stabilization treatment is 15°C to 60°C, which is 3°C or more, preferably 5°C or more lower than the color developing tank, and more preferably 20°C to 38°C. In addition, the shorter the treatment time, the better from the viewpoint of rapid processing, but it is usually 20 seconds to 10 minutes, most preferably 20 seconds to 3 minutes, and in the case of multiple tank stabilization treatment, the first stage tank should be used in a shorter time. It is preferable that the treatment time in the subsequent tank is long.

In particular, it is desirable to perform the treatment sequentially with a treatment time 20% to 50% longer than in the previous tank. Further, it is preferable to perform the stabilization treatment process using a multi-stage tank, and use a backflow method in which the replenisher is replenished from the final stage tank and sequentially overflows to the previous stage tank, since the amount of replenishment can be reduced. After the stabilization treatment according to the present invention, no rinsing treatment is required at all, but rinsing stabilization by rinsing with a small amount of water in a very short time, surface cleaning, etc. can be optionally performed as necessary. In particular, transport supports such as endless belts and sorters that transport photographic materials should be stabilized by rinsing with a small amount of water (preferably standing water) or a sponge.

It is preferable to wash it while wetting it with water.

When stabilizing directly after the fixing process of the present invention without substantially going through a water washing process, a short-time silver recovery tank (bath ) etc. may be provided. Note that after the stabilization treatment, a draining bath containing a surfactant or the like may be provided, but preferably, a silver recovery bath, a draining bath, etc. are not provided. These additional treatments can also be carried out by spraying or painting.

In the present invention, the stabilizing solution and the ion exchange resin can also be treated while being brought into contact with each other. This can be done by placing the ion exchange resin in a cloth bag or the like and bringing it into direct contact with the stabilization tank where the photosensitive material is being processed, or by placing chemical fibers etc. in the resin column or filter case directly connected to the stabilization tank. Indicates that it is placed in a prepared bag or the like and brought into contact with a stabilizing liquid. Further, after the overflow liquid of the stabilizing liquid of the present invention comes into contact with the ion exchange resin, at least a part thereof can be used as the stabilizing liquid. To do this, take out the stabilizing liquid from the stabilizing tank, separate it from the stabilizing tank, contact it with the ion exchange resin by column method or mixing method, and then put at least a part of it into the stabilizing tank. Show that. In this case, "putting into the stabilizing tank" means that the liquid can be put as a replenisher, but preferably it means returning the liquid to the stabilizing tank after ion exchange treatment in a circulation system, regardless of the replenishing system.

The ion exchange resin may be brought into contact with the stabilizing bath in any tank when the stabilizing bath is multi-tank, but it is preferably treated in the tank immediately after the fixing process. More preferably, this treatment is carried out in two or more tanks, particularly preferably in all tanks.

When there is only one stabilizing bath, a preferred embodiment is to put the ion exchange resin in a resin column and directly connect it to the stabilizing bath. In a preferred embodiment when there are two stabilizing baths, the ion exchange resin is placed in a resin column or filter case, and directly connected to and brought into contact with the first tank immediately after the fixing process, and more preferably brought into contact with the second tank in the same manner. . . 3 stabilizing baths
In the case of more than one species, a preferred embodiment is to directly connect and contact them in the same way as described above in the first tank immediately after the fixing process, and more preferably to directly connect and contact them in a tank of a stabilizing bath other than the first tank. That's true. As mentioned above, it is most preferable to directly connect the ion exchange resin and the stabilizing solution to the stabilizing tank, but if the automatic processor does not have enough space to install the resin column and filter case, increase the overflow or replenishment amount. Alternatively, the stabilizing solution forcibly removed from the stabilizing bath may be brought into contact with the ion exchange resin and returned to the stabilizing bath. When there is only one stabilizing bath, the taken out stabilizing liquid is brought into contact with an ion exchange resin using a resin column, and the stabilizing liquid after contact is returned to the stabilizing tank. In this case, it is preferable to add a stabilizing liquid component after contact. When there are two or more stabilizing baths, the overflow and resin column are used to bring the stabilizing bath into contact with the ion exchange resin from the foremost tank near the fixing process, and the mixture is returned to the stabilizing bath on the drier side. In this case, it is desirable to add back the stabilizing liquid component.

Furthermore, although it is possible to reuse the stabilizing solution after contact with the ion exchange resin as a replenisher, in this case it is desirable to add a stabilizing solution component.

In addition, it is preferable that the above-mentioned ion exchange resin be brought into contact with a stabilizing solution, then brought into contact with a fixing solution, and then regenerated. In particular, in the case of an anion exchange resin, silver recovery can also be performed by regenerating the resin, which is effective. big.

The case where the stabilizing liquid is brought into contact with the ion exchange resin has been described above, but this is not limited to electrodialysis treatment (see patent application (C) filed on May 16, 1980) and reverse osmosis treatment (see patent application (C) filed on May 16, 1981). Patent application filed on May 16, 1959 (A)
Reference) etc. can also be used.

The negative stabilizing liquid used when the photographic material to be processed is negative will be described below.

An aldehyde derivative is added to the negative stabilizing liquid to improve the storage stability of photographic images.

The aldehyde derivative has the following general formulas (1) and (2).
Alternatively, at least one selected from among the aldehyde compounds and aldehyde adducts represented by (3) is used. These additions stabilize the dye image and improve the physical properties of the light-sensitive material.

General formula (1) RJ -CHO General formula (2) % formula % General formula (3) In the formula, R1 is a hydrogen atom, a formyl group, an acetyl group, an acetonyl group, a hydroxy group, or an alkoxy group,
Represents a formyl group, an amino group, a hydroxyimino group, an alkyl group having 1 to 5 carbon atoms which may be substituted with a halogen atom, etc., R2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R3 is an alkyl group which may be substituted. A good alkyl group having 1 to 5 carbon atoms, N is an alkali metal, R4 and R5 are hydrogen atoms or optionally substituted alkyl groups having 1 to 5 carbon atoms, n is 0
Represents an integer from ~4.

Specific examples of compounds represented by the above general formula are described below, but the present invention is not limited thereto.

[Exemplary compounds represented by general formula (1)] 1 Formaldehyde 2 Acetaldehyde 3 Propionaldehyde 4 Inbutyraldehyde 5 N-Butyraldehyde 6 N-Valeraldehyde 7 Invaleraldehyde 8 Methylethylacetaldehyde 9 Trimethylaldehyde 10 N-Hexaldehyde 11 Methyl -n-propylaldehyde 12 isohexaldehyde 13 glyoxal 14 malonaldehyde 15 succinic aldehyde 16 glutaraldehyde 17 adibaldehyde 1 day methylglyoxal 18 acetoacetic aldehyde 20 glycolaldehyde 21 ethoxyacetaldehyde 22 aminoacetaldehyde 23 betaine aldehyde 24 Chloral 25 Chloracetaldehyde 28 Dichloroacetaldehyde 27 Promal 28 Dibromoacetaldehyde 29 Iodoacetaldehyde 30 α-Chlorpropionacetaldehyde 31 α
-Bromopropionacetaldehyde [exemplified compound represented by general formula (2)] 1 Formaldehyde sodium bisulfite 2 Acetaldehyde sodium bisulfite 3
Propionaldehyde Sodium Bisulfite 4 Butyraldehyde Sodium Bisulfite [Exemplary Compound Represented by General Formula (3)] 1 Succinic Aldehyde Sodium Bisulfite 2 Glutaraldehyde Sodium Bisulfite 3
β-Methylglutaraldehyde Sodium bisbisulfite 4 Maleic acid dialdehyde Sodium bisbisulfite The compound represented by the above general formula is preferably used in an amount of 0.01 to 50 g per negative stabilizing liquid 11, more preferably Good results are obtained when adding 0.05 to 20 g.

Various additives can be added to the negative stabilizing liquid as necessary. For example, water droplet prevention agents such as siloxane derivatives, pH adjusters such as boric acid, citric acid, phosphoric acid, acetic acid, or sodium hydroxide, sodium acetate, potassium citrate, hardeners such as potash alum, chromium alum, etc.
It is optional to add additives to improve or extend the processing effect, such as organic solvents such as methanol, ethanol, and dimethyl sulfoxide, dispersants such as ethylene glycol and polyethylene glycol, and other color tone modifiers.

Further, the negative stabilizing liquid may be partitioned into two or more sections in order to increase the length of the countercurrent flow path, similar to the above-mentioned stabilizing liquid. Further, the method of preparing the replenisher, the amount of replenishment, and the processing temperature are the same as those for the stabilizing solution.

Further, in the present invention, a stilbene-based fluorescent brightener can be used in the color developing solution or stabilizing solution for color paper, and the fluorescent brightener includes a compound represented by the following general formula (4).

General formula (4) where R6, R2 and Rδ are hydroxyl group, chlorine,
Halogen atoms such as bromine, morpholino groups, substituted or unsubstituted alkoxy groups (e.g., methoxy, ethoxy, methoxyethoxy, etc.), substituted or unsubstituted aryloxy groups (e.g., phenoxy, p-sulfophenoxy, etc.), substituted or unsubstituted alkyl groups (e.g., methyl, ethyl, etc.), substituted or unsubstituted aryl groups (e.g., phenyl, methoxyphenyl, etc.), amino groups, substituted or unsubstituted alkylamino groups (e.g., methylamino, ethyl Amino, propylamine, dimethylamino, cyclohexylamino, β-hydroxyethylamino, di(β-hydroxyethyl)amino, β-sulfoethylamino, N-(β-sulfoethyl)-N-methylamino, N-(β- hydroxyethyl)-N-methylamino, etc.).

The fluorescent whitening agent represented by the general formula (4) is stabilized by H
It is used in a range of 0.2 to Log per L, preferably in a range of 0.5 to 3.0 g.

[Example] Examples will be described below based on the drawings.

FIG. 6 is a sectional view of essential parts of an automatic developing machine showing a specific example of the tank configuration shown in FIG. 3.

In FIG. 6, a supply section 4 for supplying exposed and undeveloped color negative film (negative photosensitive material) 2 or color paper (positive photosensitive material) 3 is provided on the front side of the developing machine body l, and on the rear side. A take-out section 5 is provided, from which the processed photosensitive material 2.3 is taken out.

Between this supply section 4 and take-out section 5, that is, the developing machine main body l
Inside, there are a color developing tank 6, a bleaching tank 7, a rinsing stabilizing tank 8, and a fixing tank 9, which are arranged successively from the supply section side to the takeout section side.
, a first stabilization tank 10A, a second stabilization tank 10B, a third stabilization tank 10G, and a drying section 11 are provided.

A large number of guide rollers 12 are provided in each of the processing tanks 6.7.8.9, IOA, IOB, and IOC, and the drying section 11.

For example, endless belts 13 and 14, which are a pair of conveying carriers, are hung around the guide roller 12, and the endless belts 13 and 14 convey the negative photosensitive material 2 and the positive photosensitive material 3, respectively. Each of these endless belts 13
．． 14 is adapted to be driven by a drive motor 15 provided from the supply section side. Note that 16 indicates a winding portion of the photosensitive material 2 or 3.

A holding section 17 is provided in the supply section 3, and an exposed but undeveloped negative photosensitive material 2 or positive photosensitive material 3 is set in this holding section 17. And negative photosensitive material 2
Alternatively, the positive photosensitive material 3 is supported at its end by the endless belt 13 or 14 via a clip (not shown), and is conveyed by the endless belt 13 or 14.

The color developing tank 6, bleaching tank 7, rinsing stabilizing tank 8, fixing tank 9, first stabilizing tank 10A, second stabilizing tank 10B, and third stabilizing tank 10G are constructed as shown in FIG. has been done. That is, the color developing tank 6 is filled with the color developing solution, and the processing tanks 7, 8, 9, 10A10B, and IOC located after the color developing tank 6 are also filled with each of the processing solutions. ing. The replenisher supply to each processing tank is as shown in Fig. 3 above, and in particular, the first stabilization layer (ST (a)) IOA, the second layer (ST (b)) IOB, and the The three-layer (ST(c)) IOCs are connected so that the liquid level changes so that the overflow flows from the third tank to the second tank and from the second tank to the first tank in a countercurrent manner. The overflow liquid from the third tank 10G is discharged from the first tank 10A to the outside of the tank. Of course, the number of stabilizing tanks may be one or two, but a multi-tank countercurrent system has the advantage of high stabilization efficiency and the need to replenish a small amount of replenisher.

In the figure, reference numeral 18 indicates a blade or squeeze portion made of a pyramid-shaped blade plate or the like, which effectively prevents liquid from being brought into the next tank from the front tank.

Next, a specific example of an automatic developing machine in which the processing tank arrangement shown in FIG. 4 is implemented will be described with reference to FIG. 7. Note that this embodiment also shows an example in which even the cooling water pipes are omitted.

That is, FIG. 7 is a sectional view of essential parts showing an embodiment of an automatic developing machine for color negative film according to the present invention.

In the figure, 101 is a color negative film that has been photographed.
102 is connected to the automatic developing machine main body 10.
It is installed on the side wall of 4.

The color negative film 102 of the film magazine attached to the mounting part 101 is transferred from the main body entrance part 105 to the main body 10.
4, a color developing tank 10B, a bleaching tank 107, a rinsing stabilizing tank 108, a fixing tank 108, and a first stabilizing tank 110A.
After passing through the second stabilizing tank 110B and being automatically developed, it is dried in the drying section 111 (with an openable/closable lid), taken out from the main body outlet 111A, and then subjected to cutting and other processes to become a product. Become.

Color developer tank 10B, bleach tank 107, rinse stabilization tank 10
8. The fixing tank 109, the first stabilizing tank 110A, and the second stabilizing tank 110B are sequentially arranged in parallel as shown in the figure, and each tank is provided with a roller for conveying the negative film, and the color negative film 102 is turned into a liquid. It is configured so that a predetermined treatment is performed while it is immersed. In addition, each tank 106 to 110
An opening/closing lid is provided on B to prevent evaporation and take maintenance into account.

In the automatic developing machine of this embodiment, a cooling chamber 112 is provided adjacent to the color developing tank 106. A fan 113 is provided on the outer wall of the cooling chamber 112, and an outside air introduction hole 114
An appropriate number of holes are also provided. The cooling chamber 112 also serves as a control system equipment room and houses the control section 116. The control unit 116 turns the large-capacity electric heater 117 and the small-capacity electric heater 118 ON-OF according to an input signal of the liquid temperature of the color developing tank 106 detected by the temperature sensor 115.
F control is performed to control the temperature for heating, and the fan 113 is also controlled from ON to FF to perform temperature control for cooling.

In this regard, conventional automatic developing machines have only the large-capacity electric heater 117 as a heating system, and as a cooling system, water piping is connected to a corrugated pipe arranged near the bottom of the color developing tank 106, and water is used as a cooling medium. A cooling method was used. In this conventional example, when the capacity of the color developer tank 106 is 20, the color developer tank 10EI is operated 3 times during the operating time (approximately 12 hours).
Approximately 10,001 g of tap water is required to maintain the temperature at 8°C.

However, according to this embodiment, when the outside temperature is 25°C, 3
By simply rotating the exhaust fan 113 on the stand, the liquid temperature in the color developing tank 10 flt can be adjusted to 38°C ± 38°C during the operating time (approximately 12 hours).
The temperature range could be controlled within 0.15°C. That is, according to this embodiment, the cooling water used in the conventional example can be omitted.

There is no need for that water piping. In the heating system in this embodiment, the large capacity electric heater 117 (and small capacity electric heater 118) is used to raise the liquid temperature to 38°C during start preparation, and the small capacity electric heater 118 is used during running processing. The liquid temperature was controlled using As for the cooling system, three fans 113 continued to operate during the operating time.

In the figure, reference numeral 118 denotes a liquid circulation stirring device housed in the control system equipment room/cooling room 112, and a liquid feeding pump 121 and a liquid cleaning device are installed in the middle of a passage 120 connecting the upper and lower parts of the color developing tank 106. A filter 122 is provided.

Note that the cooling effect can be increased by increasing the contact area, such as by providing fins on the wall surface of the surface of the color developing tank 1013 in contact with the cooling chamber 112.Furthermore, if this passage 120 is made of a spiral pipe, the cooling effect can be increased, and the filter effect can be improved. In addition, effective stirring can be achieved. Furthermore, the mounting position of the fan 113 is not limited to this embodiment, and may be on the top plate side or the like. 12
Reference numeral 5 designates a blade or squeeze portion such as a pyramid-shaped blade plate, which effectively prevents liquid from being brought into the next bath from the previous bath.

In addition, in the drawing, 123 indicates a drying section, and 124A and 124B indicate waste liquid tanks.

The first stabilizing tank 110A of this embodiment is a stabilizing liquid that has image stabilization and piping prevention effects, and its main purpose is a desalination bath. On the other hand, the second stabilizing bath 110B is a treatment bath containing a surfactant, formalin, etc., and is intended to prevent uneven water droplet staining. In this case, a solution containing only a surfactant may be used.

Also in the embodiment shown in FIGS. 6 and 7 above,
A treatment liquid having the above-mentioned composition is used in the column and tank within the concentration range of the present invention.

[Effects of the Invention] According to the present invention, there is provided an automatic developing machine that does not substantially have a rinsing tank, which has a rinsing stabilization tank between the bleaching tank and the fixing tank, and has a rinsing stabilization tank between the bleaching tank and the fixing tank. Since the structure is such that the treatment is performed with a treatment liquid having a dissolved substance concentration of at least 500 pp+a, it is possible to solve the above-mentioned technical problems of the present invention as well as to solve the technical problems of the present invention. Compared to other tank configurations, it is ideal for high-temperature, rapid processing, significantly improves development performance despite being waterless, and prevents the mixing of bleaching solution components into the fixer. can be minimized and prevent deterioration of fixer components.
■It can also prevent the fading of cyan dyes due to bleach components that have changed in the fixing solution, such as ethylenediaminetetraacetate iron (divalent), and has the effect of being able to stabilize images after processing. demonstrate.

[Brief explanation of the drawing]

FIGS. 1 to 5 are block diagrams showing the processing tank configuration of an automatic processor according to the present invention, and FIG. 6 is a block diagram of an automatic processor showing a specific example when the tank configuration shown in FIG. 3 is implemented. FIG. 7 is a sectional view of essential parts showing an embodiment of an automatic developing machine for color negative film according to the present invention. In the drawing, CD is a color developing tank, BL is a bleach tank, and STI'l
indicates a rinsing stabilization tank, Fix indicates a fixing tank, and ST indicates a stabilization tank. aocae ↑

Claims (1)

[Claims] (1) An automatic developing machine having substantially no washing tank,
A rinsing stabilization tank is provided between the bleaching tank and the fixing tank, and the concentration of dissolved substances in all treatment tanks is at least 500p.
An automatic developing machine for color photographic materials, characterized in that it is processed with a processing solution of pm or higher. (2) The automatic developing machine for color photographic materials according to claim 1, further comprising a stabilizing tank in the next step of the fixing tank. (3) Claim 1 or 2, characterized in that the color developing tank does not have a heat exchange type cooling device using tap water.
An automatic developing machine for color photographic materials as described in Section 1. (4) A color photograph according to claim 1, 2 or 3, characterized in that the processing temperature of the processing tank other than the color developing tank is 3°C or more lower than that of the color developing tank. Automatic developing machine for photosensitive materials. (5) An automatic developing machine for color photographic materials as set forth in claim 2, 3, or 4, characterized in that the stabilizing tank consists of two stabilizing tanks having different functions.