JPH0196653A - Method for processing photographic sensitive material by single tank and automatic development processing device - Google Patents

Abstract

PURPOSE:To enable rapid processing with a single tank by executing stabilization processing at least twice by using a liquid stabilizer. CONSTITUTION:The stabilization processing is executed at least twice by using the liquid stabilizer ST at the time of processing a photographic sensitive material 20 by using the single processing tank 71 and repeatedly supplying and discharging a color developing soln. CD, a bleach-fix bath BF and the liquid stabilizer ST to and from the processing tank 71. The automatic developing device for disk films which eliminates the delay in processing service, is as small as to be installable even in a narrow store, allows easy operations even by unskilled clerks and provides stable and good processing performance is thereby obtd.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a method for processing photographic materials using a single tank, which is preferable for application to a small-sized automatic processor that processes a small number of photographic materials, and an automatic processing method for photographic materials. The present invention relates to a development processing apparatus. Specifically, a photographic disk-shaped photographic material (herein referred to as a disk film) that has been photographed is set in an automatic processor as a film unit without taking it out from a light-shielding structure (herein referred to as a cartridge). .

This is applied to a small automatic processor for disc film that automatically takes out the disc film from the set film unit, guides it to the processing section, develops it, and then automatically discharges the processed disc film outside the machine. The present invention relates to a preferable single-tank processing method for photographic materials and an automatic processing apparatus.

[Prior Art] Conventionally, in order to develop disc film, a cartridge opener separate from the automatic processor is used to destroy the cartridge, take out the stored disc film, and put it into a cylindrical body called a magazine. A large number of disc films are transferred and the entire magazine is transferred to an automatic developing machine for development processing.

The processing solution is divided into a plurality of processing tanks and stored in a plurality of processing tanks, and the photographic material is sequentially conveyed through each processing tank and subjected to immersion processing.

Regarding such automatic processors for disc film, please refer to the complete Kodak disc film system (photo industry,
April 1982 issue, pages 26-41).

In the case of 351III11 film and Oneten film.

Due to the spread of small automatic processing machines called minilabs, services are now available for up to one hour, but in the case of disc film, processing facilities are unevenly distributed.
Currently, it takes about three days from the date of request, which is one reason why disc films are not popular.

In order to eliminate the above-mentioned delays in processing services, the present inventors have developed a system that is small enough to be placed in a narrow store, easy to operate even for unskilled store staff, stable, and We have been conducting research on automatic development for disc films that provides good processing performance, and have already made several new proposals.

A series of studies have found that treatment using a single treatment tank is preferable, considering the problems of downsizing the equipment and interlocking control of mechanisms.

[Problems to be Solved by the Invention] It has been found that in processing using a single processing tank, there is a risk that the bleach-fix solution remains in the processing tank and causes contamination of the color development processing solution in the next processing. In order to prevent this, it is conceivable to carefully wash the processing tank with washing water or the like every time a single processing is completed, dry it, and then reuse it, but this is too complicated and time-consuming. Therefore, the final stabilization treatment (including water washing, stabilization treatment, and water washing substitute stabilization treatment) can be carried out for a certain period of time or more, but the treatment time is too long and the request for short treatment time cannot be satisfied. There was found.

The present invention has been made in view of the above, and it not only performs stable processing in a short time, but also prevents the bleach-fix solution from remaining in the processing tank and contaminating the color developing processing solution for the next processing, causing variations in photographic performance. The main purpose of the present invention is to clarify a method for processing photographic light-sensitive materials in a single tank and an automatic processing apparatus that do not cause the above-mentioned problems. This will become clear from the attached drawings.

[Means for Solving the Problems] A method for processing photographic materials that achieves the above object of the present invention uses a single processing tank, and sequentially supplies a color developer, a bleach-fix solution, and a stabilizer to the processing tank. This is a method of processing a photographic material by repeating feeding and discharging, and is characterized in that the stabilizing treatment is carried out at least twice using a stabilizing solution.

Further, the automatic processing apparatus of the present invention that achieves the above object uses a single processing tank, and repeatedly supplies and discharges a color developing solution, a bleach-fixing solution, and a stabilizing solution to the processing tank in order to produce a photographic material. The automatic development processing apparatus is characterized by having a structure in which the stabilizing solution is repeatedly supplied and discharged two or more times during the stabilization processing.

Hereinafter, details of the present invention will be explained with reference to the accompanying drawings.

First, a preferred automatic developing apparatus to which the present invention is applied, in which the photographic material to be processed is a single disk film, will be described with reference to the accompanying drawings.

FIG. 1 is a perspective view showing an outline of a compact automatic developing machine for disk film. All that is required is to insert the film unit 10 into the insertion slot 30 in the orientation shown, and the film unit 10 is automatically opened. Cartridge 11 is taken in, fed 4M, and held at a predetermined position by a mechanism described later.
Only the lower end side of the disc film 20 is opened and the stored disc film 20 is dropped downward.

40 is a running member, and both ends are guide rails 41°41
The worm 42 performs linear reciprocating motion by rotation of a worm 42 that is rotated by a motor (not shown).

A holding member 43 that is biased in the direction of the arrow is provided on the lower surface of the traveling member 40, and when the film unit 10 to be processed is inserted into the insertion slot 30 by a certain depth in the orientation shown in the figure, the holding member 43 is pressed in the direction of the arrow. , the exposure window 14 and its back side in the film unit 10 engage with the holding member 43. If the worm 42 is rotated in the forward direction in this state, the film unit 10 is transported to the position shown by the imaginary line while being suspended from the lower surface of the traveling member 40.

When the film unit 10 is conveyed to a predetermined position, when the number of rotations of the motor or other types of sensors is detected, a driving means such as a solenoid (not shown) is activated to move the light shielding plate 50 in the direction of the arrow. Push it out, and close the insertion port 30 part in a light-shielding state.

In the illustrated embodiment, when the film unit 10 is guided to the position indicated by the imaginary line, the stopper 51 for regulating the rear end position moves simultaneously with the light shielding plate 50, thereby preventing the destruction of the cartridge as described below. Regulates the rear end when

Reference numeral 52.52 denotes a push-out pin that is driven by a solenoid (not shown) or the like to reciprocate in the direction of the arrow. In synchronization with this operation, the periphery of the opening 12.12 of the exposure window side plate 11 is supported from the back side by a support member (not shown). As a result, when the push-out pins 52.52 are moved to the left in the drawing, the lower end of the exposure window side plate 11 does not move due to the support of the support member from the back side, and only the lower end of the label side plate]3 is moved. 5
2, the bond between the exposure window side plate 11 and the label side plate 13 is broken only at the lower end.

In addition to the push-out pins 52 and 52, the label side plate 1
A member that simultaneously pushes out the lower ends 16 of 3 may be used in combination.

When the destruction of the lower end of the cartridge is completed, the push-out pins 52 and 52 return to their original positions together with the back support member (not shown), and the swinging member 53 then reciprocates in the direction of the arrow to remove the cartridge from the lateral direction. Repeats the rocking motion of pressing and releasing pressure.

At this time, the pressing and pressing may be continuous or discontinuous, and furthermore, it may be a repetition of (pressing-pressing release) or (pressing-pressing-pressing release), and there is no particular limitation.

As a result, the cartridge is laterally bent by compression, the broken lower end becomes open, and the stored disc film 20 falls into the guide section 60 provided below.

When the disc film 20 falls (completely taken out from the cartridge), it is detected by a sensor using infrared light provided below, and the disc film 20 swings.

The M movement of the member 53 is stopped.

The disk film 20 that has fallen into the guide section 60 is stopped by the stop collar 61, and then moved to the spindle shafts 62, 6.
A match is made for 3. That is, the spindle shaft 62.
63 moves in the direction of the arrow and engages with the central core portion of the disc film 20. At this time, the tip of the spindle shaft 62 is formed in a convex shape, and the tip of the spindle shaft 63 is formed in a concave shape so that engagement with the disk film 20 can be easily and reliably performed. When the engagement of the disk film 20 with the spindle shaft 62, 53 is completed, the stopper 61 performs an escape operation in the direction of the arrow.

70 is a processing section, and when the processing tank 71 is raised or the spindle shaft 62.63 is lowered, the processing tank 71 extends up to the vicinity of the central core of the disk film 20 held by the spindle shaft 62.63. The disk film 20 is immersed in the processing liquid therein and is subjected to rotational processing by rotation of the spindle shafts 62 and 63.

Supply/discharge of the processing liquid, temperature control, and drying are performed as follows.

The photographic processing solution is preferably one that has been adjusted to a liquid state that does not require any measures other than at least temperature adjustment, such as a color developer (CD solution), a bleach-fix solution (BF solution), and a water-washing alternative stabilizing solution. The liquids (ST liquids) are separated and stored in containers 74.

The lower end of the container 74 is immersed in a hot water bath 75, and the temperature is adjusted to a constant level by heating means such as an electric heater.

As shown in FIG. 2, guide pipes 76 for color development, bleach-fixing, and stabilization processing solutions are arranged while immersed in hot water in a hot water bath 75, and the amount of processing solutions present in these pipes is as follows: The amount is not enough to process one or more disk films, so even if the entire processing liquid in the tank 74 does not rise to the appropriate temperature for processing, once the processing liquid in the guide tube reaches the appropriate temperature, processing can be carried out. Since the process can be started quickly, it is useful in terms of energy saving and prevention of deterioration of the process liquid when the process is used intermittently and the number of processes is small.

The processing liquid is supplied to the processing tank 71 through the control valve 77 and the guide path 78, with the type and amount of the processing liquid being supplied controlled by a control system (not shown).

It should be noted that the temperature of the processing liquid is likely to be lower than that of the processing heavy hot water due to the temperature being taken away by the supply piping, the processing tank, and the disk film 20 itself, so the following measures are taken.

First, before the color development processing solution is supplied, the processing tank is preheated with warm air. The hot air is preferably generated by a hot air generator 65 used in the drying process described later. For example, in the illustrated embodiment of the apparatus, the hot air generated by the hot air generator 65 is As shown, the water is supplied from above the guide section 6o through the guide section 60 to the processing tank 71 located below.

In this way, when the preheating of the processing tank 71 is completed,
Next, one color development processing solution is supplied, but the initial supply is as follows:
After being stored in the processing tank 71 for only a few seconds to warm the processing tank 71, the discharge valve 79 is opened to discharge it to the waste tank, and the necessary amount of color developing processing solution is supplied again. In the case of supplying the bleach-fix processing solution, such measures are unnecessary since the processing tank 71 has already been sufficiently warmed by the color development processing.

Although not shown, it may be possible to supply warm air from the hot air generator 65 into the processing liquid guide path 78 and to supply the warm air to the processing tank 71 through the guide path 78. .

Once the stabilization process is completed, the hot air generator A165
As a result, while supplying hot air through the guide section 60 and rotating the disc film 20, dry explosion of the processed disc film 20 is performed. At this time, as the disc film 20 rotates, the processing liquid attached to the disc film 20 may be scattered around due to centrifugal force.
This can be effectively prevented by supplying hot air through the guide section 60.

When the series of processes described above are completed, the disc film 2
0 is pulled up from the processing tank 71 and dropped into a guide section 72 arranged in parallel with the processing tank 71. The disc film 20 dropped into the guide section 72 is transferred to the guide path 73 immediately through the guide section 72 or by rotating the guide section 72 clockwise in the drawing, and is transferred downward while rotating in the guide path 73. It is housed in a case 80 prepared for.

Note that the drawing shows a state in which the entrance of the guide path 73 is already in communication with the outlet of the guide section 72, and during the developing process, the processing tank guide section 10 is moved by the linear movement of the support member, and the ivy is moved. For example, the entrance of the guide path 73 is shifted toward the processing tank 71 and is shielded from light. Therefore, when discharging the processed disc film, the processing tank 71
, it is necessary to linearly move the block forming the guide portion 72 to the illustrated state. It is also possible to configure the entrance of the guide path 73 to be in a light-blocking state by the rotational movement of the block.

The case 80 is preferably made of hard transparent synthetic resin and is used to prevent the surface of the disc film from being scratched, and more preferably, the disc film 20 is
It is constructed so that it can be set for printing or projection while it is stored in the storage compartment.

As shown in the figure, a plurality of cases 80 are prepared in succession in a state of being biased in the direction of the arrow within the frame, and when the processed disc film 20 is stored in the leading case 81, the pushing member 82 operates in the direction of the arrow to eject the case 81 of 20 disk films from the machine, and the case 80 for the next use is guided to the leading position.

Incidentally, in the above description, only one protective case is prepared, and this does not exclude a mode in which the protective case is prepared in the discharge section by the operator each time the processing is performed.

The light shielding plate 50 and the stopper 51 are returned to their original positions in conjunction with or before or after the ejecting operation of the processed disc film, and the empty cartridge 11 is ejected out of the machine through the insertion port 30 by the reverse rotation of the worm 42. .

The stabilization treatment in the present invention may be ordinary water washing or stabilization treatment, but treatment using a stabilizing solution as an alternative to water washing is preferably used.

Here, "processing with a water-washing alternative stabilizing solution" refers to a stabilizing treatment that is performed immediately after processing with a processing solution that has a fixing ability (stabilizing solution or bleach-fixing solution) and does not substantially involve washing with water. The processing liquid used for the stabilization treatment is called a washing alternative stabilizing solution, and the processing tank is called a washing alternative stabilizing bath (tank).

In the following description, the stabilizing liquid is not limited to the water and the washing substitute stabilizing liquid, but includes ordinary washing water and the stabilizing liquid.

Examples of compounds preferably used in the stabilizing solution include chelating agents having a chelate stability constant of 8 or more for iron ions, and these are preferably used to achieve the object of the present invention.

Here, the chelate stability constants are L, G, 5illen
・A.E. Martell, “5tabilit”
y Con5tants of Me-talion
Complexes”* The Chemical
5ociety, London' (1964),
Written by S. Chaberek-A. E. Marte11;
'Organic Sequestering Age
nts”, a constant generally known by Wiley (1959) and others.

Examples of chelating agents having a chelate stability constant of 8 or more for iron ions that are preferably used in the stabilizing liquid include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, SSa phosphoric acid chelating agents, polyhydroxy compounds, and the like. Note that the above-mentioned iron ion refers to ferric ion (Fe 3 *
) means.

Specific examples of compounds of chelating agents having a chelate stability constant of 8 or more with ferric ions include, but are not limited to, the following compounds: ethylenediamine diorthohydroxyphenylacetic acid , diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminenipropionate, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, transcyclohexanediamine Tetraacetic acid, glycol ether diamine tetraacetic 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-diphosphonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexamethalin. and particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,
1-diphosphonic acid, among others, 1-hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

The amount of the above chelating agent used is 0.01 to 1 Jl of stabilizing solution.
The amount is preferably 50 g, more preferably in the range of 0.05 to 20 g.

Furthermore, ammonium compounds are particularly preferred as compounds to be added to the stabilizing solution.

These are supplied by ammonium salts of various inorganic compounds, including ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, and fluoride. , ammonium, acidic ammonium fluoride, ammonium fluoroborate, ammonium arsenate, ammonium bicarbonate, ammonium hydrogen fluoride,
Ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate,
Ammonium acetate, ammonium adipate, ammonium laurintricarboxylate, ammonium benzoate,
Ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium phthalate, ammonium hydrogen tartrate, ammonium thiosulfate, ammonium sulfite, ammonium ethylenediaminetetraacetate, secondary ethylenediaminetetraacetic acid Ammonium iron, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,4.6-)-linitrophenol ammonium and the like. Among these ammonium compounds, ammonium thiosulfate is particularly preferred in achieving the effects of the present invention.

The amount of ammonium compound added is 1. OX 10-' or more is preferred, more preferably 0.001 per sentence of stabilizer
~5.0 mol, more preferably 0.002 mol
~1.0 mol.

Further, it is desirable that the stabilizing solution contains sulfite to the extent that bacteria will not be generated.

The sulfite to be contained in the stabilizing solution may be any organic or inorganic substance as long as it releases sulfite ions, but inorganic salts are preferred, and specific preferred compounds include sodium sulfite, potassium sulfite, and ammonium sulfite. , ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfide, sodium cartaraldehyde bisbisulfite, sodium cohelic aldehyde bisbisulfite, etc. It will be done.

The above sulfite is present in the stabilizing solution at least 1.0 x 10-'
It is preferable to add the amount of mol/l,
More preferably 5 X 10-' mole/vertical to 1, OX
It is added in an amount of 10-1 mol/cm. Although it may be added directly to the stabilizing solution, it is preferable to add it to the stable replenisher.

The stabilizer used in the present invention desirably contains an anti-pyre agent, which can further improve sulfurization prevention and image preservability.

Preferable anti-spill agents to be added to the stabilizer of the present invention include sorbic acid, benzoic acid compounds, phenol compounds, thiazole compounds, and lysine compounds.

Guanidine compounds, carbamate compounds, triazole compounds, 1 morpholine compounds, quaternary phosphonium compounds, ammonium compounds, cylindrical compounds, isoxazole compounds, propatoolamine compounds, sulfamide compounds.

These are pyronone compounds and amino compounds.

The benzoic acid compounds include salicylic acid, hydroxybenzoic acid, and ester compounds of hydroxybenzoic acid, such as methyl ester and ethyl ester.

There are propyl esters, butyl esters, etc.

Preferred are n-butyl ester, isobutyl ester, propyl ester and salicylic acid of hydroxybenzoic acid, and more preferred is a mixture of the three hydroxybenzoic acid esters.

The phenolic compound is a compound that may have a halogen atom, a nitro group, a hydroxyl group, a carboxylic acid group, an amino group, an alkyl group (especially an alkyl group whose alkyl group is a C1-6 alkyl group), or a phenyl group as a substituent. Among them, preferred are ortho-phenylphenol, ortho-cyclohexylphenol, nitrophenol, chlorophenol, cresol, guaiacol, aminophenol, phenol and the like.

The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, and is preferably 1,2-benzisothiazolin 3-one, 2-methyl-4-isothiazolin 3-one, or 2-octyl-4-isothiazolin. 3-one, 5-chloro-2-methyl-4-isothiacyli-3-one, 2-(4-thiazolyl)benzimidazole.

Specifically, pyridine compounds include 2,6-dimethylpyridine, 2,4,6-)limethylpyridine, radium-2
-Pyridinethiol-1-oxide and the like, preferably radium-2-pyridinethiol-1-oxide.

Specifically, guanidine compounds include cyclohexidine,
Examples include polyhexamethylene biguanidine hydrochloride, dodecylguanidine hydrochloride, etc., and dodecylguanidine and its salts are preferred.

Specific examples of carbamate compounds include methyl-1-(butylcarbamoyl)-2-benzimidazole carbamate and methylimidazole carbamate.

Specific examples of morpholine compounds include 4-(3-nitrobutyl)morpholine and 4-(3-nitropropyl)morpholine.

Quaternary phosphonium compounds include tetraalkylphosphonium salts, tetraalkoxyphosphonium salts, etc.
Preferred are tetraalkylphosphonium salts, and more specific preferred compounds are tri-n-butyl-tetradecylphosphonium chlorite and triphenyl-nitrophenylphosphonium chloride.

Specific examples of quaternary ammonium compounds include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, alkylpyridium salts, and more specifically dodecyldimethylbenzylammonium chloride, dodecyldimethylammonium chloride, and laurylpyridinium. There are chloride etc.

・Specifically, urea-based compounds include N-(3,4-dichlorophenyl)-N'-(4-chlorophenyl)urea, N
-(3-trifluoromethyl)-N"-(4-chlorophenyl)urea and the like.

Specific examples of isoxazole compounds include 3-hydroxy-5-methyl-isoxazole.

Proptool amino compounds include n-proptools and isoproptools, specifically DL-2-benzylamino-1-proptool%3-diethylamino-
1-propanol, 2-dimethylamino-2-methyl-
1-propatur, 3-amino-1-propatur, idopropaturamine, diisopropaturamine, N
, N-dimethyl-isopropanolamine, and the like.

Specifically, sulfamide compounds include 0-nitrobenzenesulfamide, p-aminobenzenesulfamide, fluorinated sulfamide, 4-chloro-3,5-dinitrobenzenesulfamide, and α-amino-p-toluenesulfamide. famid, sulfanilamide, acetosulfaguanidine, sulfathiazole.

Examples include sulfadiazine, sulfamethacine, sulfamethacin, sulfine oxazole, homosulfamine, sulfamidine, sulfaguanidine, sulfamethizole, sulfapyrazine, phthalisosulfathiazole, succinylsulfathiazole, and the like.

Specific examples of pyronone compounds include dehydroacetic acid and the like.

A specific example of the amino acid compound is N-lauryl-β-alanine.

Specific examples of triazole compounds include 2-aminotriazole, benzotriazole, and 5-methyl-benzotriazole.

Among the above-mentioned anti-spill agents, compounds preferably used in the present invention are thiazole compounds, sulfamide compounds, and pyronone compounds.

The amount of anti-piping agent added to the stabilizer is 0.
It is preferably used in a range of 0.001 to 30 g, more preferably in a range of 0.003 to 5 g.

The stabilizing solution in the present invention preferably contains a metal salt in combination with a chelating agent.

Such metal salts include Ba, Ca, Ce,
Co, In.

La, Mn, Nj, Bi, Pb, Sn, Z
It is a metal salt of n, Ti, Zr, Mg, AiL, or Sr, and can be supplied as an inorganic salt such as a halide, hydroxyl, compound, sulfate, carbonate, phosphate, or acetate, or as a water-soluble chelating agent. The usage amount is per liter of stabilizer I
It ranges from X 10-' to IX 10-" mol, preferably from 4x 10-' to 2x 10-" mol.

In addition to the above, aldehydes may be contained in the stabilizer of the present invention. Here, aldehydes refer to compounds having an aldehyde group.

As for specific compounds.

l Formaldehyde 2 Acetaldehyde 3 Propionaldehyde 4 Isobutyraldehyde 5 N-Butyraldehyde 6 N-Valeraldehyde Isovaleraldehyde 8 Methyl ethyl acetaldehyde 9 Trimethyl acetaldehyde 10 N-Hexaldehyde 11 Methyl-n-butylacetaldehyde 12
Isohexaldehyde 13 Glyoxal 14 Malonaldehyde 15 Succinic aldehyde]6 Glutaraldehyde 17 Acetaldehyde 18 Methylglyoxal 19 Acetoacetic aldehyde 20 Glycolaldehyde 21 Ethoxyacetaldehyde 22 Aminoacetaldehyde 23 Betainaldehyde 24 Chloral 25 Chloracetal Dehyde 26 Dichloroacetaldehyde 27 Promal 28 Dichloroacetaldehyde 29 Iodoacetaldehyde 30 α-Chlorpropionacetaldehyde 31
α-bromopropionacetaldehyde 32 Furfural can be mentioned.

The above aldehydes are 0.1 to 50g per liter of stabilizing solution.
It is preferable to contain it in the range of 0.5 to 10.
The content is preferably within the range of g.

The stabilizing liquid used in the present invention contains at least one compound selected from the following - Soft formula [11], - Soft formula [11], and a water-soluble organic siloxane compound.

In view of its effect on the purpose of the present invention.

Particularly preferred.

General formula [I] A-0-(B), -xt In the formula, A is a monovalent organic group 1, for example, having 6 to 20 carbon atoms.
, preferably an alkyl group of 6 to 12, hexyl,
An aryl group representing heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc., or substituted with an alkyl group having 3 to 20 carbon atoms, and preferably an alkyl group having 3 to 12 carbon atoms as a substituent. and propyl and butyl.

Represents pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc.

Examples of the aryl group include phenyl, tolyl, xylyl, biphenyl or naphthyl, preferably phenyl or tolyl. The positions where an alkyl group is bonded to an aryl group are ortho and meta.

Any position may be used, B represents ethylene oxide or propylene oxide, m represents an integer from 4 to 50, sX
2 represents a hydrogen atom, 5O3Y or LkP (hYt).

Y represents a hydrogen atom, an alkali gold E (NA, K or Li, etc.) or an ammonium ion.

General formula [■] R.

a In the formula, R, , n, , R, and R7 are each a hydrogen atom,
It represents an alkyl group or a phenyl group, and the total number of carbon atoms in R4, Rs, R6, and R7 is 3 to 50. Indicates an anion such as a sulfonic acid group.

The above-mentioned water-soluble organic siloxane compounds are 1, for example, JP-A No. 47-18333, JP-B No. 55-51172, JP-A No. 55-51172;
1-37538, JP-A-49-62128, and US Pat. No. 3,545,970, etc., it means a general water-soluble organic siloxane compound.

Next, specific representative examples of the compounds represented by the general formulas [I] and [II] and water-soluble organic siloxane compounds of the present invention will be listed, but the invention is not limited thereto.

(Example of compound represented by soft formula [I]) I-I CiJ*10 (CJ<0)*oHr-2Cm
HltOCCxsHsO)ssHI-3CaHtoO(
CJ40) JOJaI-4C5oHt+0 (CJ40)
tsPOJa*1-5 CaHsv Q 0(CJ
<O) molI-6C91119Q o(c2n, o
)4soffsaI-10C91119Q O(C
:111110)28HI-12Cs1(,s Q
0(CJJ)r. 11 (Example of compound represented by soft formula [11]) (Water-soluble organic siloxane compound) C3H&+OC,114hOH CJs+0CdL +1゜0H C3H6+ 0CJ4h OCNz m-498・l11-5 CI・m-71i:H3 m-8(: , H・C3■a+0CJ4 h 0CJs (ChCHJ hH a+bm30 (CH2CH20+-IIH a+b=41) Among the water-soluble organic siloxane compounds, the compound represented by the following soft formula [m] particularly exhibits the desired effect of the present invention. Therefore, it is more preferably used in the present invention.

In the general formula [■CO(CH*)--(OCI(□C)1.)Q-Ra formula,
R8 represents a hydrogen atom, a hydroxy group, a lower alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, propyl, etc.), and R9+ RIG and R11 each represent may be the same or different; n represents an integer of 1 to 4; p and q are 1 to 4;
Represents an integer of 15.

These compounds represented by the soft formulas [I] and [II] and the water-soluble organic siloxane compounds may be used alone or in combination. Further, good effects can be obtained when the amount added is in the range of 0.01 to 20 g per 11 stabilizers.

Furthermore, other compounds that can be added to the stabilizing solution in the present invention include organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), p) l! Although there are buffering agents (phosphoric acid, borate, hydrochloric acid, sulfuric acid, etc.) or surfactants, the amount of these compounds added depends on the pH of the stabilizer according to the present invention.
Any compound may be used in any combination as long as it is necessary to maintain the color photographic image's stability during storage and does not adversely affect the occurrence of precipitation.

The pl+ of the stabilizer used in the present invention is not particularly limited, but is preferably in the range of pH 0.5 to 12.0,
More preferably, the pH is in the range of 5.0 to 9.0, particularly preferably in the range of pH 6.0 to 9.0.

The processing temperature during stabilization is 50°C or less, especially 15°C.
°C to 50 °C is preferred, more preferably 30 °C to 45 °C
°C range is better, and the shorter the treatment time from the viewpoint of rapid processing, the better, but usually 20 seconds to 10 minutes,
The most preferred time is 30 seconds to 90 seconds.

The stabilization treatment according to the present invention is preferably carried out 2 to 20 times, more preferably 4 to 10 times.
The composition of the stabilizing liquid may be different from one time to another.

The processing method of the present invention is color development-bleach-fixing-stable processing, and the total processing time is preferably within 6 minutes, more preferably within 5 minutes, and particularly preferably within 2 minutes. The processing time ranges from 1 minute to 3 minutes and 30 seconds, and it is most preferable to immerse a portion of the disk film in the processing solution and perform the processing while rotating.

[Example〕 The present invention will be explained below using experimental examples.

Sample disc film Konishiroku Photo Industry Co., Ltd. disc film Konic
a IIRDisc Film was used.

Potassium carbonate 30 g Sodium sulfite 2.5 g Diethylenetriaminepentaacetic acid 2.0 g Hydroxylamine sulfate 2.5 g 6-Aminopurine
0.1 g sodium bromide
1.3g potassium hydroxide 1.
0.g Color developing agent (CD-4) 0
．． 0.3 molar water was added to make the IQ, and the pH was adjusted to 10.2 with 50% sulfuric acid and potassium hydroxide.

Ferric ammonium complex salt of ethylenediaminetetraacetic acid (ED)
TA FeI[I] 0.5 dry ammonium iodide 500g polyvinylpyrrolidone (K value 17) 30g aqueous ammonia (282)
The pH was adjusted to 11 with 10 ml of water, and the pH was adjusted to 5.6 with acetic acid and aqueous ammonia.

Stable liquid 1st stable liquid Water only (tap water) 2nd stable liquid Exemplary compound 1 (formaldehyde) Ig exemplified compound I-51g 3rd stable liquid 5-chloro-2-methyl-4-isothiazolin-3-one 0.01g2 -Methyl-
4-Isothiazolin-3-one 0.01 g Hexamethylenetetramine 2.0 g Ammonium sulfite 1.0 g Conidax (manufactured by Konishi Rokushanu Kogyo Co., Ltd.) Sml water was added to finish to lH.

Experiment 1: The above sample disk film was subjected to the following treatment 10 times in a row using the automatic processor shown in the figure, and then the yellow dye density of D wax was compared between the 1st and 10th treatments.
Table 1 shows the 10th concentration when the concentration was 0%.

Color development processing solution volume: 1 ml, solution temperature: 48°C, processing time: 1 minute, rotation speed: 20
0rp■, Bleach-fix processing solution volume 15m, solution temperature 55°C, processing time 1 minute, rotation speed 2
00 rpm, stabilization treatment (water washing treatment) 30 tsfl of water at a temperature of 48 ° C. (first stabilization liquid) was continuously supplied to the treatment tank, 0 rotation speed was 200 rpm, treatment time was 1 minute, Experiment 2: In Experiment 1, the stabilization treatment was performed using the following invention. The only difference was in the method.

Water with a stable treatment temperature of 48°C (first stable liquid) 10+si was collected in a treatment tank and treated for 16 seconds (rotation speed 200 rp),
This process of discharging within seconds was repeated three times.

Experiment 3: The only difference from Experiment 2 was that a second stabilizing solution was used as a stabilizing treatment.

Experiment 4: The only difference from Experiment 2 was that a third stabilizing solution was used as a stabilizing treatment.

Table 1 As is clear from Table 1, D wax is 15 in comparison
3%, which was found to be unfavorable as there was a large variation between the 1st and 10th times. On the other hand, in the present invention, the D wax hardly changed between the first and the 10th time, and the process was stable, which was found to be very preferable.

[Effects of the Invention] According to the present invention, it is possible to perform rapid processing using a single tank, and to effectively prevent fluctuations in photographic performance due to contamination of the color development processing solution by the bleach-fixing solution. It is possible to achieve the above objectives.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing an example of an automatic developing apparatus of the present invention, and FIG. 2 is a schematic diagram of a hot water bath. In the figure, each symbol indicates the following. rO: Film unit 11: GL light window side plate 12: Opening 1 Conilabel side plate 14: Exposure window 20: Disk film 30: Insertion slot 40: Running member 41 Guide rail 42: Worm 43: Holding member 5a: Light shielding plate 51: Stopper 52: Push-out pin 53: Swinging member 60: Guide section 61: Stopper 62 Nissin spindle shaft 63 Nissin spindle shaft 65: Hot air generator 70: Processing section 71: Processing tank 72: Guide section 73: Guide path 74: Processing Liquid tank 75: Hot water bath 76: Guide pipe 77: Control valve 78: Guide path 79: Discharge valve 80: Case 81: Case 82: Push-out member

Claims (5)

[Claims] (1) A method of processing a photographic material by using a single processing tank and repeating sequentially supplying and discharging a color developing solution, a bleach-fix solution, and a stabilizing solution to the processing tank, the method being stable as the stable processing. 1. A method for processing a photographic material using a single tank, characterized in that processing is carried out at least twice using a liquid. (2) A method for processing a photographic material using a single bath according to claim 1, wherein the photographic material to be processed is a disk film. (3) A method for processing a photographic light-sensitive material using a single bath according to claim 2, wherein the number of sheets of photographic light-sensitive material to be processed at one time is from one to ten or less. (4) A method for processing a photographic material using a single bath according to any one of claims 1 to 3, wherein the stabilizing liquid is a washing substitute stabilizing liquid. (5) An automatic processing apparatus for processing a photographic material by using a single processing tank and repeatedly supplying and discharging a color developing solution, a bleach-fixing solution, and a stabilizing solution to the processing tank in sequence, the processing device comprising: An automatic development processing apparatus characterized by having a configuration in which a stabilizing solution is repeatedly supplied and discharged two or more times during processing.