JPS59151155A - Method for processing color photograph - Google Patents

Abstract

PURPOSE:To bleach and fix rapidly a color photograph without exerting unfavorable influence on the photographic characteristics by adding a specified compound to a bleach-fix bath contg. a ferric complex salt or its preceding bath. CONSTITUTION:A compound represented by formula I (where n is 1, 2 or 3; each of R1 and R2 is H, 1 or 2C akyl or 1-3C acyl; both of them are not H; and they may bond to each other to form a ring), e.g. a compound represented by formula II is used. When an exposed color photographic silver halide material is color-developed and desilvered, about 2X10<-6>-2X10<-1>mol/l said compound is added to a bleach-fix bath contg. a ferric complex salt or its preceding bath behind a color developing bath. Said method shows an especially remarkable effect when applied to a color reversal photosensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photographic processing methods. The details relate to an improved bleach-fixing method. In particular, the present invention relates to an improved method and a 1"lt composition which feature the use of a bleach accelerator to enhance the bleach-fixing power.

Generally, the basic steps in the processing of silver halide color photographic materials are a color development step and a desilvering step.

That is, a silver halide color photographic material is exposed to light,
Enter the color development process. Here, the halogen f silver is reduced by the color developing agent to form oxidized coloring dust, and the oxidized color developing agent reacts with the coloring agent to form the 1III image of the dye. give. Afterwards, the color photographic material is subjected to a desilvering process. Here, the silver produced in the -IJ step is oxidized by the action of an oxidizing agent (commonly referred to as a bleaching agent), and is then removed by a complexing agent, commonly known as a fixing agent.

Therefore, the photographic material VC that has undergone these steps produces only one dye image. The actual cultivation process includes the two basic steps of opaque development and desilvering described above, as well as l[!
I11 Elephant! 4. It includes auxiliary steps to maintain the true physical quality or to improve the preservation of the image. For example, excessive softening of the photosensitive layer during processing? Examples include a hardening agent to prevent the development reaction, a stop bath to effectively stop the development reaction, an image stabilization bath to stabilize the image, and a film removal bath to remove the backing R4fr of the support.

In addition, the above-mentioned 7ζ desilvering step may be carried out in one step using a concentrated fixing bath in which a bleaching agent and a fixing agent coexist, or may be carried out in two steps, a bleaching bath and a fixing bath, using separate baths.

Generally, red blood salt is used as an oxidizing agent in bleaching solutions. However, the disadvantages of bleaching solutions using red blood salt are that the bleaching solution must be replaced when it is exhausted, and that ferricyanide ions and their reduced forms are emitted due to overflow during processing and carried into the washing water after bleaching. The ferrocyanide ion undergoes photochemical oxidation to completely generate cyanide U. These cyanide compounds are highly toxic and cause great harm.

On the other hand, potassium dichromate, ferric ion complex salts, persulfates, quinones, @salts, etc. have traditionally been used as internal polishing materials other than red blood salts, but they have weak oxidizing power and are difficult to handle. It has its drawbacks.

In recent years, in color photographic materials, from the viewpoint of rapid and simple processing and prevention of environmental pollution, ferrous ion complex salts (e.g., aminopolycarboxylic acid ferric ion complex salts, etc.), especially EDT A-iron (III The 7C whitening treatment method is mainly used for 7C complex salts.

Ferric ion complex salts are sometimes used as bleaching agents in color photographic paper (Germany).
No. 6θj, No. 77A, No. 410, British 'Jihoki 74'
A, , t A No. 7, same 5. ″?33,0ft
No., same No./, θ/41, 3rd issue': ψ's Meipa 111 Ho).

However, bleach fixatives containing ferric and ferric ion complex salts
- due to weak acid r
Silver? However, it is rarely used in color photographic materials that use silver iodobromide.

Therefore, it is desirable to increase the bleaching power (or oxidizing power) of the 7f solution by using a λ iron ion/complex salt.

The object of the present invention is, firstly, to provide a novel bleaching accelerator that does not adversely affect photographic properties, and a color photographic processing method using the same to perform a white fixing process. It's about getting. The second object is to obtain a rapid color photographic processing method using such a bleach accelerator. Thirdly, how to quickly bleach and fix color photographic materials with photographic sensitivity? It's about getting.

As a result of various studies, the present inventors found that a compound represented by the following general formula may be added to a bleach-fixing bath or a pre-bath (defined as a bath between a color developing bath and a bleach-fixing bath) containing a ferrous ion complex salt. By containing the above-mentioned object, the above object was achieved.

It is an integer from n to 3. R1 and R2 represent a hydrogen atom, a lower alkyl group having 2 carbon atoms, or an acyl group having 1 to 3 carbon atoms (however, both R1 and R2 are not hydrogen atoms). TI (t and R2 may form a ring with each other. Preferred compounds are compounds in which either R1s R2 is -CU CH3 or -COC2Hs and the other is a hydrogen atom, or R1 and R2 are both CH3 or C2
This is a compound that is H5.

Specific examples of the compounds of the general formula used in the present invention include the following, but the present invention is not limited to these exemplified compounds.

Is the complex of the present invention a ferrous ion complex salt? It is an excellent bleaching accelerator in the cutting fixer.

The intermediates of the present invention can be easily synthesized by known methods, and typical examples are shown below.

Compound ('') synthesis method thiourea 76? This KN-(,2-chloroethyl)-tmethylamine salt 1 is dissolved in ethanol-zsotnl. l! Ethanol M solution of 21 vol. 31 liters! 00rn
Add 7 JD of the solution and heat under reflux for 6 hours. After the reaction, the mixture is cooled and mixed with 2,000 ml of ethyl acetate and 2,000 ml of groin.

Collection fig♂f'r ('l1fy) mp'7''~J
``Cc then obtained thiuronium salt 33?r total cold water 30
Dissolve θtnlVc and add 1. ? r
An aqueous solution containing toOtrtl is added to perform hydrolysis. The reaction solution was extracted with ether soomi, dried, and distilled under reduced pressure to obtain the desired product.

)) pJ /θg0c Yield J-, xyr +1
5%).

Compound (41) Co-aminoethanethiol 77'?rk acetic acid 300ml
Dissolve the VC, and add acetic anhydride to it gradually for 2 minutes under full stirring. After dropping, heat on a hot water bath for 1 hour and cool. Acetic acid, water acetic acid? After distillation, an acetyl compound is obtained by distillation under reduced pressure.

1) p43 /i<t~iig'c Collect'ik7/,
'l! rt+40%).

Acetyl form/27rk ethanol 20 mlvcmI
Js, then cool it down and add 10.3 fl of hydrogen peroxide solution.
Drop r. After concentration under reduced pressure, the reaction product becomes candy-like, and if left standing, crystals will form.

ITI pg 7°C collection Jij'? r (3J%).

Other compounds can also be synthesized according to these synthesis methods.

The crystal whitening accelerator used in the present invention is dissolved in a bleach fixing bath or an ID prebath (a bath after color development W, ironing and before bleach-fixing treatment) at an arbitrary concentration of 65% depending on the type and purpose of the product. However, the amount of about λ x 10 to about 2 x 10-1 mol per lt of solution is about 1
It is often used again, preferably /×lθ ~×1
Use within the range of 0 mol.

No. 1 used in pear cutting and l- of the present invention! The iron ion complex salt preferably uses an organic fak compound as a ligand, especially an organic chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or a salt thereof. Polycarboxylic acid manganese is preferred because its salts are highly valent and there is relatively little risk of causing pollution.

These saliva fluids are excellent in that they do not have the disadvantages of red blood salt prohibition, such as the following. First, use red blood salt 1 (
Jshi (', λ The white liquor is getting tired and the bleaching solution has to be replaced, jjL2 is over 70% during processing.
- Are ferricyanide complex ions and ferrocyanide complex ions discharged when brought into washing water after bleaching and ferrocyanide oxidation caused by photo-1 arsenic oxidation? Highly toxic cyanide? It has disadvantages such as generating and causing great harm ♀.

Examples of these aminopolycarboxylic acids and aminopolyphosphones or their IMs can be listed below. Namely, ethylenediamine triacetic acid (ethylenediamine/tetraacetate, its disodium salt, diammonium tAAs tetra(trimethylammonium) salt, tetrapotassium salt, tetrasodium salt, trisodium diethylenetriamine (tetraacetate),
(diethylenetriamine, ntaacetic acid, its pentasodium salt, etc.), ethylenediamine-N-1β-4xethyl)-N,N', N'-triamine (this acid, its trisodium salt, triammonium Fa l etc.)
, propylene shea mince], Utori
(this acid, its trisodium salt, etc.), zoclohexanediaminetetraacetic acids (this acid, its disodium salt, etc.), other iminodiacetic acids, dihydroxyethylglycines, ethyl etherdiaminetetraθ1mic acids,
Glycol ether diamine tetraacetic acids, ethylenediaminetetrapropionic acids, phenylenediaminetetraacetic acids, 7,3-diaminopropanol N-N14
N'.

N'-tetramethylenephosphonic acids, ethylenediamine N, N, N', N'-tetramethylenephosphonic acids, l
, 3-propyleneamine-N,N.

N/, N/-tetramethylenephosphonic acids.

Examples of base materials for forming salts with aminopolycarboxylic acids and aminopolyphosphonic acids include caustic alkali (alkali metal hydroxide), ammonia, and amines. Examples of alkali metals include sodium, potassium, and lithium, and examples of amines include methylamine, diethylamine, triethylamine, butylamine, alkylamines, U-ring ring amines such as nocrohexolamine, aniline, and m-)luidine. and heterocyclic amines such as pyridine, morpholine, and lysine.

The ferric ion complex salt may be added to the bleach-fixing bath in the form of a complex. Also, ferric salts (e.g. ferrous sulfate, ferric chloride,
Ferric nitrate, ferrous ammonium sulfate, ferric phosphate, etc.) and a chelating agent such as aminopolycarboxylic acid or aminopolyphosphonic acid are added to the bleach-fixing bath and the An iron ion complex salt may be formed. When adding in the form of a complex, one type of complex salt may be used,
Further, complex salts of more than these types may be used. On the other hand, when using a ferric salt and a chelate (all arsenic agents) to form a heavy substance in a solution, one or more types of ferric salts may be used. In addition, seven types of chelating agents may be used. Alternatively, more than one type of chelating agent may be used. In any case, the chelating agent may be used in excess of the amount required to release the so-called "iron ion complex".

The fixing agent used in the bleach-fix solution of the present invention is a conventional fixing agent (for example, thiosulfate such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate; sodium thiocyanate, ammonium diocyanate, thiocyanic acid). Thiocyanates such as potassium; ethylenebisthioglycolic acid, 3.t-
Water-soluble silver halide solubilizers such as thioether compounds such as dithia-/, l-octanediol, etc. can be used alone or in combination in an amount of 1j-2j or more.

The content of each component in the bleach-fix bath is approximately 0, i~1 mol for the iron ion complex per bleach-fix solution, and approximately 0 for the fixing agent.
1-! ~ μmol.

In addition to the above-mentioned additives, sulfates (eg, sodium sulfate, potassium sulfite, and ammonium sulfite) can all be added to the bleach-fixing bath. Furthermore, 11 compounds having already known bleach-fixing accelerating properties (for example, Japanese Patent Publication No. 1973.
Polyamine compounds described in s-J Za3 Otsu Publication, thiourea derivatives described in Japanese Patent Publication No. Shogu J-♂j''01, German Patent No. 1, /, 27.

Iodide described in No. 71j Akito, Germany's Permit No. 61
,．． 4110, the polyethylene oxides described in German Patent No. 1. Lid 0. The nitrogen-containing heterocyclic compounds described in the specification of No. f12, other thioureas), etc., may be present in one or more types. In addition, the bleach-fix solution p l-
In use, 1 is usually approximately θ~g, θ, particularly preferably Y'iJ-, θ~7.0.

The bleach-fixing bath used in the present invention contains a complex salt of ferric ion and the above-mentioned novel bleach accelerator;
Examples include ammonium, alkali metal chlorides, and iodine. ] may also be included.

Honuramei's Kinpaku I liquid further contains boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, >47 acid, sodium phosphate,
p[l buffering capacity of citric acid, sodium citrate, tartaric acid, etc.? Inorganic acids, organic acids and salts thereof can be added.

When the chemicals used in the bleach-fix bath mentioned above are used in combination with the bleach accelerator of the present invention, do they form a bleach-fix composition? It can be prepared.

The above bleach-fix solution or composition thereof can be used as a solution used in the bleach-fix step or as a replenisher for the bleach-fix solution in use.

The present invention is applicable to halogenated color paper, color negative film, color reversal film, color positive film, etc. It can be applied to any processing of all the color light-sensitive materials used, and can enhance the effect of promoting desilvering. The present invention is more effective for color negative films and color reversal photosensitive materials, and is particularly effective for color reversal photosensitive materials.

When the bleach accelerator of the present invention is added to a bleach fixing solution or a prebath (for example, the first stop and bath), silver can be sufficiently bleached and fixed in a short period of time.

Halogen monoarsenic color photographic photosensitive material used in the present invention t・↓
The iodine content in the iodine arsenic is not particularly limited, but it is preferably about / -, i' molt, more preferably 3 to 7 molt.

The processing steps for color reversal sensitive materials are usually, for example, black and white development (trough) → stop (bath) → washing with water → fogging (bath) → washing with water → color development (bath) → stop (bath) → (during film (bath)) The order is → washing with water → bleach-fixing (bath) → washing with water → stabilization (bath) → drying. Further, during these steps, a pre-bath, a pre-hardening bath, a neutralization bath, etc. can be provided. On the other hand, a stabilizing bath, washing with water before and after bleaching and fixing, etc. can be omitted from the above steps.

The covering bath is made of t-butylamine borane, natriuno,
It is also possible to use a processing bath containing all of the borohydride and Sr+lT[) complexes and cover the coloring field and in front of the image before color development. Also, by adding a fogging agent (e.g. t-butylamine borane, sodium borohydride, etc.) to the color developing solution, a fogging bath can be used. Can be omitted. It's a good thing, the cover bath can be converted into light again.

The treatment temperature of each treatment step can be about 2θ°C to 70°C, preferably 30°C to 70°C.

Suitable for processing π color processing method, inverted color feeling f4
1 M, coupler 4 contained in the photographic emulsion.
It may be an "inner type" sensitive material, or it may be an "outer type" sensitive material containing the coupler in the total color developing solution (in short, especially in the present invention Vi
(Applicable to reversal color sensitive materials of any design) Commonly used color developing solutions, black-and-white developing solutions (for color reversal processing), stop solutions, etc. can be used.

For example, as the color development mass 1 solution for color reversal processing, the one mentioned in the Examples is typical, but in addition to this, for example, ethylenediamine can also be added to this developer.

The processing steps for color negative light-sensitive materials are usually 11 hours long, for example, photocolor development (bath) -> bleach-fixing (bath) -> washing and drying resistance. Also, during these steps, color development JJ? , A stop (bath), a hardening film (bath), water washing, etc. may be provided between 1.1 and bleach-fixing, and a bath, etc. may be provided between the white fixing and washing. .

The treatment temperature of each treatment step can be about 2θ to 70°C.

Commonly used color developing solutions, stop solutions, hardening solutions, stabilizers and the like can be used.

In addition, photographic silver emulsions and other hydrophilic colloid liquids that can be used in color sensitive materials processed by the color processing method of the present invention and their preparation methods, as well as photographic additives (for printing or photographic element materials), are available. ) For information on NariSearch Disclos
ure J magazine 2 (I 7) 107~/1
Those described on page 0 can be used as appropriate.

EXAMPLE An Ecolor reversal photographic material was prepared by coating each layer on a triacetate film base in the following order.

1st layer (red-sensitive emulsion layer) Coating liquid: Red-sensitive silver iodobromide emulsion (silver iodide niamol%)
and cyan coupler emulsion (cyan coupler/-hydroxy-μm-reco-.2-n-dodecylnaphthamide, dibutyl phthalate as coupler bath agent) and silver/
The mud is poured so that the molar ratio of couplers becomes Jf, 0.

Coated silver amount: 1. sW　Af//Pn　.

No. 21 Hair #f Intermediate layer) A gelatin intermediate layer containing di-t-amyl hydroquinone dispersed therein.

3rd F@ (green-sensitive emulsion layer) Coating solution: green-sensitive silver iodobromide emulsion (silver iodide = t mol%)
and magenta coupler emulsion (as magenta coupler/
-(J,≠,4.-trichlorophenyl) -J
-[3-(,z,μm di-t-amylphenoxyacetamide]benzamide]-j-pyrazolone, tricresyl phosfeld as coupler solvent) and total iron/coloror molar ratio of 7. Mix it so that it becomes j.

Coated silver J[; /, 191117 m2 of No. I# with yellow filter layer) One layer of filter consisting of yellow colloidal silver and gelatin.

No.! Skin (night-sensitive emulsion layer) Coating liquid: Sensitive silver iodobromide emulsion (Yellow coupler emulsion) , Hezy t-amylphenoxy)butanamide]acetanilide, the coupler solvent and (7 dibutyl phthalate) are mixed such that the silver/coupler molar ratio is f,0/.

Standard cloth weight: O1 length 1197m.

After the color reversal film was exposed to light (exposure for 77,700 seconds through a light wedge using a tungsten lamp as a light source), the following reversal process was performed.

Processing process Temperature Time First development (black and white) Stopped for 37OCj Minutes at 37°C Washing with water 37°C for 4 minutes Color development @ (Add brushing agent) Stopped at 37°C for minutes
371 2 minutes water wash 37°C, 2 minutes bleach-fix 37°ca minute or 6 minutes water wash 37°C 2 minutes stable -30 seconds drying 37・C Sodium sulfite to, oil-phenyl-3-pyrazolidone 0.32 Hydroquinone J', Qf Sodium carbonate (-hydrate) μ/, Of Potassium bromide
! , ot potassium iodide (l aqueous solution) 1.0 ml rhodan potassium (/N aqueous solution) to, oml sodium hydroxide λ, θrnl (io ti water bath solution) Add water /, ot composition of stop solution Sodium acetate JOf ice Acetic acid fil Add water Total 4ik it Original color development 1 Composition of liquid Benzyl alcohol j, 0ml Sodium hydroxide o, sy Diethylene glycol 3.0d Sodium hexametaphosphate !, θ? Sodium sulfite
λ,oy potassium bromide λ
, oy μm amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sesquisulfate monohydrate) 10.09 Citrazic acid O, Guameta boric acid o, sy Sodium metafoate tetrahydrate 77, Of sodium boric acid Robo Biride 0. /f Add water to total amount
/, Of-iron(nr)-EDTA-,2Na
lJ o yEDTA-uNa
S? 1NH4) 28203 (70% by weight aqueous solution)/
J' Occ Na2SO34', jf N 1-1.4 (,1)i
/Jcc water? In addition
/ Composition of stabilizing solution Formalin (37%) /θec Fuji Drywell TCC water? In addition, the total amount of the above-mentioned bleach-fix solution, and the same amount of the compound of the present invention (the above-mentioned f.
What is the number? For each /, j1i' / /=, 1 g of edge-based fixing was performed for 6 minutes with the added solution. The binding M remaining in the film after processing (highest size 181 parts and lowest opening 2 places) was determined by fluorescent X-ray analysis, and the results are shown in Table 1.

As is clear from the results of this experiment, the bleach-fixing bath using the compound of the present invention has a greater desilvering promoting effect than the compound described in KUS Patent No. 3r73zaj (FB-/). It can be seen that it has

Example 2 The same procedure as in Example 11 was carried out, except that a bleach-fix solution having the formulation shown in Me below was used in place of the bleach-fix solution used in Example.

The obtained 7ζ results are shown in Table 4.

Shio 1! Composition of white fixer iron(III)-EDTA-jNa i,
2o S'El)TA-, 2Na
S? Nl-J4F3r
/ / OS'tNI(,4)2S203(7
0 double stitch water #liquid) 10θCC Na2SO3It, jf NI-140H/ jcc water? In addition, /l As is clear from this experimental result, in the case of pear white fixed layer bath using the compound of this Komei, especially when using the compound described in US Patent No. 3r23s'tr (B-, 2), It can be seen that this also has a large desilvering promoting effect.

Example ■ A red-sensitive silver iodobromide emulsion (silver iodide 7 molt) was added with l-hydroxy 7-μm chloro J- as a cyan coupler.
By emulsifying and mixing n-dodecylnaphthamide, green sensitive odor f
/-(2', ≠') as a magenta coupler in the llS emulsion (Iodine and Arsenic mole).

t′-trichlorophenyl)-3-(J″-(,2″′
Da'-di-t-amylphenoxyacetamide)-benzamide)-S-pyrazolone was emulsified and mixed, and α- (2-Methylbenzoyl)-acetol (λ'-chloroj'-dodecoxycarbonyl) anilide was emulsified and mixed, and a depression was made on a triacetate film base using the fib, yc color negative photographic light-sensitive material for the following experiment. I did this.

For the emulsification of each coupler, diptylphthalate and trichlorphosphate were used as coupler solvents, sorbitan monolaurate and sodium dodecylbenzenesulfonate were used as milking agents, and /-1p- Nonylphenoxyditrioxyethylene)butane-≠-sulfonic acid sodium saccharide lauric acid ester as a 7P auxiliary agent (li57JII L 7ζ).

After this film was exposed to light, the following processing was performed.

At size 7ζ, the silver h1 remaining in the highest sample sample after treatment was determined by fluorescent X-ray analysis.

) and the results are shown in Iwa.

Processing process Color development phenomenon 1 phenomenon, 2a'c /, 2 minutes stop solution bath 7 minutes hardening bath
Washing water, bleach fixing bath, 5 minutes water
washing g abduction
Composition of dry color developer Benzyl alcohol j lne Caustic soda o, sy Diethylene glycol 3rnl Hexametaphosphoric acid sorter '21/ Sodium fluorosulfate, 2? Potassium bromide 21μm amino-
3-Methyl-N-ethyl-β-hydroxyethylaniline sesquisulfate monohytre), tf metaboric acid θ, 32 Navox 77f Water? In addition
Total amount / stop solution r acidic soda 309
Glacial acetic acid J' tnl
Add water and make the total amount / hardening bath Sodium hexametaphosphate 11 Horsand
l water salt, 207 formalin (3
7chi) lθml! Bleach-fix solution ethylenediaminetetraacetic acid, iron fil+) thorium (,
dihydrate) and 07 Ethylenediaminetetraacetic acid, unodium (-l hydrate) /j7 Sodium carbonate l hydrate /7ii'foric acid
Ammonium associate acid aqueous solution / Bleach enhancer (Table ■
)/! V ptiij,, t and add water and make it 1? :,
.

/ As is clear from the results of this experiment, in the case of the Sayama fixing bath using all the fossil substances of the present invention, IC: -3 to F'-3), the 4 samurai had a 3g73za31- It can be seen that it has a greater desilvering promoting effect than when using all of the F-H compounds in the field (FB-J).

Embodiments of the present invention are described below.

/) The complex of ferric ion is a di-iron complex salt for aminopolycarboxylic acid. Processing method for color photographs.

, 2) /・C? The color photographic material used as a support is at least -I+! It has a silver halide emulsion layer of j, and the silver halide emulsion layer of f is composed of an iodine emulsion having an iodine content of about 1 to 10 molar. Color photographic processing ε described in iliα of claim F.

3) The range of interest for the bleaching accelerator in the silver emulsion in the bleach-fixing bath is from 2 x 10-6 to 2 x 10' mol/l. Color photographic processing methods.

μ) The bleach-fixing bath of the bleach accelerator, the concentration of +A in the bleach-fixing bath, +A is /X/(7'fzi and 3-x10
-2 mol/l color photographic processing method according to the claims.

j) The compound represented by the general formula (1), (2), (
3), (4) Also, the color photographic processing method described in the scope of the patent MRI, which is a product of 51.

6) The content of ferric ion complex salt in the bleach-fixing bath is about 0. / ~,! , Omob/l.

-30゛

Claims (1)

[Claims] In a color photographic processing method in which an exposed silver halide color photographic light-sensitive material is subjected to at least a color development treatment and a desilvering treatment, a bleach-fixing bath containing a ferrous ion complex salt or a Vi pre-bath (
A color photographic processing method characterized in that a compound of the following general formula is contained in a bath (defined as a bath used after color development and before processing with a bleach-fix bath).