JPH02171748A - Color photograph development bath and method - Google Patents

Abstract

PURPOSE: To accelerate development of the lowest yellow layer and to obtain a good color balance by using two developing baths different from each other in a content of a developer and that of halides. CONSTITUTION: The silver halide photosensitive material having at least 3 photosensitive silver halide emulsion layers containing cyan and magenta and yellow couplers different in spectral sensitivity on a reflective support is imagewise exposed and developed in 2 steps by using the developing baths I and II, and the bath I contains a developer more than the bath II and the bath I contains the halides less than the bath II, thus permitting the development of the lowest yellow layer to be accelerated and a good color balance to be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a light-sensitive silver halide emulsion layer comprising at least three light-sensitive silver halide emulsion layers of different spectral sensitivities, each associated with a cyan coupler, a magenta coupler and a yellow coupler, on a reflective layer support. The present invention relates to a color photographic developing bath for developing silver halide materials.

Here, development takes place in developer baths I and II, provided that in the state of use of the developer baths, the developer content in developer bath (1) is greater than in developer bath II and the halide content in developer bath (2) is less than in developer bath II. stomach.

In short, the method accelerates the development of the bottom yellow layer,
Provides fairly good color balance.

Standardized processing processes exist for many photosensitive silver halide recording materials. Thus, a photographic recording material of any origin comprises, for example, at least one blue-sensitive silver halide emulsion layer containing a yellow coupler, at least one green-sensitive silver halide emulsion layer containing a magenta coupler and a cyan coupler. A true-to-type method is used to make color prints using transparent color negative film from color negative paper comprising at least one red-sensitive silver halide emulsion layer.
It can be processed by O-TYPE).

In a widely practiced method for processing color negative papers known as the EP2 method or Agfacolor development AP92 method, exposed color negative papers are subjected to color development, bleaching, fixing, washing and drying. be done. This bleaching and fixing step may be a combination of bleaching and fixing, while the washing step may be replaced by a stabilizing step.

Development of this color occurs in 210 seconds. Considerable efforts have been made to shorten this time, but until now by using capable negative papers consisting essentially of silver bromide emulsions with only small chloride contents (less than 20 mol% Cf). They have failed to develop new methods that can be successfully carried out on a commercial scale.

The only commercially used method in recent years has a development time of 45 seconds, but mainly uses silver chloride emulsions (more than 15 mol% Cl).
(RA-4 method), which requires color negative paper containing . This method takes advantage of the known fact that chloride emulsions can be developed more rapidly than bromide emulsions.Development of the top layer of a color material can be carried out as soon as the photographic material is immersed in the developing bath of one of the processes described above. Start.

The halides liberated during the reduction of silver halide penetrate into the underlying emulsion layer with the developer solution and complicate development. The third, lowermost emulsion layer of a material containing three spectrally differently sensitive silver halide emulsion layers is particularly disadvantaged. Furthermore, the development of the lowest layer is
This is hindered due to the decrease in developer concentration due to consumption in the upper layer and due to increased diffusion paths. In the case of developing a color image in which the lowest emulsion layer forms a dye image with a yellow component,
Improper development of this layer results in a blue cast appearance.

These disadvantages occur more often with accelerated processing methods since short development times add to the effects mentioned above. However, these developments were also observed using standard EP2 or AP92 methods.

The developer bath in this process is regenerated during continuous processing to replace the developer consumed during the development process. It is desirable to keep the regeneration rate to a minimum in order to minimize spillage, ie to divert as little liquid as possible to regeneration.

This requires a high concentration of developer in the regenerator, but unfortunately this is not possible as the CD3 developer used in this method is only poorly soluble, thus complete development of the bottom layer is problematic. becomes.

Furthermore, the activity of the developer is unavoidably impaired by the high halide content produced considering the minimum regeneration rate.

In standard regeneration methods, the developer concentration in the in-use solution is lower than in the regeneration solution, while the concentration of halide in the fecal solution is higher than in the regeneration solution. This results in the layer being exposed and developed to an undesirable combination of low color developer content and high halide content during swelling.

In the case of ordinary color paper, the silver bromide or silver bromide chloride emulsion that is mainly used releases bromide ions to an increased extent during development, and these bromide ions have a strong development hindering effect in contrast to chlorine ions. There is the added difficulty of doing so.

It is therefore an object of the present invention to provide a processing method in which the disadvantages attributable to improper development of the lowermost emulsion layer are eliminated, and at the same time low regeneration speeds can be used for overflow-free processes. It is.

It has now been discovered that this objective can be achieved by a two-stage development requiring only one regeneration solution.

The present invention allows development to occur in developer baths I and II, provided that in the usage state of the developer baths, the developer content in developer bath I is greater than that in developer bath II, and the halide content in developer bath 1 is greater than that in developer bath II. A light-exposed silver halide emulsion layer comprising on a reflective layer support at least three light-sensitive silver halide emulsion layers of different spectral sensitivities, each associated with a cyan coupler, a magenta coupler and a yellow coupler, characterized in that The present invention relates to a color photographic developing bath for developing silver halide materials.

The concentration of the developer is preferably 0, O1 in developer bath I.
~0.03 mol/Q, more preferably 0.014~0.
0.023 mol/Q, and preferably 0.002 to 0.02 mol/Q, and more preferably 0.005 to 0.023 mol/Q in developing bath (1). The range is O1 mol/Q.

The concentration of halide in developer bath I is preferably 0.00.
15 to 0.015 mol/Q, more preferably 0.004
-o, oog mol/Q, and in developing bath (1) preferably 0.017 to 0.04 mol/Q, more preferably 0.02 to 0.03 mol/Q.

The present invention also relates to a process for developing exposed color photographic materials using developer baths I and II as described above, wherein the residence time of the color photographic material in developer bath I is less than 50% of the total development time.

The residence time of the color photographic material in developer bath I is preferably between 10 and 20% of the total development time.

This two-stage development optimally provides the layer with high developer concentration for low halide content. Developer solution containing optimal activity capacity (high developer content versus low halide content)
is 50% or less of the total development time, preferably 10-20%
is captured by the layer during swelling in the development stage (1) within a limited residence time of .

The development starting with development step (3) consumes only a small amount of developer corresponding to the short residence time, so that the preferred ratio of high developer concentration to low halide content is substantially constant in the working solution of the first developer bath. becomes constant. The color photographic material thus prepared is then completely developed in a second developer bath.

Therefore, the concentration of the developer in the second bath in use condition is considerably lower and the concentration of halide is correspondingly higher than in the first developer bath.

Development in the various emulsion layers therefore follows a concentration gradient, with the preferred development conditions resulting from developer bath I being maintained longest in the lowest layers. Here again, the density present towards the end of development is approximately the same as that of the second bath.

Another advantage of the present invention is that only one regenerant solution is required, bath I
This means that it is added to Regenerants are best added based on the theory of concentration balancing.

This ensures that there is no overflow since the volume conveyed is equal to the inflow volume of regeneration solution.

The regeneration solution is transferred from bath I to bath II by the photographic material. For safety reasons, the overflow of bath I is connected to that of bath II.

Furthermore, when the process is carried out continuously, it is advantageous to add wetting agents and complexing agents to the developer solutions (1) and (H) to facilitate penetration of the solutions into the emulsion layer and to bind calcium ions from the gelatin and water. It is.

Suitable complexing agents for complexing calcium ions are, for example, the known aminopolycarboxylic acids, among others. Representative examples of such aminopolycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid (EDTA), 1,2-diamino-2-hydroxypropyltetraacetic acid, diethylenetriaminepentaacetic acid, NIN'-bis-(2-hydroxybenzyl )-ethylenediamine-N,N-diacetic acid, hydroxyethylethylenediaminetriacetic acid, cyclohexanediaminotetraacetic acid and aminomalonic acid.

Other calcium complexing agents are polyphosphates, phosphonic acids, aminopolyphosphonic acids and hydrolyzed I; polymaleic anhydrides such as sodium hexametaphosphate,
These are 1-hydroxyethane-L1 diphosphonic acid, aminotrimethylenephosphonic acid, and ethylenediaminetetramethylenephosphonic acid. ■-Hydroxyethane-1.
1-diphosphonic acid also acts as an iron complexing agent.

Furthermore, it is advantageous to add iron complexing agents to the reproducing solution.

Special iron complexing agents are e.g. 4,5-dihydroxy-1,3
-benzenedisulfonic acid, 5,6-cyhydroxy 1.
2,4-benzenetrisulfonic acid and 3,4°5-trihydroxybenzoic acid.

Calcium complexing agents are preferably used in amounts of about 0.2 to about 1.8 moles per mole of developer to complex calcium.

The iron complexing agent is used in an amount of about 0.02 to about 0.2 moles per mole of developer.

Particularly suitable primary aromatic amine developers are p-phenylene diamines and especially N,N-dialkyl-p-phenylene diamines in which the alkyl groups and aromatic nuclei are substituted or unsubstituted. Examples of such compounds are N, N-
Diethyl-p-fuynylenediamine hydrochloride, 4-N,N
-diethyl-2-methylphenylenediamine hydrochloride, 4
-(N-,r-+R-N-2-methanesulfonylamine ethyl)-2-methylphenylenediamine sesquisulfate l hydrate, 4-(N-ethyl-N-2-hydroxyethyl)-2-methylphenylene diamine sulfate and (/4-N, N-diethyl-2,2'-methanesulfonylaminoethylphenylenediamine hydrochloride. It is also advisable to add whitening agents, white couplers and antioxidants to the solution. Suitable antioxidants are, for example, hydroxylamine and diethylhydroxylamine and also sulfides, which preferably contain 5 g/
Used in amounts up to 12.

Other ingredients include optical brighteners, lubricants such as polyalkylene sulfates, surfactants, stabilizers such as heterocyclic mercapto compounds or nitrobenzimidazole, and agents for establishing the required pH value. The developer solution may be doped with benzyl alcohol or may be free of benzyl alcohol.

The developer according to the invention is preferably 7 or more, more particularly 9 to 13
It is an aqueous alkaline solution with a pH value in the range of . Known buffers such as alkali carbonates and alkali phosphates are used to establish this pi value.

In the state of use, the pH value of developer bath I is higher than that of developer bath II.

When the two-stage development according to the invention is used in the EP2 or AP92 process (total development time 210 seconds), color photographic materials are developed in which the silver degenide emulsions generally contain at least 70 mole % bromide.

The silver halide emulsion layer of the color photographic recording material subjected to two-stage development according to the invention in the course of accelerated development according to the RA-4 method with a development time of 45 seconds contains at least 80 mol %, preferably at least 95 mol %. % chloride.

Ready-to-use solutions can be prepared from the individual components or from so-called concentrates in which the individual components are dissolved in more concentrated form. This concentrate can be formulated in such a way that so-called regenerants can be prepared therefrom. That is, a solution in which each component is somewhat more concentrated than the ready-to-use solution, on the one hand, dilution and the addition of the starting material, preferably KC (2 or KBr), gives a ready-to-use solution, and on the other hand, the components are consumed during development or It is added continuously to the developer solution in use to replace chemicals displaced from the developer solution by overflow or by developed material.

Since halide ions are removed from the photographic material by development, they usually do not need to be added except to freshly prepared developers.

However, if the halide is added externally to the developer regeneration solution, or if it is possible to replace the halide impurities with other developer components, then the development problem may be affected. ? ) The concentrations of halide ions in I and ■ vary correspondingly. The halide concentrations mentioned above are based on the use of a halide-free developer regeneration solution.

After development, the photographic material is stopped, bleached, fixed, washed and dried in the usual manner. The bleaching and fixing may be combined into a single bleaching/fixing step, while washing may be replaced by a stabilizing column. If the bleach or bleach/fix bath is sufficiently acidic, there is no need for a stop bath.

Example 1 The following layers were applied to a paper layer support coated on both sides with polyethylene. All amounts shown below are per 1 m1.

1. Gelatin 20 containing KNO3 and chromium alum
0 mg base layer.

2. Adhesive layer with 320 mg of gelatin.

3. 1600 mg gelatin, 1.0 mmol yellow coupler 2,5-dioctylno\hydroquinone 27.
A blue-sensitive silver bromide chloride emulsion layer (20 mole % chloride) of 450 mg of A g N0 containing 7 mg and 650 mg of tricresyl phos7ate. Particle size 0.8μm
The emulsions were prepared by the double jet method, thickened, washed and redispersed in gelatin by conventional methods. The weight ratio of gelatin and silver (as AgNO2) is 0
．． It was 5. The emulsion was then ripened to optimal sensitivity with 60 μmol thiosulfate per Ag mole and AgN0.
530 mg green-sensitive silver bromide chloride emulsion layer (20 mole % chloride).

6. 1550 mg of gelatin, sensitized to the blue spectral range and stabilized with a compound corresponding to the formula below.

4. Gelatin 1200mg, 2.5-dioctylhydroquinone 80mg and thiocresyl phosphate loo
mg middle layer.

5. 750 g of gelatin sensitized with the compound of the following formula, 0.625 mmol of magenta coupler α-(3-t-butyl-4-
Hydroxyphenoxy)-myristic acid ethyl ester 118mg 52.5-dioctylhydroquinone 43m
g, 343 mg of dibutyl phthalate and CH.

285 mg of UV absorber, 80 mg of dioctyl hydroquinone and 650 mg of tricresyl phosphate 7ate.
mg middle layer.

7. 1470 mg of gelatin sensitized with the compounds shown in the table below
, 0.780 mmol cyan coupler dibutyl phthalate 285 mg and tricresyl phosphate 122
A red-sensitive and silver bromide emulsion layer containing 400 mg of A g N Os (20 mole % chloride).

8. Protective layer of 1200 mg of gelatin, 134 mg of UV absorber used in the 6th layer and 240 mg of tricresyl phosphate.

9. Gelatin 400mg and the formula below of curing agent corresponding to 400 mg of curing agent.

The following compounds were used as color couplers: Yellow coupler: Magenta coupler: Cyan coupler In the control example, the color photographic material described above was subjected to a step process.
Wedges were exposed and processed under standard processing conditions: Developer 210 seconds 38°C bleach/fix bath
90 seconds 38°C washing 210 seconds
In-use conditions were developed using a regeneration rate of 60 mQ7 m2 with no overflow for 33°C dry developer.

The following composition: Tank solution with developer in use Regenerant water 960m4
960m12 diethyl glycol 30mQ
30mQ benzyl alcohol 10+++Q
20m12 Diethylenetriaminepentaacetic acid (DTPA) g g (HEDP) Hydroxyamine sulfate potassium sulfite g 1.5g Phate l hydrate (CD3) Whitening agent W 2g Potassium bromide 2.8g Potassium carbonate 30g pH value, corrected with K OH 1000 Whitening agent W g g g 10g 11.5 Bleach/fix tank solution, working condition water 950m
+Disodium disulfite 8g Ammonium thiosulfate 80g Ammonium ethylenediaminetetraacetate 55g Silver
3gpH value 6.8
(corrected with acetic acid) Shoulder gradation
Sensitivity data for the treated step wedges with respect to on) and maximum density are shown in Table 1.

EXAMPLES IN ACCORDANCE WITH THE INVENTION Exposed step wedges were developed in Developers I and II in accordance with the invention.

Use conditions were created with the same regeneration rate/m2 and the same developer regeneration composition as the control example.

Processing conditions: Developer I 30 seconds 27°C Developer n
180 seconds 38°C bleach/fix bath 90
Composition of the 38°C washing and drying bath: 210 seconds 33°C Sensitivity data for the step wedge are shown in Table 1.

Table 1 Tank solution Tank solution water 950m (2950m
12 diethylene glycol 30m12 30m (
2 Benzyl alcohol 15m12 10m (2
DTPA 3g 3gHE
DP, 60% by weight 0.5m (20.5m (+hydroxylamine sulfate 3g 1.5g CD
3 8g 3g whitening agent W
2 g lg potassium bromide
0.3g 3.5g potassium carbonate
30g 30gpH value 11.0
10.3 The bleach/fix solution had the same as-used composition as the control example.

Processed rows with respect to shoulder stage and maximum density
Control example 1,90 3.00 2.90 2.20
2,50 2.42 Example The above comparison shows that for the cyan and magenta values, the values obtained in the control example with respect to the shoulder stage and maximum density of the lowest yellow layer are too poor in terms of color balance. show.

The process according to the invention accelerates the development of the bottom yellow layer and the high shoulder step and maximum density thus obtained provides a considerably better color balance.

Example 2 A color photographic recording material was produced by applying the following layers in the indicated order to a layered support of paper whose screen was coated with polyethylene. All quantities shown are based on l m2. For the applicable silver halide,
The corresponding amount of AgNO3 is shown.

Layer combination: 1st layer (substrate layer): Gelatin 0.2g 2nd layer (
Blue sensitive layer): Gelatin 1.38g Yellow coupler Y 0.95g White coupler W 0.2g AgNO3 containing tricresyl phosphate (TCP) 0.29g
0.63 g blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.8 μm) Third layer (protective layer): Gelatin 1.1 g 2.5-
Dioctylhydroquinone 0.06g Dibutyl phthalate (DBP) 0.06g 4th layer (green photosensitive layer): Gelatin 1.08g Magenta coupler M 0.41g Luester 0.16g2.5
-Dioctylhydroquinone 0.08gDBP
0.34gTCP
A g N containing 0.04g
Os 0 , 45 g of a green-sensitive silver halide emulsion (99.5 mol % talloride, 0.5 mol % bromide)
, average particle diameter 0.6 μm).

5th layer (UV absorption layer): UV absorber 2.6-dioctylhydroquinone CP corresponding to gelatin 1.15g 6th layer (red sensitive layer): Gelatin cyan coupler C 0.6g 0.045g 0.04g 0 .75g 0.36g TCP 0.3
6 g of A g N O30, 3 g of a red-sensitive silver halide emulsion (99.5 mol % chloride, 0.5 mol % bromide, average grain diameter 0.5 μm).

7th layer (UV absorption layer): Gelatin 0.35g UV absorber (5th layer and F[)) 0.15g TCP
0.2 g 8th layer (protective layer): Gelatin 0.9 g Hardening agent H 0.3 g The coupler used has the following formula: I C,H In the following control example, the photographic material described above was Wedges were exposed and processed under standard processing conditions as follows: Development 45 seconds 35°C bleach/fix bath
45 seconds 35°C wash 90 seconds 33°C dry A regeneration rate of 5 Q mQ/m2 without overflow was used to create service conditions for the developer.

Bath composition: Water 960mα Diethylene glycol 3Qm(2 Ethylenediaminetetraacetic acid 2g Potassium sulfite O,1g 960m(2 30m(2g 0.3g Sodium chloride 3g 0.3gCD3
3g 10gPotassium carbonate 20g 20gpH value 1
The 0.1 11.3 bleach/fix solution had the same composition as Control Example 1, but the pH value was 5.5 (corrected with acetic acid).

shoulder gradation
Sensitivity data for the treated step wedges in terms of ion) and maximum density are shown in Table 2.

Example according to the invention Exposure I; step wedge according to the invention Developer I
and Developed in ■.

Use conditions were created with the same regeneration rate/m2 and the same developer regeneration composition as the control example.

Processing conditions: Developer T 6 seconds 27°C Developer n
39 seconds 35°C bleach/fix bath
45 seconds 35°C wash 90 seconds 33°C 85% by weight m12 nl Composition of the drying bath: Sensitivity data for the processed step wedges with respect to shoulder stage and maximum density are shown in Table 2.

2nd surface water 5Qm12 Diethylene glycol 30m4 50mff 0no2 0- Control example 2.
25 2.70 2.80 1.85 2゜50 2
．． 60 Ethylenediaminetetraacetic acid 2g 2g Potassium sulfite 0.2g O, 1g Sodium chloride 0.5g 3g CD3
8g 3g potassium carbonate 20
g 20 g pH 10,110,8 The bleach/fix solution had the same as-used composition as the control.

EXAMPLE The above comparison shows that for the cyan and magenta values, the values obtained in the control example with respect to the shoulder step and maximum density of the bottom yellow layer are too good for the color balance.

The process according to the invention accelerates the development of the bottom yellow layer and the high shoulder stage and maximum density thus obtained gives a much better color balance.

Characteristics and aspects of the present invention are as follows: (1) Development takes place in developer baths I and II, provided that in the state of use of the developer baths, the developer content of developer bath I is greater than that in developer bath II and the development occurs in developer baths I and II; At least three light-sensitive silver halide emulsion layers of different spectral sensitivities associated with a cyan coupler, a magenta coupler and a yellow coupler, respectively, characterized in that the halide content in the bath I is lower than in the developer bath H. A color photographic developing bath for developing exposed silver halide material on a layer-resistant support.

2. The concentration of developer is 0.01 to 0.0 in developer bath I.
3 mol/Q and 0.002 to 0.02 in developing bath H
The photographic developing bath of 1 above, which is mol/a.

3. The concentration of the developer is 0. O14~0.
023 mol/Q and 0°005 to 0.005 in developing bath ①.
The photographic developing bath of the above 1, which is O1 mol/Q.

4. The concentration of halide in developer bath I is 0.0015~
0.015 mol/Q and 0.017 to 0.017 in developing bath ■
The photographic developing bath of 1 above, which has a concentration of 0.04 mol/Q.

5. The concentration of halide in the developing bath is 02004~0
．． 008 mol/Q and 0°02 to 0.02 in developing bath H.
The photographic developing bath of 1 above, which has a concentration of 0.03 mol/Q.

6. A method for developing an exposed color photographic material using the two developer baths I and II of 1 above, wherein the residence time of the color photographic material in developer bath I is 50% or less of the total development time.

7. The method of 6 above, wherein the residence time of the color photographic material in the bath processing is 10 to 20% of the total development time.

8. The pH value of developing baths ① and ① in use is 9 to 1.
3. A method for developing an exposed color photographic material using two developer baths I and II according to 6 above.

9. A method for developing an exposed color photographic material using two developing baths I and II according to 6 above, in which the pH value of developing bath (1) in use is higher than the pH value of developing bath (2).

10. The method of 6 above, wherein the regeneration is performed by adding a regeneration solution to the developer bath I.

11. The method of 6 above, in which the developer bath II is regenerated by the solution carried by the color photographic material from the developer bath T.

Claims (1)

[Scope of Claims] 1. Development occurs in developer baths I and II, provided that in the use state of the developer baths, the developer content in developer bath I is greater than that in developer bath II, and the halide content in developer bath I is higher than that in developer bath II. comprising on a reflective layer support at least three light-sensitive silver halide emulsion layers of different spectral sensitivities, each associated with a cyan coupler, a magenta coupler and a yellow coupler, characterized by less than in developer bath II. A color photographic developing bath for developing exposed silver halide materials. 2. A method for developing an exposed color photographic material using two developer baths I and II according to claim 1, wherein the residence time of the color photographic material in developer bath I is less than 50% of the total development time. .