JPH03180842A - Bleaching bath and bleaching/fixing bath - Google Patents

Abstract

PURPOSE: To impart biodegradability to a bleaching bath and a bleach-fixing bath and to make the bleaching effect moderate by using a specified iron (III) complex salt as a complexing agent. CONSTITUTION: An iron (III) complex salt represented by formula I is used as >=20% of a complexing agent contained in a bleaching bath or a bleach-fixing bath. In the formula I, X is CH2 , CH2 =CH2 or CHOH. Nitrilomonoacetic dipropionic acid represented by formula II may be used as the complex salt. Only the complex salt may be used as the complexing agent and the complex salt may be used in combination with other complexing agent such as EDTA.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to bleaching baths and bleaching/fixing baths for processing silver halide color photographic materials with environmental considerations in mind.

To summarize the present invention, biodegradable bleaching and bleaching/fixing baths with moderate bleaching efficacy contain 20% by mole of the complexing agent.
The above includes an iron (IH) complex salt represented by the following formula (1) % formula % where X represents CH2, CH2-CH2 or CHOH.

Iron complex salts of aminopolycarboxylic acids, such as the iron ammonium complex salt of ethylenediaminetetraacetic acid, are widely used to bleach the silver formed during the development of color photographic materials. This compound and similar complexing agents used for this purpose are hardly biodegradable.

Bleaching baths containing iron complex salts of readily biodegradable complexing agents, such as nitrilotriacetic acid, do not exhibit sufficient bleaching edge when bleaching color photographic materials under normal conditions of pH 6-8.

The problem addressed in the present invention is to provide a bleaching/fixing bath suitable for processing halogen silver color photographic materials, containing readily biodegradable components, and capable of providing sufficient bleaching power. The goal was to develop a bath.

This problem is solved by the following formula (1) %Formula%] () where X represents CH□, CH2CH2 or CHOH. The problem was solved by bleaching baths and bleaching/fixing baths consisting of complexing agent iron(III) complexes.

The complexing agent represented by formula (I) may be a single substance or a mixture.

A preferred compound represented by formula (1) is nitrilomonoacetic dipropionic acid corresponding to the following formula %.

The remaining up to 80 mole %, or preferably at most 20 mole %, of the complexing agent is a known complexing agent such as ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, nitrilomonopropionic diacetic acid or nitrilotriacetic acid. In a preferred embodiment, only complexing agents according to the invention are used.

In addition to the iron complex according to the invention, the bleaching bath contains halogen compounds for rehalogenating the silver, and the bleaching/fixing bath contains thiosulfate and sulfite.

Halogen compounds that are compatible with bleach baths are, inter alia, the chlorides and bromides of sodium, potassium and ammonium. Ammonium or sodium thiosulfate is known as thiosulfate; - sodium thiosulfate or ammonium sulfite is known as sulfite.

Ready-to-use bleach baths and bleach/fix baths are
Contains each component at the following concentrations: Bleach Bath Iron(III) Complex 0.05 1. Omol/1
Halogen compound 0.1 2.5 mol/1 Bleach/fixing bath Iron(III) complex 0.04-0.4 mol/
1 thiosulfate 0.2-2 mol/1 sulfite 0.02-0.3 mat/1 Furthermore, both columns preferably contain not more than 1.3 mol/1 of free complexing agent.

The pH value of the bleaching bath is preferably 1-8 and the pH value of the bleaching/fixing bath is preferably 4-8.

The bleaching baths and bleaching/fixing baths according to the invention are characterized in that the silver halide emulsion is primarily AgBrSAgBr1°AgBrC.
1. Particularly suitable for the processing of silver halide color photographic recording materials having a good AgC1 content. The color photographic material comprises, on an opaque or transparent support (e.g. paper or cellulose triacetate film laminated on both sides), at least one layer of sensitive blue light, at least one layer of edge-colored light, and at least one layer of edge-colored light. A red-sensitive silver halide emulsion layer, at least one yellow coupler layer, at least one magenta coupler layer, and at least one cyan coupler layer corresponding thereto are coated.

The bleaching and bleaching/fixing baths according to the invention process a halogen silver color photographic material comprising the following steps: exposure, development, optionally stopping, bleaching and fixing or bleaching/fixing, rinsing, optionally stabilizing and drying. The rinsing can be omitted if a stabilizing bath is used at the end of the process.

These treatments can also be carried out continuously, with each treatment bath being continuously regenerated.

The bleach baths and bleach/fix baths described in the examples were tested for their degree of bleaching (silver remaining in the treated material).

Quantification of residual silver: After exposure, process as described below and photo-Matic
PM8030 infrared silver detector (Denmark, Ph.

To-Matic) was used to measure the amount of silver remaining in the black part of the step wedge image of the photographic material.

Information regarding the biodegradability of the complexing agents used in the bleach baths according to the invention is reported in the literature: Federal Commission for the Vast Wastes of German Chemical Companies (BUA), Verlag Chemie Wines Heim, 198
7, published by BUA-Substance Information (BU
A-S toff-bericht) 5 :-Triacetic acid (1986, 10).

Example 1 (Invention) The layers were coated on a transparent cellulose triacetate support in the following order.

All amounts shown below are per 1 m2.

The amount of silver halide to be applied is the same as the corresponding AgN0. It is expressed as the amount of

All silver halide emulsions contain 0.1 g of 4-hydroxy-6-methyl 1.3.3 per 100 g of AgNO3.
a, stabilized by 7-chitraazaindene.

1st layer (antihalation layer) Black colloidal silver 0.2g gelatin
1.2g UV absorber UU-1
0.1g Ultraviolet absorber UV-20.2g Tricresyl phosphate 0.02g Dibutyl phthalate 0.03g 2nd layer (Micrato intermediate layer) Micrato Ag (Br, I) AgNO3,0,2 for emulsion
5g average particle size, 0.07μm; silver iodide, 05mol% gelatin 1.0g color coupler RM-10.05g tricresyl phosphate
0.10 g 3rd layer (low sensitivity red light layer) AgNO, 2.2 g silver iodide, 4 mol%: average particle size,
0.45μm; spectrally sensitized gelatin to red light
2.0g tricresyl phosphate (TCP
) Colorless cyan coupler C- emulsified in 0.5 g
1.0.6g cyan color coupler RM-150mg: and DIR coupler emulsified in TCP 20mg
DIR-130mg 4th layer (high sensitivity red light layer) AgN03.2.8g: Silver iodide, 8.5 mol%; Average particle size, 0.8 μm; Spectrally sensitized gelatin to red light
1.8g dibutyl phthalate (DBP)
Colorless cyan coupler C- emulsified with 0.15g
20.15g 5th layer (separation layer) Gelatin 0.7gDBP O
, 0.2 g of 2,5-diisooctylhydroquinone emulsified with 15 g of Ag(B) containing 4.5 mol% of silver iodide and spectrally sensitized to green light. r, I) AgN0° 1.8g: Average particle size, 0.4μm Gelatin 1.6g Magenta coupler M-1 (latex coupler)
Mask coupler emulsified in 0.6g TCP 50mg YM-150mg DIR coupler emulsified in DBP 20mg
DIR-230mg DIR coupler emulsified in 60mg TCP
DIR-3somg 7th layer (highly sensitive green light layer) Ag (Br, AgNO for
32.2 g; average particle size, 0.7 μm Spectrally sensitized gelatin to green light 1.4 g TCP 0
．． Magenta coupler M-20 emulsified with 45g,
15g Mask coupler similar to layer 6, emulsified with 30mg TCP 30mg layer 8 (separation layer) Gelatin 0.5gDBP 0
．． 0.1 g of 2,5-diisooctylhydroquinone emulsified with 0.08 g 9th layer (yellow filter layer) Ag (yellow colloidal silver sol) 0.2 g Gelatin 0.9 g DBP 0.16 g
2,5-diisooctylhydroquinone emulsified with
0.2 g 10th layer (low sensitivity blue light layer) 30.6 g AgNO for Ag (Br, I) containing 4.9 mol% silver iodide: average particle size, 0.45 μm Gelatin 0.85 g TCP
Yellow coupler Y-10 emulsified with 0.7g,
7g DIR coupler D emulsified with 0.5g TCP
IR-30.5g 11th layer (high sensitivity blue layer) Ag containing 9.0 mol% silver iodide (Br, Ag for
NOs 1.0 g; average particle size, 0.9 μm Gelatin 0.85 g TCP 0
．． Yellow coupler similar to the 10th layer, emulsified with 3 g 0.3 g 12th layer (protective and hardening layer) Mickle) Ag (Br, I) AgNO3,0 for emulsion
, 5 g; Average particle size, 0-07 μm; Silver iodide, 0.5 mol% Gelatin 1.2 g Hardening agent expressed by the following formula 0.4 g (CH2=CH-3O2-
CHa CONHCH2)z - 1.0 g of formaldehyde scavenger represented by the following formula The structures of the compounds used in Example 1 are each represented by the following formula: Ultraviolet absorber V-1 N X : weight of y Ratio = 7:3 Σ The photographic material described above was exposed with a step wedge and processed as follows: Developer bath 3 minutes 15 seconds 37.8°C bleach bath
4 minutes 20 seconds 38°C Rinse 1 minute 5 seconds 38°C Fixing bath 4 minutes 20 seconds 38°C Rinse 3 minutes 15 seconds 38°C Finishing bath 1 minute 5 seconds 38°C Each processing bath has the following composition.

Developer water 800ml Potassium carbonate 37.5g Sodium sulfite
4.25g potassium iodide 1.2
mg Sodium bromide 1.3g Hydroxyl, amine sulfate 2.0g Diethylenetriaminepentaacetic acid 2.0g 4-(N-Ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 4°75g Add water 1 Make it a little.

pH 10.0 Bleach bath A Water 600ml nitrilomonoacetic dipropionic acid 5g Fe(NOs)s'9 H2O 109g Ammonium bromide 150g Ammonium nitrate 16g Aqueous ammonia (25% by weight) Approximately 120ml Adjust pH to 4.2 with aqueous ammonia or acetic acid Adjust.

Add water to make 1 liter.

Fixing bath water 800ml Ammonium thiosulfate solution (58% by weight) 62ml Ethylenediaminetetraacetic acid 1.3g Sodium hydrogen sulfite 1°3g Sodium hydroxide
Add 2.4g water to make 1 liter.

pH 6.5 Finishing bath water 800ml formalin (37% by weight) 3ml polyoxyethylene
p-monononylphenyl ether 0
．． Add 5g of water to make 1 liter.

The measurement results of residual silver are shown in Table 1 below. The color image obtained was correct.

Example 2 (comparative example) Exposure and processing were performed as described in Example 1.

The developer, fixing bath and finishing bath had the same composition as in Example 1.

Bleach bath B Water 600m1 EDTA
- Iron (III) - Ammonium 9 g Acetic acid (80% by weight) Approximately IQml Ammonium bromide 150 g Ammonium nitrate 16 g Adjust the pH to 6.0 with aqueous ammonia or acetic acid.

Add water to make 1 liter.

The measurement results of residual silver are shown in Table 1 below.

Table 1 Bleach bath Silver detector reading 1 4 4 1) A value of 6 or more indicates the presence of residual silver.

As can be seen from Table 1, the bleaching effect of bleaching bath A according to the invention containing a biodegradable complexing agent is superior to that of non-biodegradable ED.
Comparable to the bleaching effect of typical bleaching bath B containing TA. Bleach tests show that bleach bath A according to the invention does not produce leucocyan dye, whereas a typical bleach bath containing EDTA shows a significant loss of cyan dye at certain pi values.

Example 3 (Invention) A color photographic recording material suitable for the processing method according to the invention was produced by applying each layer in the following order on a paper support laminated on both sides with polyethylene. All amounts shown below are per 1 m2. The amount of silver halide applied is expressed in terms of the corresponding amount of AgNO3.

Layer arrangement 1st layer (support layer) Gelatin 0.2g 2nd layer (blue-sensitive layer) Gelatin 1.38g Yellow coupler Y 0.95g Contains tricresyl phosphate (TCP) 0.29g, AgNO30.63g Silver halide emulsion sensitive to blue light prepared from (silver chloride, 99.5 mol%: silver bromide, 0.5 mol%; average grain size, 0.8 μm) Third layer (protective layer) Gelatin 1. 1g 2.5-Dioctylhydroquinone 0.06g Dibutyl phthalate (DBP) 0.06g 4th layer (bad edge colored light layer) Gelatin 1.08g Magenta coupler M 0.41g 2.5-Dioctylhydroquinone 0.08g DBP 0.34g TCP
Contains 0.04g, AgNO
A silver halide emulsion spectrally sensitized to green light prepared from 30.45 g (silver chloride 99.5 mol%; silver bromide 0.5
Mol%; average particle size, 0.6 μm) 5th layer (ultraviolet absorbing layer) Gelatin 1.15 g UV absorber corresponding to the following formula 0.6 g 2.5-dioctylhydroquinone 0.045 g TCP 0.04 g 6th layer ( (Red-sensitive light layer) Contains gelatin 0.75g cyan coupler C0.36g TCP O.36g,
A silver halide emulsion spectrally sensitized to red light prepared from 3 g of A g N Os 0 (silver chloride, 99.5 mol %; silver bromide, 0.05 mol %; average grain size, 0.5 μm)
) 7th layer (ultraviolet absorbing layer) Gelatin 0.35g Ultraviolet absorber same as 5th layer 0.15g TCP
0.2g 8th layer (protective layer) Gelatin 0.9g Hardening agent 0.3g corresponding to the following formula The structures of the compounds used in Example 2 are each represented by the following formula: The photographic material was exposed with a step wedge overlay and processed as follows: Development 45 seconds bleach/fix 45 seconds rinse 90 seconds dry Each processing bath had the following composition: 35°C 35°C Approximately 30°C Developer water 900ml ethylenediaminetetraacetic acid (EDTA) g hydroxyethane diphosphonic acid (HEDP) (60% by weight) 0.5ml sodium chloride
2g N,N-diethylhydroxylamine (85% by weight)
5m1 4-(N-ethyl-N-2-methanesulfonylaminoethyl)-2-methyl-phenylenediamine % sulfate-permanent (CD3) (50% by weight) 8m
1 Potassium carbonate 25g Adjust pH to 10 with KOH or H2SO4.

Add water to make 1 liter.

Bleach/fixing bath A Water 800ml nitrilomonoacetic dipropionic acid 0g Fe (NOs)s 9 H2O 50g aqueous ammonia (25% by weight) Approximately 40ml sodium sulfite 10g ammonium thiosulfate 80g Adjust pH to 6.0 with aqueous ammonia or acetic acid Adjust.

Add water to make 1 liter.

The measurement results of residual silver are shown in Table 2 below. The color image obtained was correct.

Example 4 (comparative example) Exposure and processing were performed as described in Example 3.

The developer had the same composition as in Example 3.

Bleach/fixing bath A Water 800ml EDTA
Iron (III) ammonium 745g Sodium sulfite 10g Ammonium thiosulfate 80g Adjust the pH to 6.0 with aqueous ammonia or acetic acid.

Add water to make 1 liter.

The measurement results of residual silver are shown in Table 2 below.

Color images were adequate.

obtained Table 2 Bleaching/fixing bath Silver detector reading n 4 4 11 (a value of 3 or more indicates the presence of residual silver.

Table 2 shows the excellent bleaching effect of bleach/fix bath A according to the invention containing a biodegradable complexing agent.

Its bleaching effect is based on non-biodegradable EDTA as a complexing agent.
The bleaching effect is comparable to that of a typical bleach/fix bath B containing:

The main features and aspects of the invention are as follows.

1 20 mol% or more of the complexing agent has the following formula (I) HOO
Bleaching baths and bleaching/fixing baths containing iron(III) complex salts, represented by: CCH2N CCH2-X-C0OH] 2(I) where X represents CH2, CH2-CH2 or CHOH.

2. The bleaching bath and bleaching/fixing bath according to item 1, wherein 80 mol % or more of the complexing agent is represented by formula (2).

3. Bleaching and bleach/fix bath according to claim 1, characterized in that the complexing agent is nitrilomonoacetic dipropionic acid.

Claims (1)

[Scope of Claims] 1. 20 mol% or more of the complexing agent has the following formula (I) HO
OC-CH_2-N-[CH_2-X-COOH]_2
In the formula, X is CH_2, CH_2-CH_2 or CHO
Bleaching baths and bleaching/fixing baths containing iron (III) complex salts, represented by: