JPH07502131A - developer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] developer The present invention relates to a photographic developer for use in photographic color development, especially redox development. Regarding liquid.

Redox (or RX) amplification development treatment is described, for example, in British Patent No. 1, 268.12. No. 6, No. 1.399.481, No. 1.403.418 and No. 1, 56 It is described in No. 0.572. In such processing, color materials are not developed. to create a silver image (which will contain a very small amount of silver), and then the silver image is redoxed. catalyzes amplification of the dye to form a dye image. The redox amplification solution contains reducing agents, e.g. For example, color developing agents and silver images that are more powerful than silver halides and act as catalysts. An oxidizing agent is included that oxidizes the color developing agent in the presence of the image. oxidized color development Image agents react with color couplers (usually included in photographic materials) to produce image colors. form an element. The amount of dye formed is similar to that of the image as in traditional color development methods. It depends on processing time or color coupler utilization rather than the amount of silver in it. child A special application of the technique is silver chloride color photographic paper, especially photographic papers with low silver levels. This is the case with the development process.

However, since this amplification solution contains both an oxidizing agent and a reducing agent, Width liquids are inherently unstable and will degrade during storage. This instability is caused by During the process, complex transition metal ions such as manganese (Mn) and/or disulfone Gelatin of photographic materials such as acid catechol rCDS J, rTIRON J TM Seasoning of species present in the layer catalyzed by g).

In conventional RA-4 type developers, this catalytic effect is caused by calcium ions or transitions. It forms fairly stable soluble complexes with metal ions, and free metal ions, especially Iflm or higher metals that allow ferric ions to exist only in trace amounts can be substantially reduced or eliminated by adding sequestering agents. Wear. Such metal ion sequestering agents include, for example, diethylamine triamine. pentaacetic acid r　DTPAJ or 1-hydroxy-ethylidene-1,l-diphosphone polyacetic acid such as alkylidene-1,1-diphosphonic acid such as acid rHEPAJ can be given.

Co-pending UK Patent Application No. 9125687.5, filed on the same date as this application, contains a single one metal ion sequestrant, more particularly a combination of two or more metal ion sequestrants 81% The combination has a surprising stabilizing effect in preventing catalytic decomposition of photographic bleaching solutions. is disclosed.

In the redox developer field, single metal compounds such as ``rDTPA'' or its salts While the addition of on-blocking agents to the redox amplification solution has a very slight stabilizing effect , a combination of two or more sequestering agents is inherent in photographic film coatings. Substantial contact effects caused by seasoning of or impurities added to this coating. It was found that this effect produced a synergistic effect that showed a strong inhibition. Furthermore, the effect of this prevention is For example, the removal of the contact effect of Mn and/or rcDs is greater than that of Mn and/or rcDs. or the stability of RX developer surprisingly compared to seedless controls such as rCDS J. This is a significant improvement in the In fact, this stability makes such solutions satisfactory. Significantly reduces the amount of time-dependent replenishment fluid (TDR) typically required to maintain operating conditions It can be improved to the extent that it is reduced and even reduced to zero.

Therefore, according to the present invention, hydrogen peroxide or a substance capable of releasing hydrogen peroxide, a color developer, etc. prevents the catalysis of reducing agents such as image agents and impurities from photographic film coatings; combinations for complexing with transition metal ions to increase solution stability. A redox amplification solution consisting of two or more sequestering agents is proposed. Served.

One type of sequestering agent present according to the present invention is an alkyl carboxylic acid, a phosphorus at least one phosphoric or sulfonic acid condensed with one or more argyl hydrogens. polyalkylcarboxylic acids, phosphonic acids or sulfonic acids containing amine groups , this is expressed by the formula (1) [where Xl and X2 are the same or different (, respectively , hydrogen atom, straight chain or branched alkyl group having 1 to 6 carbon atoms, hydroxyl group , carboxyl group, sulfonyl group, phosphonyl group or group Z (however, Z; (In the formula, a, b, c and d are the same or different, and each has a hydrogen atom and a carbon number of 1 ~6 straight or branched chain alkyl groups, hydroxyl groups, carboxyl groups, sulfonyl group or phosphonyl group) or either Xl and/or X2 is a repeating unit of A or B It may be, Y is as defined for a, b, c and d, or a group Z or a group B (wherein X2 and X4 are the same or different and defined earlier for Xl and X! (as is the case) and The sum of m, n and r is an integer from 1 to lO, and (CHl), the group (C1, ), or (cl), one or both of the hydrogen atoms in each group has 1 to 6 carbon atoms. may be substituted with a straight-chain or branched alkyl group, x', x'', x' and at least one of X4 is a carboxyl group, a sulfonyl group or a phosphonyl group or a salt thereof] It can be expressed as

An example of a compound of formula (I) which is particularly suitable is ethylenediaminetetraacetic acid rEDTAJ , propylene diaminetetraacetic acid "PDTA", nitrilotetraacetic acid rNTA J However, the most preferred one is diethylenetriaminepentaacetic acid rDTPAJ, which These compounds are generally used in the form of their corresponding tetra- or penta-sodium salts. .

In a preferred embodiment for carrying out the present invention, the compound of formula (1) or a salt thereof is , alkylidene-1,I-diphos such as a compound of formula (n) as defined below. sulfonic acid and/or a polyhydric acid such as a compound of formula (III) as defined below. Combine with any droxylphenyl.

The compound of formula (I[) is 0 x O (In the formula, X is a hydrogen atom, a halogen atom, or a hydroxyl group, and n is 0 to 12 ) in particular 1-hydroxy-ethylidene-1,l-diphosphonic acid (X=O HSn=1).

The compound of formula (I[I) is (In the formula, R1, R2, R3 and R4 are the same or different, and each is a hydrogen atom, Straight chain or branched alkyl group having 1 to 6 carbon atoms, hydroxyl group, sulfonyl group or carboxyl group), especially dihydroxyphenylsulfone (°catechol disulfone) rCDS J) or rTIRON It is J.

In a further preferred aspect, the present invention allows hydrogen peroxide or hydrogen peroxide to be released. substances, reducing agents such as color developing agents, and impurities emanating from photographic film coatings. complexed with transition metal ions to prevent catalysis and increase solution stability. a compound of formula (II) as defined above and/or as defined above; as defined above in combination with any of the compounds of formula (III) as defined above. A redox amplification solution comprising a compound of formula (I) or a salt thereof is provided.

In a more preferred aspect of the present invention, the redox amplification solution contains a compound of formula (I[) and consisting of a compound of formula (I) or a salt thereof in combination with both a compound of formula (■) and a compound of formula (■) . Most preferably, the redox amplification solution is diethylenetriaminepentaacetic acid rDTP. AJ or its salt and l-hydroxy-ethylidene-1,1-diphosphonic acid rll Consists of EPA.

These metal ion sequestering agents are any one in the range of 1.1 to 20:I by volume. Can be combined in a ratio of two components, in which case which component is present in greater amount You may do so. Each sequestering agent is liter, preferably 1-1-1 O/liter of redox solution, most preferably Add in an amount of 2 to 6.5 mL/liter of redox solution.

Compounds that can release hydrogen peroxide include metal peroxides, such as sodium percarbonate. Compounds containing hydrogen peroxide in their crystal structure: sodium perborate and sodium persulfate Other peroxy compounds, such as butyl peroxide or bean peroxide. Contains soluble growth peroxides such as silica.

Hydrogen peroxide or compounds such as those mentioned above will oxidize the color developing agent within a reasonable amount of time. Add in sufficient quantity to Conveniently commercially available 3006 hydrogen peroxide ．． 5 to 100 mL/L of amplification bath IL, preferably about 5 mL/L, or Equivalent amounts of hydrogen peroxide, such as 8% or 3%, can also be used.

Generally, the reducing agent used as a color developing agent is p-aminophenol or p-phenylene. It can be any primary aromatic amine such as a diamine. to use The color developing agent used is 4-amino-N,N-diethylaniline hydrochloride. Lido, 4-amino-3-methyl-N,N-diethylaniline hydrochloride, 4 -Amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfur ate, and preferably N-ethyl-N-β-methanesulfone-amidoethyl -3-methyl-4-aminoaniline (CD3).

The reducing agent is added in an amount of about 1-20 g/L, preferably 2-5 g/L.

The redox amplification solution preferably maintains the pH at the required level, usually around pHlo. one or more acids, alkalis or alkali metal carbonates, carbonates / with a buffering agent such as a bicarbonate buffer or a phosphate buffer.

Since a hydrogen ion is created for each atom of metallic silver that is formed, hydroxyl This solution must be sufficiently buffered to create a large saucer of on. . As pll increases, the color developing agent becomes a more powerful reducing agent for silver; This results in higher speeds of photographic development. However, a high pll will cause the developer to empty. more sensitive to atmospheric oxidation and thus more protection from developer or oxygen. is necessary. Antioxidants such as diethylhydroxylamine are advantageously used. can be done.

The redox amplification liquid of the present invention can be used with any kind of photographic silver halide color material. can be used. Such materials and their possible constituents are, for example, K enneth Mason Publications, Emsworth.

Research Disclosure published by Hants, UK e Item 308119, December 1989. But long Among these, materials based primarily on silver chloride emulsions are preferred.

The present invention also relates to hydrogen peroxide or substances capable of releasing hydrogen peroxide, such as color developing agents. It prevents the catalytic action of reducing agents such as as defined above for complexing with transition metal ions to increase the Compounds of formula (I[) as such and/or compounds of formula (I[I) as defined above] from adding a compound of formula (I) as defined above together with any of the The present invention provides a photographic color development processing method including a redox amplification step.

This redox amplification step may be followed directly by a bleaching step, using an intermediate stop bath. Good too.

Photographic materials to be processed preferably contain low levels of silver to reduce light scattering. preferably at least 80%, preferably at least 9096 based on emulsions consisting of silver chloride, in particular substantially pure silver chloride.

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples. Needless to say, this is not something that can be done.

Example 1 A developer-amplifying solution (DEVAMP) having the following composition was prepared.

Ingredient concentration Potassium carbonate 10.0g/L Potassium bromide 1. Omg/L Potassium chloride 0.35 g/L CD3 (color developing agent) 3.5g/LHtOa (3096) 5.0mL /LpH10,3 Temperature 35°C Prepare each of the following solutions in raw water containing an equivalent amount of calcium carbonate of approximately 200 ppm. and transferred to a glass cylinder held at 35°C in a water thermostat.

1. Above solution + 1-hydroxy-ethylidene-1,1-diphosphonic acid r 60% solution in water of HEPAJ 0.6g/L2, 1 + diethylenetriamine 6.5 mL/L3 of a 40% solution of the pentasodium salt of pentaacetic acid rDTPAJ in water, 1 + 5 ppm manganese (as manganese sulfate) 10 catechol disulfone RT rCDS J 0.5g/L4, 2 + 5ppmMn + 0.5g/L rCD5''5, the above solution of the pentasodium salt of DTPA J in water 40% solution 6.5mL/L 6, 5 + 5ppmMn + 0.5g/LrCD5” sometimes DEVAMP To monitor the activity of the solution, small pieces of exposed photographic paper were processed.

The results of the stability test in the red Dmax reflection density section for neutral exposure are shown in Figure 1. Indicated by f.

The stability of the solution l containing only the sequestering agent rHEPA steadily decreased.1. It lost 20% Dmax in 5 hours and similarly contained only the sequestering agent rDTPAJ. The solution dropped to less than 50% Dmax in the first 2 hours. D of solution 3 max fell more rapidly and completely lost its activity in about 20 minutes.

However, solutions 2.4 and 6 showed no obvious loss of stability over 3 hours. Surprisingly, solution 4 was the most stable, showing 8096 activity even after 7.5 hours. Retaining the activity, solution 2 gradually drops to 50% activity after this time and solution 6 at 5 o'clock. After a while, 85% activity was retained.

Similar results were found for green and blue Dmax, which are shown in Figures 2 and 3, respectively. . The results for green Dmax reflect the results for red Dmax, and the results for blue Dmax The results for max are 6 for solution 4 close to the maximum activity after 7.5 hours. A similar trend is shown except that there was an unexpected increase in activity after hours. these The results clearly indicate that either rDTPAJ or rF (EPAI (solution 2) or rcDsJ (Solution 6), a significant improvement in stability is obtained. to show that Contains both rHEPAJ and rcDs without rDTPAJ This improvement is not seen for the solution (Solution 3). However, the most stable In the EVAMP solution, rDTPAJ, rHEPA'' and rCDSJ are all present. (solution 4).

Example 2 A developer-amplifying solution having the composition shown in Example 1 was prepared, and the equivalent amount of calcium carbonate was about 200 pp. Prepare each of the following solutions in tap water containing m and store them at 35°C in a water thermostat. Transferred to a retained glass cylinder.

1. In Example 1, containing 0.6 g/L of a 60% solution of rHEPAJ in water. Similar solution 1 2,] + 2 mL/L rDTPAJ3, I + 4 mL/L rDTP AJ4, I + 6.5mL/L rDTPAJ5, 4 + loppm Manganese (as manganese sulfate) +0.6g/L rCDS J In solutions 2-4 above, rDTPAJ is a 4096 solution of its pentasodium salt. used in the form of

rDTPA'' and Mn/r from time to time for a total of 7.5 hours as above. To monitor the stability effects of CDS J, a small piece of exposed photographic paper was exposed. Image processed.

The stability test results for the red Dmax reflection density item for neutral exposure are graphed in Figure 4. Indicated by f.

The stability of solution l decreased steadily from the beginning, losing 20% Dmax in less than 2 hours, Then, after 7.5 hours, it rapidly decreased to 30% of its original value.

There was only a slight loss of stability until 4 hours had elapsed for solutions 2-4; The liquid decreased by 6596.62%, 55% and 69% after 7.5 hours, respectively.

In this example, the most increased stability was in the presence of rHEPAJ. The surprisingly small amount of rDTPA required to provide a new increase in rDTPA It will be noted that the lowest amount of J was found.

However, as for example 1, unexpectedly adding Mn/rCDS J and the observed impurities normally associated with these impurities in the absence of rDTPA J. The presence of all three sequestering agents despite their beneficial catalytic effects Better results were obtained showing that optimal results can be obtained by

The results of a similar experiment for blue Dmax are shown graphically in FIG. repeat However, solution 1 has the lowest stability, which drops to 54% after the monitoring ends. However, in this case, no significant difference was observed between solutions 2.3 and 4. All were down by only about 75% at the end of the period. Also, solution 5 was released after 7.5 hours. also proved to develop maximum stability with only a slight decrease to 88%.

Example 3 Comparing solutions 2 and 4 in Figure 1, there is an unexpected increase in stability that appears to be essentially responsive. Mn or rCDS in combination with rDTPAJ and rHEPA A similar experiment was set up to test and establish whether J. Red Dmax anti The solutions tested for stability in terms of stability were as follows.

1. Same solution as in Example 1: 0.6 g of a 60% solution of rHEPAJ in water /L + 2 mL of 40% solution of pentasodium salt of rDTPAJ/L2, 1 + rCDS J (0.6 g/L) 3, I + rcDsJ (0.6 g/L ) + 2.5ppmMn4, 1 + rcDs” (0,6g/L) + 10 ppmMn5, 1 + 2.5ppmMn 6, 1 + 10ppmMn The results shown graphically in Figure 6 show the stability of any solution up to 5 hours. This shows that there is no significant decline in the After that, Mn-containing rCDS J The solution without it falls below 6096 after 8 hours and is reflected close to solution l. On the other hand, those to which rCDS J was added but no Mn were added after this time. 85% stability was reserved.

These results include rDTPAJ, rllEPA' and rCDSJ/Mn. An obvious explanation for the surprisingly high stability of solutions containing rDTPAJ CDS artificially added to the gelatin layer of photographic materials together with rHEPAJ and rHEPAJ. ” indicates the presence of impurities.

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Claims (20)

[Claims] 1. hydrogen peroxide or substances capable of releasing hydrogen peroxide; reducing agents such as color developing agents; and impurities from photographic film coatings, increasing solution stability. a combination of two or more of them for complexing with transition metal ions to A redox amplification solution containing at least one metal ion sequestering agent. 2. Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X1 and X2 are the same or different. Each may be a hydrogen atom, a straight chain or branched chain alkali having 1 to 6 carbon atoms, and Kill group, hydroxyl group, carboxyl group, sulfonyl group, phosphonyl group or is the base Z (however, Z= ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, a, b, c and d are the same or different, and each has a hydrogen atom and a carbon number of 1 ~6 straight or branched alkyl groups, hydroxyl groups, carboxyl groups, sulfur (honyl group or phosphonyl group)) or either X1 and/or X2 is a unit of manipulation of A or B It may be, Y is as defined for a, b, c and d or a group Z or a group B ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (wherein X3 and X4 are the same or different, as defined for X1 and X2 ) and The sum of m, n and r is an integer of 1 to 10, and (CH2)m group, (CH2 )n group or (CH2)r group, one or both of the hydrogen atoms has a carbon number of 1 Optionally substituted with ~6 straight-chain or branched alkyl groups. However, X1, X2 , at least one of X3 and X4 is a carboxyl group, a sulfonyl group or a phosphor group. is or contains a honyl group or a salt thereof], a compound of formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, X is a hydrogen atom, a halogen atom, etc.) or hydroxyl group, n is 0 to 12) and/or the compound of formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R1, R2, R3 and R 4 are the same or different, and each is a hydrogen atom, a straight chain or branched chain having 1 to 6 carbon atoms chain alkyl group, hydroxyl group, sulfonyl group or carboxyl group) The redox amplification solution according to claim 1, which is formed in combination with any compound. . 3. Compounds of formula (I) or salts thereof, compounds of formula (II) and compounds of formula (III) The redox amplification solution according to claim 2, which consists of a combination of substances. 4. Formula (I) in which at least one of X1, X2, X3 and X4 is a carboxylic acid group The redox according to any one of claims 2 and 3, consisting of a compound of Amplification solution. 5. Claims in which the compound of formula (I) is diethylenetriaminepentaacetic acid or a salt thereof The redox amplification solution according to any one of items 2 to 4. 6. Claim No. 1, wherein the compound of formula (I) is ethylenediaminetetraacetic acid or a salt thereof. The redox amplification solution according to any one of Items 2 to 4. 7. Claims in which the compound of formula (I) is propylenediaminetetraacetic acid or a salt thereof The redox amplification solution according to any one of Items 2 to 4. 8. Claims 2 to 3, wherein the compound of formula (I) is nitrilotetraacetic acid or a salt thereof. The redox amplification solution according to any one of Item 4. 9. The compound of formula (II) is 1-hydroxy-ethylidene-1,1-diphosphonic acid The redox amplification solution according to any one of claims 2 and 3. 10. Claimed in which the compound of formula (III) is dihydroxyphenyl sulfonate. The redox amplification solution according to any one of the ranges 2 and 3. 11. Diethylenetriaminepentaacetic acid or its salt, 1-hydroxy-ethylidene- Consisting of a combination of 1,1-diphosphonic acid and dihydroxyphenylsulfonate , the redox according to any one of claims 1 to 5, 9, and 10. amplification solution. 12. The ratio of any two components is within the range of 1:1 to 20:1 by volume (however, any may be present in greater amounts) Redox amplification solution as described. 13. Add end compounds in an amount of 0.05-100 mL/1 liter of redox solution The redox amplification solution according to any one of the above claims. 14. The redox according to claim 13, wherein the amount of each compound is 2 to 6.5 mL. amplification solution. 15.30% hydrogen peroxide from 0.5 to 100 mL/L of solution, preferably about 5 mL/L. The redox amplification according to any one of the above claims, which is used in an amount of a solution. liquid. 16. The reducing agent is N-ethyl-N-β-methanesulfone-amidoethyl-3-methylene. 4-Aminoaniline The redox according to any one of the above claims amplification solution. 17. A claim that the reducing agent is added in an amount of about 1 to 20 g/L, preferably 2 to 5 g/L. The redox amplification solution according to any one of the above items. 18. Reducing hydrogen peroxide or substances capable of releasing hydrogen peroxide, such as color developing agents improves solution stability by blocking the catalytic action of impurities from chemicals and photographic film coatings. The combination of two or more products for complexing with transition metal ions to increase involves a redox amplification step consisting of adding further sequestering agents. A photographic color development processing method. 19. The redox amplification solution is one according to any one of claims 1 to 17. 19. The method according to claim 18. 20. Claim No. 18 in the photographic color development processing method recited in Claim No. 18 Use of the redox amplification solution according to any one of Items 1 to 17.