GB2284067A - Photographic developers - Google Patents
Photographic developers Download PDFInfo
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- GB2284067A GB2284067A GB9323925A GB9323925A GB2284067A GB 2284067 A GB2284067 A GB 2284067A GB 9323925 A GB9323925 A GB 9323925A GB 9323925 A GB9323925 A GB 9323925A GB 2284067 A GB2284067 A GB 2284067A
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- Prior art keywords
- developing solution
- black
- compound
- carbon atoms
- white
- Prior art date
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- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- -1 alkali metal salts Chemical class 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 239000012992 electron transfer agent Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 29
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 18
- 235000010323 ascorbic acid Nutrition 0.000 claims description 13
- 239000011668 ascorbic acid Substances 0.000 claims description 13
- 229960005070 ascorbic acid Drugs 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 7
- RGZRSLKIOCHTSI-UHFFFAOYSA-N hydron;n-methylhydroxylamine;chloride Chemical compound Cl.CNO RGZRSLKIOCHTSI-UHFFFAOYSA-N 0.000 claims description 6
- 150000000996 L-ascorbic acids Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 3
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical group OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002211 L-ascorbic acid Substances 0.000 claims description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003289 ascorbyl group Chemical class [H]O[C@@]([H])(C([H])([H])O*)[C@@]1([H])OC(=O)C(O*)=C1O* 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 16
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 4
- 150000002443 hydroxylamines Chemical class 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229940072107 ascorbate Drugs 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- WYMDDFRYORANCC-UHFFFAOYSA-N 2-[[3-[bis(carboxymethyl)amino]-2-hydroxypropyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)CN(CC(O)=O)CC(O)=O WYMDDFRYORANCC-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GMPKIPWJBDOURN-UHFFFAOYSA-N Methoxyamine Chemical compound CON GMPKIPWJBDOURN-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- 239000004285 Potassium sulphite Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 238000012505 colouration Methods 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 2
- 235000019252 potassium sulphite Nutrition 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VSNHCAURESNICA-NJFSPNSNSA-N 1-oxidanylurea Chemical compound N[14C](=O)NO VSNHCAURESNICA-NJFSPNSNSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- VSNHCAURESNICA-UHFFFAOYSA-N Hydroxyurea Chemical compound NC(=O)NO VSNHCAURESNICA-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- DQPBABKTKYNPMH-UHFFFAOYSA-N amino hydrogen sulfate Chemical compound NOS(O)(=O)=O DQPBABKTKYNPMH-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- VDEUYMSGMPQMIK-UHFFFAOYSA-N benzhydroxamic acid Chemical compound ONC(=O)C1=CC=CC=C1 VDEUYMSGMPQMIK-UHFFFAOYSA-N 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229960001330 hydroxycarbamide Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- CPQCSJYYDADLCZ-UHFFFAOYSA-N n-methylhydroxylamine Chemical compound CNO CPQCSJYYDADLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000000837 restrainer Substances 0.000 description 1
- HBROZNQEVUILML-UHFFFAOYSA-N salicylhydroxamic acid Chemical compound ONC(=O)C1=CC=CC=C1O HBROZNQEVUILML-UHFFFAOYSA-N 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 235000019187 sodium-L-ascorbate Nutrition 0.000 description 1
- 239000011755 sodium-L-ascorbate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/43—Processing agents or their precursors, not covered by groups G03C1/07 - G03C1/42
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/30—Developers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/305—Additives other than developers
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
A developing solution for processing black and white photographic comprises as a main developing agent (i) an ascorbic acid type compound of the general formula I:- <IMAGE> wherein R is a hydroxylated alkyl group having 1 to 4 carbon atoms or alkali metal salts of such compounds (ii) an electron transfer agent as a superadditive developing agent eg. a pyrazolidone or metal and (iii) a hydroxylamine of the general formula II:- <IMAGE> or salt thereof, wherein R1 is hydrogen, an all group having 1 to 4 carbon atoms which may be substituted, an aryl group which may be substituted, together with an alkali to bring the pH of the developing solution above 8.
Description
Entitled: Photographic Developing Solution
This invention relates to ascorbic acid based developing solutions for use with silver halide photographic materials.
Ascorbic acid based black and white developing solutions are being used to an increasing extent because ascorbic acid does not suffer from the same defects that hydroquinone could suffer from. However ascorbic acid based developing solutions are not free from defects and one of these defects is that solutions1 especially ready-to-use solutions, ie not concentrated solutions, discolour very rapidly when exposed to atmospheric conditions at the basic pH necessary for photographic processing.
It is the object of the present invention to provide an additive which stabilises such solutions against the development of such discolouration.
Therefore according to the present invention there is provided a method of processing black and white photographic material in a working strength developing solution which comprises as the main developing agent an ascorbic acid type compound of the general formula I:
wherein R is a hydroxylated alkyl group having 1 to 4 carbon atoms or alkali metal salts of such compounds, and an electron transfer agent as a superadditive developing agent, in the presence of a hydroxylamine compound of the general formula II:
or a salt thereof, wherein R1 is hydrogen, an alkyl group having 1 to 6 carbon atoms which may be substituted, an aryl group which may be substituted, together with an alkali to bring the pH of the developing solution above 8. Preferably the pH of the solution is in the range of 9.5 to 11.
Examples of substituents in the R1 group are a water-solubilising group such as hydroxy, sulphonic acid or carboxylic acid groups. Examples of other substituents in the R1 group are alkyl or aryl groups.
In one method of the invention the hydroxylamine compound of formula II is present in the ascorbic acid based working strength developing solution. In another method of the invention the hydroxylamine compound of formula II is present in the black and white photographic material which is being processed. A combination of these two methods may also be used.
According to a preferred embodiment of the invention there is provided a working strength black and white developing solution which comprises per litre of solution 5 to 15g of an ascorbic acid type compound of the general formula I:
wherein R is a hydroxylated alkyl group having 1 to 4 carbon atoms or alkali metal salts of such compounds and an electron transfer agent as a superadditive developing agent, together with 1 to 5g of a hydroxylamine compound of the general formula II:
or a salt thereof, wherein R1 is as defined above together with an alkali to bring the pH of the developing solution above 9.5.
Most preferably the pH of the developing solution is within the range of 9.5 to 11.
Preferred examples of ascorbic acid type compounds included in general formula I are L-ascorbic acid, and D-iso ascorbic acid. The preferred compounds of formula II are hydroxylamine and N-methyl hydroxylamine.
Most conveniently these hydroxylamines are added to the solution as their hydrochloric acid salt as the hydrochloric acid salts of these hydroxylamines are the commercially available compounds. Alternatively the salts with sulphuric acid or other convenient acids may be used. It is to be understood that under the pH conditions of use such salts substantially revert to the free hydroxylamine compound. It is also to be understood that under the pH conditions of use the ascorbic acid compound is substantially in the anionic form.
The preferred electron transfer agents which act as super-additive developing agents are metol and pyrazolidinone compounds of the general formula III
wherein R1 and R2 are each hydrogen, alkyl groups having 1 to 4 carbon atoms or hydroxy alkyl groups having 1 to 4 carbon atoms, R5 is an aromatic ring which is optionally substituted and R3 and R4 are each hydrogen, alkyl groups having 1 to 4 carbon atoms or phenyl.
Preferably there is present in the working strength black and white developing solution as just set forth an alkali metal sulphite. Most preferably potassium sulphite or sodium sulphite are used. A suitable concentration of alkali metal sulphite is from 5 to 20 g/litre.
Preferably the pH of the ready to use developing solution is about 10.1 to 10.4 and sufficient sodium or potassium carbonate is present in developing solution to attain this pH range. Alternatively a suitable pH may be achieved by the use of caustic alkali, or borate or other basic salts.
Other classes of compound which may be present in the developing solution include restrainers such as potassium bromide, antifoggants such as benzotriazole compounds, and sequestering agents such as ethylenediamine tetra-acetic acid, (EDTA) diaminopropanol tetraacetic acid (DAPTA) and diethylenetriamine pentaacetic acid (DTPA), or phosphonic acids such as l-hydroxyethylidene l,l-diphosphonic acid, diethylenetriamine penta (methylene phosphonic acid), ethylenediamine tetra (methylene phosphonic acid) and nitrolotris (methylene phosphonic acid) and alkali metal salts thereof.
When the compound of formula II is present in the black and white developing solution as just set forth the discolouration of the solution to an unacceptable level is delayed for at least 20 days at ambient temperature. This is shown in the Example which follows.
The Example I which follows also shows that a large number of hydroxylamines and related compounds not covered by formula II were tested in the developing solution instead of the compounds covered by formula II but none of these increased the period of acceptable colour change to the same extent as the compounds of formula II. Examples of these compounds not covered by formula II are hydroxyurea,
O-methylhydroxylamine, N,N diethylhydroxylamine, benzoylhydroxamic acid, salicylhydroxamic acid, and hydroxylamine-O-sulphonic acid.
A number of hydroxylamines have been used as preservatives in colour developing solutions which of course have an entirely different formulation to the black and white developing solutions as just set forth. In particular N,N-diethylhydroxylamine has found great commercial use as a preservative in colour developing solutions but as stated above this compound does not act when present in the ascorbic acid developing solutions as just set forth to delay the onset of an unacceptable colouration. It is a surprising and novel feature of the present invention that the effect is restricted to the compounds of formula II, and that similar compounds do not show the effect, even those such as N,N-diethyl hydroxylamine which has been used in colour developing solutions.
To some extent hydroquinone based developing solution discolour over a period of days but not to the same extent as ascorbic acid based developing solutions. However, when the compounds of formula II were added to hydroquinone based developing solutions a large increase in the rate of discolouration of the developing solutions was observed, and this invention is therefore not of use in hydroquinone based developing solutions.
The preferred superadditive developer of formula III is l-phenyl-4-methyl-4-hydroxymethyl-pyrazolidin-3-one which is hereinafter referred to as developing agent A. Most preferably this is present in the working strength developing solution at a concentration of 0.2 to 0.8g/litre
The preferred compounds of formula II, which as hereinbefore stated are hydroxylamine hydrochloride and N-methyl hydroxylamine hydrochloride, can be added to the ready-to-use developing solution as solids.
Alternative compounds of formula II in which the group R is substituted by carboxylic or sulphonic acid groups may be prepared by the methods mentioned in Belgian Patent 558 501.
The accompanying Examples will serve to illustrate the invention.
Example I
The following ascorbate based developing solution was prepared:
Potassium sulphite (65% w/v) 15cm3
DTPA Na5 (37% w/v) 6.8cm3 Developing Agent A 0.5g
Sodium-L-Ascorbate 10g Potassium Bromide lg
Benzotriazole 0.02g
Potassium Carbonate 20g
Water - > 1L pH 10.50
To litre portions of this solution these were added
Hydroxylamine hydrochloride 7g
N-methyl hydroxylamine hydrochloride 7g
Standard - no addition
N, N diethylhydroxylamine 5g
O-methyl hydroxylamine 5g
Hydroxyurea 5g
These solutions were left standing for 20 days and the colour of the solutions was measured initially and then every five days. The change in light absorbance at 400nm was determined.
An absorbance of 0.1 is a light yellow colour but an absorbance of 0.6 is a dark yellow to orange colour.
These results are shown in figure 1.
From these results it can be seen that only hydroxylamine hydrochloride and N-methyl hydroxylamine hydrochloride are effective in preventing an unacceptable increase in colour of the developing solution.
Figure 2 shows the effect of different concentrations of hydroxylamine hydrochloride and N-methyl hydroxylamine hydrochloride on the developer solution of Example 1. From these it can be seen that even the lowest levels of addition of these compounds give a remarkable reduction in the colouration of freshly prepared solutions, and that a level of around 3g/litre of either compound prevents noticeable discolouration from occurring over a period of at least 15 days.
EXAMPLE 2
The ascorbate based developing solution as set out in example I was prepared. To 1 litre nothing was added, to a second 1 litre portion -l 3gl 1 hydroxylamine hydrochloride was added.
A hydroquinone based developing solution was prepared:
DTPA Na5 (37% w/v) 6.8cm3 Sodium sulphite 12g
Potassium carbonate 15g
Hydroquinone 3.5g
Developing Agent A 0.25g
Potassium bromide 0.7g
Benzotriazole 0.03g
Sodium hydroxide (67% w/v) 1.2cm3 water - > 1 L
pH - > 10.80
To 1 litre nothing was added, to a second litre portion 3gl hydroxylamine hydrochloride was added.
These four solutions were left standing for 17 days and the colour of the solution was measured at periodic intervals. The change in light absorbance at 400nm was determined and the results obtained are shown in figure 3.
It can be seen that while the addition of hydroxylamine hydrochloride is
very effective in preventing an unacceptable increase in colour of the
developer solution based on ascorbate, this addition is in fact
detrimental to the solution colour of the hydroquinone based developer.
This result illustrates that this invention is of no use in hydroquinone based developing solutions.
Claims (10)
1. A method of processing black and white photographic material in a
developing solution which comprises as a main developing agent an
ascorbic acid type compound of the general formula I:
wherein R is a hydroxylated alkyl group having 1 to 4 carbon atoms or alkali metal salts of such compounds and an electron transfer agent as a superadditive developing agent, in the presence of a hydroxylamine compound of the general formula II:
or a salt thereof, wherein R1 is hydrogen, an alkyl group having 1 to 4 carbon atoms which may be substituted, an aryl group which may be substituted, together with an alkali to bring the pH of the developing solution above 8.
2. A method according to claim 1 wherein the compound of formula II is
hydroxylamine hydrochloride or N-methyl hydroxylamine
hydrochloride.
3. A method according to either claim 1 or claim 2 wherein the
compound of formula II is present initially in the working strength
ascorbic acid based developing solution.
4. A method according to either claim 1 or claim 2 wherein the
compound of formula II is present in the black and white
photographic material being developed.
5. A black and white working strength photographic developing solution
which comprises per litre of solution 5 to 15g of an ascorbic acid
type compound of the general formula I:
wherein R is a hydroxylated alkyl group having 1 to 4 carbon atoms or alkali metal salts of such compounds, an electron transfer agent as a superadditive developing agent, and a hydroxylamine compound of the general formula II:
or a salt thereof, wherein R1 is hydrogen, an alkyl group having 1
to 4 carbon atoms which may be substituted, an aryl group which may
be substituted, together with an alkali to bring the pH of the
developing solution above 8.
6. A black and white developing solution according to claim 5 wherein
the pH is within the range of 9.5 to 11.
7. A black and white developing solution according to claim 5 wherein
the ascorbic acid of formula I is L-ascorbic acid or D-iso ascorbic
acid.
8. A black and white developing solution according to claim 5 wherein
the hydroxylamine compound of formula II is hydroxylamine
hydrochloride or N-methyl hydroxylamine hydrochloride.
9. A black and white developing solution according to claim 5 wherein
the electron transfer agent which acts as a super-additive
developing agent is metol or a pyrazolidinone compound of the
general formula III:
wherein R1 and R2 are each hydrogen, alkyl groups having 1 to 4
carbon atoms or hydroxy alkyl groups having 1 to 4 carbon atoms, R5
is an aromatic ring which is optionally substituted and R3 and R4
are each hydrogen, alkyl groups having 1 to 4 carbon atoms or
phenyl.
9. A black and white developing solution according to claim 9 wherein
the pyrazolidinone compound of formula III is l-phenyl-4-methyl-4 hydroxy-methyl-pyrazolidin-3-one.
10. A black and white developing solution according to claim 5 which
comprises from 5 to 20g/litre of an alkali metal sulphite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9323925A GB2284067A (en) | 1993-11-20 | 1993-11-20 | Photographic developers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9323925A GB2284067A (en) | 1993-11-20 | 1993-11-20 | Photographic developers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9323925D0 GB9323925D0 (en) | 1994-01-05 |
| GB2284067A true GB2284067A (en) | 1995-05-24 |
Family
ID=10745458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9323925A Withdrawn GB2284067A (en) | 1993-11-20 | 1993-11-20 | Photographic developers |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2284067A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5578433A (en) * | 1994-10-17 | 1996-11-26 | Fuji Photo Film Co., Ltd. | Processing composition and processing method for silver halide photographic materials |
| US5821041A (en) * | 1996-03-05 | 1998-10-13 | Fuji Photo Film Co., Ltd. | Liquid developer for photographic silver halide photosensitive material and development method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB958678A (en) * | 1959-09-04 | 1964-05-21 | Kodak Ltd | Photographic developer concentrates |
| GB2027920A (en) * | 1978-08-11 | 1980-02-27 | Kodak Ltd | Photographic silver halide developer composition |
-
1993
- 1993-11-20 GB GB9323925A patent/GB2284067A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB958678A (en) * | 1959-09-04 | 1964-05-21 | Kodak Ltd | Photographic developer concentrates |
| GB2027920A (en) * | 1978-08-11 | 1980-02-27 | Kodak Ltd | Photographic silver halide developer composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5578433A (en) * | 1994-10-17 | 1996-11-26 | Fuji Photo Film Co., Ltd. | Processing composition and processing method for silver halide photographic materials |
| US5821041A (en) * | 1996-03-05 | 1998-10-13 | Fuji Photo Film Co., Ltd. | Liquid developer for photographic silver halide photosensitive material and development method |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9323925D0 (en) | 1994-01-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |