US3721563A - Photographic developer concentrate - Google Patents
Photographic developer concentrate Download PDFInfo
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- US3721563A US3721563A US00183674A US3721563DA US3721563A US 3721563 A US3721563 A US 3721563A US 00183674 A US00183674 A US 00183674A US 3721563D A US3721563D A US 3721563DA US 3721563 A US3721563 A US 3721563A
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- Prior art keywords
- developing agent
- concentrate
- solution
- ascorbic acid
- developer
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- 239000012141 concentrate Substances 0.000 title claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 48
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 44
- 239000000243 solution Substances 0.000 claims abstract description 37
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 22
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 21
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 21
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 21
- -1 silver halide Chemical class 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- NPKFETRYYSUTEC-UHFFFAOYSA-N n-[2-(4-amino-n-ethyl-3-methylanilino)ethyl]methanesulfonamide Chemical group CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1 NPKFETRYYSUTEC-UHFFFAOYSA-N 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 4
- 239000012224 working solution Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- FZIPCQLKPTZZIM-UHFFFAOYSA-N 2-oxidanylpropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O FZIPCQLKPTZZIM-UHFFFAOYSA-N 0.000 description 1
- XTBFKMDOQMQYPP-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine;hydron;chloride Chemical compound Cl.CCN(CC)C1=CC=C(N)C=C1 XTBFKMDOQMQYPP-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- TVSWUKNDEBSSON-UHFFFAOYSA-N Cl.CCN(CC)c1cccc(C)c1N Chemical compound Cl.CCN(CC)c1cccc(C)c1N TVSWUKNDEBSSON-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GHXRKGHKMRZBJH-UHFFFAOYSA-N boric acid Chemical compound OB(O)O.OB(O)O GHXRKGHKMRZBJH-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000837 restrainer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/407—Development processes or agents therefor
- G03C7/413—Developers
Definitions
- ABSTRACT A phase-stable acidic photographic color developing solution which includes, in aqueous solution, a pphenylenediamine developing agent andascorbic acid.
- This invention relates to photographic color developer concentrate kits, and more particularly to an acidic photographic color developer concentrate useful as an element in such kits.
- Chemicals which are utilized to develop exposed silver halide materials are generally sold in the trade in concentrated form so that, by simple dilution with water, the ultimate user may obtain a photographic color developer working solution.
- a concentrated acidic aqueous solution of a photographic developing agent may be placed in one package of a kit, and a concentrated aqueous alkaline solution may be included in a second package thereof.
- the photographic color developer working solution may then be prepared simply by combining the packaged ingredients and diluting the same with water.
- Kit packages which contain a concentrated developing agent further ordinarily contain fairly large quantities of sulfite (as, for example, sodium sulfite) as a stabilizer for the developing agent.
- sulfite as, for example, sodium sulfite
- Dutch Pat. application No. 6,814,905 teaches that the storage stability of an aqueous p-phenylenediamine developing agent-sulfite concentrate may be improved if the molar ratio of sulfite to the developing agent is no greater than 1.5/1.0.
- sulfite/developing agent molar ratio of about 0.05/1 to about 1.0/1.0, and preferably 0.15/1 to 0.5/1
- aqueous acidic p-phenylenediamine developing agent solution concentrates which contain a stabilizing quantity of sulfite unfortunately are not phase-stable; that is, phase separation occurs upon storage which may lead to formation of a precipitate.
- phase separation occurs upon storage which may lead to formation of a precipitate.
- Shaking or mixing of the packaged concentrated developer merely causes the solution to become turbid. It is desirable, of course, that one be able to quickly prepare a working developer solution simply by opening the packaged chemical concentrates and diluting them with water.
- the invention relates to a phase-stable acidic photographic developing solution concentrate which comprises, in aqueous solution, a p-phenylenediamine developing agent and ascorbic acid in an amount sufficient to provide a mole ratio of ascorbic acid to said developing agent of from about 0.005/1 to about 0.3/1.
- the invention in another embodiment, relates to a method for the production of a photographic silver halide developer solution which comprises combining, in aqueous solution, an aqueous alkaline solution concentrate (e.g., another kit package which contains an alkaline ingredient such as potassium hydroxide, buffering ingredients such as borates, carbonates, etc.) and an acidic, phase-stable aqueous solution concentrate which includes a p-phenylenediamine developing agent and ascorbic acid, the mole ratio of ascorbic acid to the developing agent being from about 0.005/1 to about 0.3/1, as described above.
- phase-stable is meant that no phase separation can be visually detected in the solution when viewed under normal indoor lighting conditions.
- aqueous alkaline solution so described rendersthe resulting working developer solution alkaline, and so permits silver halide development to occur.
- the color development of silver halide materials involves reduction of silver halide to silver, accompanied by concurrent oxidation of a p-phenylenediamine developing agent.
- the oxidation product of the developing agent then couplesff i.e., condenses, with a color coupler which may be contained within the photographic element to form a colored dye.
- developer solution as used herein, reference is made to both developer solutions and replenisher solutions which are used to replenish depleted developer solutions.
- ascorbic acid is known to be an oxidation inhibitor, it is surprising that ascorbic acid may be employed in the acidic aqueous photographic developing solution concentrates of the invention without causing phase-separation, as described above with reference to sulfite.
- those developer concentrate solutions of the invention which contain no sulfite may develop a slightly colored appearance upon storage, it has been found that this phenomena does not have a significant affect on the utility of the developer.
- the developer concentrate solutions of the present invention additionally contain a very small compatible (i.e., not causing phase-separation) quantity of a water-soluble sulfite salt to prevent the solution from becoming colored upon storage.
- the mole ratio of sulfite salt to p-phenylenediamine developing agent should not be greater than about 0.08 to 1, and preferably is from about 0.02 to l to about 0.065 to 1.
- sulfite salt is meant compounds such as alkali metal sulfites and bisulfites; i.e., compounds which will liberate sulfite ions when dissolved in water. Sodium sulfite is preferred.
- the concentration of p-phenylenediamine developing agent in the developer solution concentrate of the invention will normally fall within the range of from about 0.5 to 1.0 molesper liter, (e.g., up to the solubility limit of the developer) although greater and lesser amounts may also be employed.
- the developer solutions of the invention are acidic, and ordinarily display a pH of less than about 5.
- the resulting solution preferably exhibits a pH of from about 1.2 to about 4.5.
- the developing agents which are especially useful in the solutions of the present invention are the p-phenylenediamine color developing agents well known in the art, especially those which form non-diffusing dyes with phenolic and reactive methylene photographic couplers.
- the p-phenylenediamine developing agents of the invention include p-phenylenediamine and the N,N-dialkyl-p-phenylenediamines and their salts such as the sulfate, hydrochloride etc. salts.
- suitable developing agents include N,N-diethyl-p-phenylenediamine monohydrochloride, 2-amino-3- diethylaminotoluene monohydrochloride, 4-amino-N- ethyl-N-(B-methanesulfonamidoethyl)-m-toluidine sesquisulfate monohydrate, 4-amino-3-methyl-N-ethyl- N-(B-hydroxyethyD-aniline sulfate, 4-amino-3-(fl methylsulfonamidoethyl)-N,N-diethylaniline hydrochloride, 4-amino-N,N-diethyl-3-(N'-methyl-flmethylsulfonamido)-aniline hydrochloride.
- the developing agent concentrates of the present invention may also contain various other additives known to the art, such as antifoggants (e.g., benzotriazole), development restrainers (e.g., bromide ion), auxiliary black and white developing agents (e.g., 3- pyrazolidone silver halide developers such as 4,4- dimethyl-B 1-phenyl-3-pyrazolidone), benzyl alcohol (as a dispersion), and the like.
- the developing solution concentrate of the invention includes in aqueous solution only the developing agent, sulfite, and ascorbic acid (plus a pH regulator, if desired).
- the aqueous alkaline solution concentrate with which the solution concentrate of the present invention is combined and diluted with a predetermined amount of water to form a working developer solution may contain an alkaline material such as potassium hydroxide and various other components such as additional sulfite, accelerators, complexing agents and buffers (such as citric acid-citrate, boric acid-borate, carbonate, etc.).
- an alkaline material such as potassium hydroxide and various other components such as additional sulfite, accelerators, complexing agents and buffers (such as citric acid-citrate, boric acid-borate, carbonate, etc.).
- Developer kits which include the developer solution concentrate of the present invention will normally be sold in unitary kit form, each kit containing two or more packages.
- a three-package developer kit was prepared, the composition of each of the packages being as follows:
- Ascorbic acid A second photographic developer kit. was also prepared, packages A and B being identical to packages A and B above, but package C having the following composition Sodium sulfite Developing agent (4-arnino- N-ethyl-N-(fl-methanesulfonamidoethyl)-mtoluidine sesquisulfate) Water to about 13 cc.
- the C and C packages both were stored at room temperature for about 8 months. At the end of this period, two phases had formed in package C (which contained no ascorbic acid). A very turbid solution resulted when this package was violently shaken. Package C (which contained ascorbic acid), in contrast, was clear and showed no evidence of phaseseparation. Thereafter, both of the C packages were diluted with water 1:100 by volume. The solution resulting from package C (which contained ascorbic acid) was much less highly colored than was the solution obtained from package C.
- Working developer solutions were preparedfrom each of the kits described above by dissolving the contents thereof in water to a volume of 1 liter. Although the contents of package C which contained ascorbic acid were rapidly dissolved, the contents of the package C (without ascorbic acid) were dissolved much more slowly.
- a phase-stable acidic photographic developing solution concentrate comprising, in aqueous solution, a p-phenylenediamine developing agent, and ascorbic acid in an amount sufficient to provide'a mole ratio of l ascorbic acid to said developing agent of from 0005-03 to l.
- the concentrate of claim 1 which additionally includes a compatible quantity of a water-soluble sulfite salt.
- An acidic aqueous solution concentrate having a pH of not greater than 5.0 and comprising a p-phenylenediamine developing agent, a water-soluble sulfite salt, and ascorbic acid, the molar ratio of sulfite to developing agent being not greater than 0.08 to l and the molar ratio of ascorbic acid to developing agent being from 0.0050.3 to l.
Abstract
A phase-stable acidic photographic color developing solution which includes, in aqueous solution, a p-phenylenediamine developing agent and ascorbic acid.
Description
United States Patent 1191 Fisch et al.
[ ]March 20, 1973 PHOTOGRAPHIC DEVELOPER CONCENTRATE [75] Inventors: Richard S. Fisch; Norman Newman;
Joel L. Bexell, all of St. Paul, Minn.
[73] Assignee: Minnesota Mining and Manufacturing Co., St. Paul, Minn.
[22] Filed: Sept. 24, 1971 [21] Appl.No.: 183,674
[52] US. Cl. ..96/66.l, 96/55, 96/56,
96/66, 96/66.4 [51 Int. Cl ..G03c 5/30, G03c 7/00 [58] Field of Search ..96/66, 66.1, 66.4, 55, 56
[56] References Cited UNITED STATES PATENTS Vittum ..96/56' James, Kinetics of Development by p-Phenylenediamine in Neutral and Moderately Alkaline Solns, Journal of Photography, Vol. 6, 1958, pp. 49-57.
Primary Examiner-J. Travis Brown Assistant Examiner-Mary F. Kelley Att0rneyKinney, Alexander, Sell, Steldt & Delahunt [5 7] ABSTRACT A phase-stable acidic photographic color developing solution which includes, in aqueous solution, a pphenylenediamine developing agent andascorbic acid.
8 Claims, No Drawings- PHOTOGRAPHIC DEVELOPER CONCENTRATE This invention relates to photographic color developer concentrate kits, and more particularly to an acidic photographic color developer concentrate useful as an element in such kits.
Chemicals which are utilized to develop exposed silver halide materials are generally sold in the trade in concentrated form so that, by simple dilution with water, the ultimate user may obtain a photographic color developer working solution.
To avoid the tendency of certain ingredients of photographic developer concentrates to react with one another, it is often desirable to provide various of these ingredients in separate packages. For example, a concentrated acidic aqueous solution of a photographic developing agent may be placed in one package of a kit, and a concentrated aqueous alkaline solution may be included in a second package thereof. The photographic color developer working solution may then be prepared simply by combining the packaged ingredients and diluting the same with water.
Kit packages which contain a concentrated developing agent further ordinarily contain fairly large quantities of sulfite (as, for example, sodium sulfite) as a stabilizer for the developing agent. Dutch Pat. application No. 6,814,905 teaches that the storage stability of an aqueous p-phenylenediamine developing agent-sulfite concentrate may be improved if the molar ratio of sulfite to the developing agent is no greater than 1.5/1.0. 0n the other hand, it is reported desirable to use sufficient sulfite in the concentrated developer solution to at least stabilize the developing agent against air oxidation (e.g., a minimum sulfite/developing agent molar ratio of about 0.05/1 to about 1.0/1.0, and preferably 0.15/1 to 0.5/1
It has been found that aqueous acidic p-phenylenediamine developing agent solution concentrates which contain a stabilizing quantity of sulfite unfortunately are not phase-stable; that is, phase separation occurs upon storage which may lead to formation of a precipitate. During preparation of the working developer solution, excessively long periods of time are required to completely dissolve the contents of the package containing the developer concentrate in the working solution. Shaking or mixing of the packaged concentrated developer merely causes the solution to become turbid. It is desirable, of course, that one be able to quickly prepare a working developer solution simply by opening the packaged chemical concentrates and diluting them with water. The necessity of physically dispersing (mixing) a precipitate during preparation of a working developer to cause dissolution of the precipitate is undesirable, since this may cause aerial oxidation of the developing agent. Moreover, the extensive mixing required to effect dissolution of a precipitate is time consuming and inconvenient, and desirably should be avoided.
It is an object of the present invention to provide an aqueous, acidic developing agent solution in concentrated form which is phase-stable upon storage.
It is another object of the invention to provide a phase-stable acidic photographic developing solution in concentrated form which can be rapidly and completely dissolved to form a photographic developer working solution, or a replenisher solution therefor.
Briefly, the invention relates to a phase-stable acidic photographic developing solution concentrate which comprises, in aqueous solution, a p-phenylenediamine developing agent and ascorbic acid in an amount sufficient to provide a mole ratio of ascorbic acid to said developing agent of from about 0.005/1 to about 0.3/1. In another embodiment, the invention relates to a method for the production of a photographic silver halide developer solution which comprises combining, in aqueous solution, an aqueous alkaline solution concentrate (e.g., another kit package which contains an alkaline ingredient such as potassium hydroxide, buffering ingredients such as borates, carbonates, etc.) and an acidic, phase-stable aqueous solution concentrate which includes a p-phenylenediamine developing agent and ascorbic acid, the mole ratio of ascorbic acid to the developing agent being from about 0.005/1 to about 0.3/1, as described above. By phase-stable is meant that no phase separation can be visually detected in the solution when viewed under normal indoor lighting conditions.
As will be understood by those skilled in the art, the
aqueous alkaline solution so described rendersthe resulting working developer solution alkaline, and so permits silver halide development to occur. As is known in the art, the color development of silver halide materials involves reduction of silver halide to silver, accompanied by concurrent oxidation of a p-phenylenediamine developing agent. The oxidation product of the developing agent then couplesff i.e., condenses, with a color coupler which may be contained within the photographic element to form a colored dye. By developer solution as used herein, reference is made to both developer solutions and replenisher solutions which are used to replenish depleted developer solutions.
Although ascorbic acid is known to be an oxidation inhibitor, it is surprising that ascorbic acid may be employed in the acidic aqueous photographic developing solution concentrates of the invention without causing phase-separation, as described above with reference to sulfite. Although those developer concentrate solutions of the invention which contain no sulfite may develop a slightly colored appearance upon storage, it has been found that this phenomena does not have a significant affect on the utility of the developer. In its preferred embodiment, the developer concentrate solutions of the present invention additionally contain a very small compatible (i.e., not causing phase-separation) quantity of a water-soluble sulfite salt to prevent the solution from becoming colored upon storage. The mole ratio of sulfite salt to p-phenylenediamine developing agent should not be greater than about 0.08 to 1, and preferably is from about 0.02 to l to about 0.065 to 1. By sulfite salt is meant compounds such as alkali metal sulfites and bisulfites; i.e., compounds which will liberate sulfite ions when dissolved in water. Sodium sulfite is preferred.
The concentration of p-phenylenediamine developing agent in the developer solution concentrate of the invention will normally fall within the range of from about 0.5 to 1.0 molesper liter, (e.g., up to the solubility limit of the developer) although greater and lesser amounts may also be employed. As mentioned, the developer solutions of the invention are acidic, and ordinarily display a pH of less than about 5. When diluted 50 fold with water, the resulting solution preferably exhibits a pH of from about 1.2 to about 4.5.
The developing agents which are especially useful in the solutions of the present invention are the p-phenylenediamine color developing agents well known in the art, especially those which form non-diffusing dyes with phenolic and reactive methylene photographic couplers. The p-phenylenediamine developing agents of the invention include p-phenylenediamine and the N,N-dialkyl-p-phenylenediamines and their salts such as the sulfate, hydrochloride etc. salts. Examples of suitable developing agents include N,N-diethyl-p-phenylenediamine monohydrochloride, 2-amino-3- diethylaminotoluene monohydrochloride, 4-amino-N- ethyl-N-(B-methanesulfonamidoethyl)-m-toluidine sesquisulfate monohydrate, 4-amino-3-methyl-N-ethyl- N-(B-hydroxyethyD-aniline sulfate, 4-amino-3-(fl methylsulfonamidoethyl)-N,N-diethylaniline hydrochloride, 4-amino-N,N-diethyl-3-(N'-methyl-flmethylsulfonamido)-aniline hydrochloride. Other useful color developing agents are disclosed in U.S. Pat. Nos. 2,552,241 and 2,566,271, and in J.A.C.S., 73, 3100-3123 (1951). Especially effective are those pphenylenediamine developing agents which contain at least one alkylsulfonamidoalkyl substituent attached to an amino nitrogen, or to a carbon atom of the phenyl ring.
The developing agent concentrates of the present invention may also contain various other additives known to the art, such as antifoggants (e.g., benzotriazole), development restrainers (e.g., bromide ion), auxiliary black and white developing agents (e.g., 3- pyrazolidone silver halide developers such as 4,4- dimethyl-B 1-phenyl-3-pyrazolidone), benzyl alcohol (as a dispersion), and the like. in one preferred embodiment, however, the developing solution concentrate of the invention includes in aqueous solution only the developing agent, sulfite, and ascorbic acid (plus a pH regulator, if desired).
The aqueous alkaline solution concentrate with which the solution concentrate of the present invention is combined and diluted with a predetermined amount of water to form a working developer solution may contain an alkaline material such as potassium hydroxide and various other components such as additional sulfite, accelerators, complexing agents and buffers (such as citric acid-citrate, boric acid-borate, carbonate, etc.).
Developer kits which include the developer solution concentrate of the present invention will normally be sold in unitary kit form, each kit containing two or more packages. The various packages will be chosen by size and shape to accommodate the various ingredients and concentrations of ingredients for each package, and will be further chosen so as to result in a total package of minimum size and weight to minimize shipping and storage costs. Accordingly, it may be desirable in some instances to place a given chemical composition (e.g., a sulfite salt) in more than one package to conservespace. a
The invention may be more easily understood by reference to the following illustrative, non-limiting example. v
A three-package developer kit was prepared, the composition of each of the packages being as follows:
Ascorbic acid A second photographic developer kit. was also prepared, packages A and B being identical to packages A and B above, but package C having the following composition Sodium sulfite Developing agent (4-arnino- N-ethyl-N-(fl-methanesulfonamidoethyl)-mtoluidine sesquisulfate) Water to about 13 cc.
The C and C packages both were stored at room temperature for about 8 months. At the end of this period, two phases had formed in package C (which contained no ascorbic acid). A very turbid solution resulted when this package was violently shaken. Package C (which contained ascorbic acid), in contrast, was clear and showed no evidence of phaseseparation. Thereafter, both of the C packages were diluted with water 1:100 by volume. The solution resulting from package C (which contained ascorbic acid) was much less highly colored than was the solution obtained from package C.
Working developer solutions were preparedfrom each of the kits described above by dissolving the contents thereof in water to a volume of 1 liter. Although the contents of package C which contained ascorbic acid were rapidly dissolved, the contents of the package C (without ascorbic acid) were dissolved much more slowly.
Two identical samples of photographic color paper containing a plurality of silver halide layers having couplers dispersed therein by the solvent dispersion technique '(see, e.g., U.S. Pat. Nos. 2,332,027 and 2,801,170) were identically exposed toa light image. One of the papers was developed in the developer solution resulting from use of the developer concentrateof the present invention (employing package C), and the other paper was developed in the other solutionJNo sensitometric differences were noted after development.
What is claimed is: v
1. A phase-stable acidic photographic developing solution concentrate comprising, in aqueous solution, a p-phenylenediamine developing agent, and ascorbic acid in an amount sufficient to provide'a mole ratio of l ascorbic acid to said developing agent of from 0005-03 to l.
2. The concentrate of claim 1 which additionally includes a compatible quantity of a water-soluble sulfite salt.
3. The concentrate of claim 2 wherein the molar ratio of said sulfite salt to said developing agent is not greater than 0.08 to 1.
4. The concentrate of claim 1 wherein said developing agent is a N,N-dialkyl p-phenylenediamine silver halide de-veloping agent.
5. The concentrate of claim 4 wherein said developing agent is 4-amino-N-ethyl-N-(B-methanesulfonamidoethyl)-mtoluidine, or a salt thereof.
6. An acidic aqueous solution concentrate having a pH of not greater than 5.0 and comprising a p-phenylenediamine developing agent, a water-soluble sulfite salt, and ascorbic acid, the molar ratio of sulfite to developing agent being not greater than 0.08 to l and the molar ratio of ascorbic acid to developing agent being from 0.0050.3 to l.
7. The concentrate of claim 6 wherein sald develop-
Claims (7)
- 2. The concentrate of claim 1 which additionally includes a compatible quantity of a water-soluble sulfite salt.
- 3. The concentrate of claim 2 wherein the molar ratio of said sulfite salt to said developing agent is not greater than 0.08 to
- 4. The concentrate of claim 1 wherein said developing agent is a N,N-dialkyl-p-phenylenediamine silver halide de-veloping agent.
- 5. The concentrate of claim 4 wherein said developing agent is 4-amino-N-ethyl-N-( Beta -methanesulfonamidoethyl)-m- toluidine, or a salt thereof.
- 6. An acidic aqueous solution concentrate having a pH of not greater than 5.0 and comprising a p-phenylenediamine developing agent, a water-soluble sulfite salt, and ascorbic acid, the molar ratio of sulfite to developing agent being not greater than 0.08 to 1 and the molar ratio of ascorbic acid to developing agent being from 0.005-0.3 to 1.
- 7. The concentrate of claim 6 wherein saId developing agent is 4-amino-N-ethyl-N-( Beta -methanesulfonamidoethyl)-m-toluidine or a salt thereof.
- 8. A method for the production of a photographic silver halide developer solution which comprises combining, in aqueous solution, an aqueous alkaline solution concentrate and an acidic, phase-stable aqueous solution concentrate which includes at least one p-phenylenediamine developing agent and ascorbic acid, the mole ratio of ascorbic acid to said developing agent being from about 0.005-0.3 to 1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US18367471A | 1971-09-24 | 1971-09-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3721563A true US3721563A (en) | 1973-03-20 |
Family
ID=22673840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00183674A Expired - Lifetime US3721563A (en) | 1971-09-24 | 1971-09-24 | Photographic developer concentrate |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3721563A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3870479A (en) * | 1971-10-15 | 1975-03-11 | Fuji Photo Film Co Ltd | Lithographic type diffusion transfer developer |
| US4155763A (en) * | 1976-09-07 | 1979-05-22 | Fuji Photo Film Co., Ltd. | Color photographic processing method |
| DE2910251A1 (en) * | 1978-03-15 | 1979-09-20 | Minnesota Mining & Mfg | COLOR DEVELOPER FOR COLOR PHOTOGRAPHIC RECORDING MATERIAL, METHOD FOR ITS MANUFACTURING AND ITS USE |
| US4232113A (en) * | 1979-03-14 | 1980-11-04 | Minnesota Mining And Manufacturing Company | Liquid concentrated developer composition, and confection ready to mix with water including it, for use in color photography |
| EP0118693A2 (en) * | 1983-02-10 | 1984-09-19 | Minnesota Mining And Manufacturing Company | Photographic color developer composition packaged in two or more concentrated parts, particularly solutions, and concentrated color developer water solution |
| US5578433A (en) * | 1994-10-17 | 1996-11-26 | Fuji Photo Film Co., Ltd. | Processing composition and processing method for silver halide photographic materials |
| EP0947879A1 (en) * | 1998-04-03 | 1999-10-06 | Eastman Kodak Company | Kit for photographic color developing bath |
| WO2000054106A1 (en) * | 1999-03-08 | 2000-09-14 | Eastman Kodak Company | New color photographic developer kit |
-
1971
- 1971-09-24 US US00183674A patent/US3721563A/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3870479A (en) * | 1971-10-15 | 1975-03-11 | Fuji Photo Film Co Ltd | Lithographic type diffusion transfer developer |
| US4155763A (en) * | 1976-09-07 | 1979-05-22 | Fuji Photo Film Co., Ltd. | Color photographic processing method |
| DE2910251A1 (en) * | 1978-03-15 | 1979-09-20 | Minnesota Mining & Mfg | COLOR DEVELOPER FOR COLOR PHOTOGRAPHIC RECORDING MATERIAL, METHOD FOR ITS MANUFACTURING AND ITS USE |
| US4232113A (en) * | 1979-03-14 | 1980-11-04 | Minnesota Mining And Manufacturing Company | Liquid concentrated developer composition, and confection ready to mix with water including it, for use in color photography |
| EP0118693A2 (en) * | 1983-02-10 | 1984-09-19 | Minnesota Mining And Manufacturing Company | Photographic color developer composition packaged in two or more concentrated parts, particularly solutions, and concentrated color developer water solution |
| US4501812A (en) * | 1983-02-10 | 1985-02-26 | Minnesota Mining And Manufacturing Company | Photographic color developer composition packaged in two or more concentrated parts, particularly solutions, and concentrated color developer water solution |
| EP0118693A3 (en) * | 1983-02-10 | 1986-03-19 | Minnesota Mining And Manufacturing Company | Photographic color developer composition packaged in two or more concentrated parts, particularly solutions, and concentrated color developer water solution |
| US5578433A (en) * | 1994-10-17 | 1996-11-26 | Fuji Photo Film Co., Ltd. | Processing composition and processing method for silver halide photographic materials |
| EP0947879A1 (en) * | 1998-04-03 | 1999-10-06 | Eastman Kodak Company | Kit for photographic color developing bath |
| FR2777094A1 (en) * | 1998-04-03 | 1999-10-08 | Eastman Kodak Co | KIT FOR CHROMOGENEOUS PHOTOGRAPHIC DEVELOPER |
| WO2000054106A1 (en) * | 1999-03-08 | 2000-09-14 | Eastman Kodak Company | New color photographic developer kit |
| FR2790840A1 (en) * | 1999-03-08 | 2000-09-15 | Eastman Kodak Co | NEW KIT FOR CHROMOGENEOUS PHOTOGRAPHIC DEVELOPER |
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