US2159466A - Reversal development of light-sensitive silver halide emulsions - Google Patents
Reversal development of light-sensitive silver halide emulsions Download PDFInfo
- Publication number
- US2159466A US2159466A US171702A US17170237A US2159466A US 2159466 A US2159466 A US 2159466A US 171702 A US171702 A US 171702A US 17170237 A US17170237 A US 17170237A US 2159466 A US2159466 A US 2159466A
- Authority
- US
- United States
- Prior art keywords
- silver halide
- light
- sensitive silver
- reversal development
- halide emulsions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052709 silver Inorganic materials 0.000 title description 14
- 239000004332 silver Substances 0.000 title description 14
- 239000000839 emulsion Substances 0.000 title description 8
- -1 silver halide Chemical class 0.000 title description 7
- 150000003464 sulfur compounds Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 229910052946 acanthite Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229940056910 silver sulfide Drugs 0.000 description 5
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 5
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 4
- 230000009965 odorless effect Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- 241001479434 Agfa Species 0.000 description 1
- FULZLIGZKMKICU-UHFFFAOYSA-N N-phenylthiourea Chemical compound NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 description 1
- 241001455617 Sula Species 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229960001748 allylthiourea Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/50—Reversal development; Contact processes
Definitions
- a further object is to provide a photographic s5 reversal process using'an intermediate bath with an odorless sulfur compound while preventing precipitation of silver sulfide.
- a further object is the provisionof a process for developing multi-color pictures according to 40 the reversal method in' which process the undesirable blackening of the color tint of the multicolor pictures is avoided.
- citric acid citric acid, sulfuric acid or phosphoric acid.
- Suitable odorless sulfur compounds for producing silver sulfide nuclei are, for example, thiourea and its derivatives, (thiosinamine), N, N-diethyl-N'-allyl thiourea, N-phenyl thiourea, N, N-diethanol-N'-phenyl thiourea. v
- the process is suitable for the reversal development of any black-and-white or color, picture, especially for producing color reversal pictures which are produced by'color forming development.
- These latter are first developed in an ordinary negative developer, then treated in an acid bath containing a sulfur compound. which is odorless and can produce silver nuclei, and then developed .in a color developer to produce a positive.
- Silver halide emulsion layers containing dyestuff components which are fast to diflusion ' such as are described in U. S. patent applications Ser. No. 72.718, filed April 4, 1936; Ser. No. 90,728, filed July 15, 1936; Ser. No. 94,340, filed August 5, 1936; Ser. No.'158.860, filed August 13.
- a multi-layer photographicmaterial in which the layers contain dyestuff components fast to diifusion is. developed after exposure in one of the usual negative developers for example that known under. the registered trade-marks Amidol or Metol", and is then treated with an intermediate bath consisting .of 1000 cc. of water, 5 -cc. of glacial acetic acid and 0.4 gram of thiosinamine. It is then developed with a color developer, for instance N, N-dlethyl-para-phenylene diamine, washed and the silver image removed with farmers Reducer, followed by further washing.
- a color developer for instance N, N-dlethyl-para-phenylene diamine
- N-allyl thiourea For instance N-allyl thiourea
- the following example illustrates the invenplurality of silver halide emulsion layers, each emulsion layers, developing said emulsion layers layer containing a color former fast to diffusion, with a developer capable of forming a dyestufi developing said photographic element by means image associated with a silver image, and removof a developer incapable of forming a dye with in: the residual silver from all the layers.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
mama May 23, 1939 BEVERSAL DEVELOPMENT OF LIGHT-SEN- SITIVE SILVER HALIDE EMULSIONS Gustav Wllmannl, Wolfen, Kreil Bitterfeld, Wilhelm Schneider, Desaan',
Bitterield, signments, to
and Richard Kethnr,
Germany, assignorl, by mesne as- Agfa Ansco Corporation, Bingbamton, N. Y., a corporation of Delaware N'o Drawing. Application October 29, 1937, Se-
mi No. 111.102. 1930 Our presentinvention relates to reversal de- Lelopment of light sensitive silver halide emulons.
It is known that the reversal development of '5 light-sensitive silver halide emulsion layers may be carried out without intermediate exposure to light if thenegative silver image is removed in the second development by means of an alkaline developer containing a small proportion of an 10 odorless sulfur compound, especially thiosinamine. It has also been proposed to use this sulfur compound not in the developing bath but in an intermediate bath or in a clearing bath containing suliite. These baths containing the sulfur compound have, however, certain disadvantages. In consequence of the-instability of the sulfur compounds, for example thiourea derivatives, abundant quantities of silver sulfide sepa- "ratein the bath whether it beneutral or alkal line. The silver'suliide. produces, particularly in the colloid form, brown tints and is not bleached I by the usual reducersuch as mercuric chloride or potassium ferricyanide used for the purpose. The reversal development with the aid of sulas fur compounds in neutral or alkaline solution is in particular little suitable for use in making multi-color pictures because in consequence of the strong blackening of the picture by the separation of black silver sulfide no useful result can so be attained.
It is an object of the present invention to avoid or minimize these dimculties and disadvantages of tl'iehitherto known reversal process.
A further object is to provide a photographic s5 reversal process using'an intermediate bath with an odorless sulfur compound while preventing precipitation of silver sulfide.
A further object is the provisionof a process for developing multi-color pictures according to 40 the reversal method in' which process the undesirable blackening of the color tint of the multicolor pictures is avoided. a
Further objects will be apparent from the de-' tailed specification following hereafter.
(5 We have discovered that by using the sulfur compound in acid-solution .the sulfur compounds is quantitatively avoided so that the disturbing precipitation of silver sulfide is prevented and also the blackening of the color 50' tint; of the multi-color picture. These acid baths have further the great advantage of a much I longer duration than: the hitherto known neutral or alkaline baths. The nature of the acid used is without importance,'its pH-value being alone dees 'cisive. The sulfur compound may be used, for
the decomposition of In Germany November 10, s
2 Claims. (01.95-88) example, in a solution of acetic acid, oxalic acid,
citric acid, sulfuric acid or phosphoric acid.
Suitable odorless sulfur compounds for producing silver sulfide nuclei are, for example, thiourea and its derivatives, (thiosinamine), N, N-diethyl-N'-allyl thiourea, N-phenyl thiourea, N, N-diethanol-N'-phenyl thiourea. v
The process is suitable for the reversal development of any black-and-white or color, picture, especially for producing color reversal pictures which are produced by'color forming development. These latter are first developed in an ordinary negative developer, then treated in an acid bath containing a sulfur compound. which is odorless and can produce silver nuclei, and then developed .in a color developer to produce a positive. Silver halide emulsion layers containing dyestuff components which are fast to diflusion 'such as are described in U. S. patent applications Ser. No. 72.718, filed April 4, 1936; Ser. No. 90,728, filed July 15, 1936; Ser. No. 94,340, filed August 5, 1936; Ser. No.'158.860, filed August 13.
1937; Ser. No. 159,518, filed August 1'1, 193 andthe U. S. Patent applications Ser. No. flied September 18, 1937; and Ser. No. 166,832. filed October 1, 1937, may be developed by the process herein described.
tion:
A multi-layer photographicmaterial in which the layers contain dyestuff components fast to diifusion is. developed after exposure in one of the usual negative developers for example that known under. the registered trade-marks Amidol or Metol", and is then treated with an intermediate bath consisting .of 1000 cc. of water, 5 -cc. of glacial acetic acid and 0.4 gram of thiosinamine. It is then developed with a color developer, for instance N, N-dlethyl-para-phenylene diamine, washed and the silver image removed with Farmers Reducer, followed by further washing.
What we claim is: v
"In a process of developing a photographic silver halide emulsion by the reversal method, the improvement which comprises interposing between the'first and the second development an 'acid aqueous intermediate bath containing a thiourea capable of forming silver nuclei within said emulsion.
for instance N-allyl thiourea The following example illustrates the invenplurality of silver halide emulsion layers, each emulsion layers, developing said emulsion layers layer containing a color former fast to diffusion, with a developer capable of forming a dyestufi developing said photographic element by means image associated with a silver image, and removof a developer incapable of forming a dye with in: the residual silver from all the layers.
said color formers, treating said photographic GUSTAV WILMANNS. element in an acid aqueous bath containing a WILHELM SCHNEIDER. thiourea capable o'i' forming silver nuclei in said v RICHARD KE'I'HUR.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEI0056337 | 1936-11-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
US2159466A true US2159466A (en) | 1939-05-23 |
Family
ID=7194335
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US171702A Expired - Lifetime US2159466A (en) | 1936-11-10 | 1937-10-29 | Reversal development of light-sensitive silver halide emulsions |
Country Status (4)
Country | Link |
---|---|
US (1) | US2159466A (en) |
BE (1) | BE424514A (en) |
CH (1) | CH216430A (en) |
FR (1) | FR828864A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2984567A (en) * | 1957-11-29 | 1961-05-16 | Eastman Kodak Co | Method for elimination of reversal reexposure in processing photographic films |
US3246987A (en) * | 1962-07-11 | 1966-04-19 | Eastman Kodak Co | Method for elimination of reversal reexposure in processing photographic elements |
US3368898A (en) * | 1963-10-17 | 1968-02-13 | Gen Aniline & Film Corp | Autopositive film and paper and emulsions therefor |
-
0
- BE BE424514D patent/BE424514A/xx unknown
-
1937
- 1937-10-29 US US171702A patent/US2159466A/en not_active Expired - Lifetime
- 1937-11-08 CH CH216430D patent/CH216430A/en unknown
- 1937-11-08 FR FR828864D patent/FR828864A/en not_active Expired
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2984567A (en) * | 1957-11-29 | 1961-05-16 | Eastman Kodak Co | Method for elimination of reversal reexposure in processing photographic films |
US3246987A (en) * | 1962-07-11 | 1966-04-19 | Eastman Kodak Co | Method for elimination of reversal reexposure in processing photographic elements |
US3368898A (en) * | 1963-10-17 | 1968-02-13 | Gen Aniline & Film Corp | Autopositive film and paper and emulsions therefor |
Also Published As
Publication number | Publication date |
---|---|
BE424514A (en) | |
CH216430A (en) | 1941-08-31 |
FR828864A (en) | 1938-06-01 |
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