US2828203A - Method of increasing clayden desensitization of photographic emulsions - Google Patents
Method of increasing clayden desensitization of photographic emulsions Download PDFInfo
- Publication number
- US2828203A US2828203A US440283A US44028354A US2828203A US 2828203 A US2828203 A US 2828203A US 440283 A US440283 A US 440283A US 44028354 A US44028354 A US 44028354A US 2828203 A US2828203 A US 2828203A
- Authority
- US
- United States
- Prior art keywords
- clayden
- exposure
- emulsion
- intensity
- density
- 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
- 239000000839 emulsion Substances 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 10
- 238000000586 desensitisation Methods 0.000 title description 10
- -1 SILVER HALIDE Chemical class 0.000 claims description 15
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 239000000975 dye Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 9
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 3
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 3
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- MTTSAJTTXKHHJZ-UHFFFAOYSA-N 2-[5-[2-(3-ethyl-1,3-benzoxazol-2-ylidene)ethylidene]-4-oxo-3-phenyl-2-sulfanylideneimidazolidin-1-yl]acetic acid Chemical compound O1C2=CC=CC=C2N(CC)C1=CC=C(C1=O)N(CC(O)=O)C(=S)N1C1=CC=CC=C1 MTTSAJTTXKHHJZ-UHFFFAOYSA-N 0.000 description 1
- UGWULZWUXSCWPX-UHFFFAOYSA-N 2-sulfanylideneimidazolidin-4-one Chemical compound O=C1CNC(=S)N1 UGWULZWUXSCWPX-UHFFFAOYSA-N 0.000 description 1
- HDXADLHTXJJVMS-UHFFFAOYSA-N 5-[2-(3-ethyl-1,3-benzoxazol-2-ylidene)ethylidene]-3-phenyl-2-sulfanylideneimidazolidin-4-one Chemical compound C(C)N1C(OC2=C1C=CC=C2)=CC=C2C(N(C(N2)=S)C2=CC=CC=C2)=O HDXADLHTXJJVMS-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 125000002820 allylidene group Chemical group [H]C(=[*])C([H])=C([H])[H] 0.000 description 1
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical compound C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 1
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical compound C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 229940043349 potassium metabisulfite Drugs 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 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
- G03C1/36—Desensitisers
-
- 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
- G03C1/08—Sensitivity-increasing substances
- G03C1/10—Organic substances
- G03C1/12—Methine and polymethine dyes
- G03C1/22—Methine and polymethine dyes with an even number of CH groups
-
- 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
- G03C1/485—Direct positive emulsions
- G03C1/48592—Positive image obtained by various effects other than photohole bleaching or internal image desensitisation, e.g. Sabatier, Clayden effect
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/141—Direct positive material
Definitions
- This invention relates. to. photography and particularly to a method of increasing the susceptibility of silver halide emulsions to Clayden desensitization.
- Clayden effect The feature which characterizes the Clayden effect is that the initial exposure of short duration to relatively high intensity light densensitizes the emulsion so that subsequent exposure to weak intensity light produces less effect than if the pre-exposure had not been given. As usually observed, .the density resulting from the two superposed exposures is less than that of the single exposure to the low intensity light.
- the elfect known as the Clayden effect has a number of practical applications. Yule and Maurer have described in'their U. S. Patent 2,691,5 86 use of the Clayden effect in preparing a pre-screened photographic material With which halftone negatives may be prepared from a continuous tone original without the use of the conventional halftone screen.
- the usefulness of such prescreened materials in the graphic arts for letterpress, lithographic and intaglio printing depends on the degree of desensitization obtainable and hence, on the degree of sensitivity of the material to the Clayden elfect.
- the emulsions which I use are those which initially, that is, without merocyanine or hemioxonol dye, are Clayden desensitizable to some degree and by the addition of these dyes become Clayden desentitizable to a useful degree.
- a silver halide emulsion which when exposed under a step tablet having 28 steps starting with approximately zero density and increasing in intervals of 0.3 density, to light from a high intensity flash lamp having 18,000 lumen seconds output in .0005 sec- 0nd, two feet from the emulsion, and without intermediate treatment is again exposed with the step tablet rotated 90,'to light from a 1000 watt tungsten lamp two feet from the emulsion, for two minutes, shows at least 0.10 log E or /3 step decrease in density between an area receiving only low intensity exposure and an area receiving the same level of low intensity exposure plus some level of high intensity exposure, when developed 1 rent 0 "ice for 2% minutes at 68 F. in a developer of the following composition:
- a suitable emulsion at any stage before coating a merocyanine or hemioxonol dye having one of the following formulas where X represents the atoms necessary to complete one of the following nuclei:
- R represents an alkyl radical, e. g., methyl or ethyl.
- Compound 1 is Example a
- compound 2 is Example 11
- compound 4 is Example 9
- compound 6 is Example 10 2,828,203 7 V c V"
- compound 9 is Example 15b of that patent.
- Compound 5 is prepared as described in Brooker and White U. S. Patent 2,165,338, being Example 7 of that patent.
- Compounds 11 and 12 are prepared as described in Keyes U. S. Patent 2,186,608.
- Example 1 To portions of a gelatino-silver halide emulsion which showed minimum Clayden effect when coated without sensitizing dye, there was added increasing amounts of l carboxymethyl 5 [(3 ethyl 2(3H) benzoxazolylidene) ethylidene] 3 phenyl 2 thiohydantoin. The separate emulsions were coated on film support, dried and prefiashed to a short duration (.0001 second) exposure to a high intensity flash lamp of approximately 18,000 lumen seconds'output, followed by an intensity scale exposure of 30 seconds duration to light from a 1000 watt tungsten lamp two feet from the emulsion. The test strips were developed 2 /2 minutes at 68 F. in the developer listed above, and the sensitivity decreasewas determined in each of the samples with the following result:
- sion according to my invention provides a useful increase in the degree of desensitization which can be obtained.
- Example 2 A coating was made and treated as in Example 1, but using as the sensitizing dye 1-carboxymethyl-5-[(3- methyl 2(3H) thiazolinylidene)isopropylidene] 3- phenyl-Z-thiohydantoin. The following results were obtained:
- Example 3 Desensitization Amount of dye, mgJmole Ag halide
- Example 3 A coating was made as in Example 1 containing 0.2 g. of the sensitizing dye per mole of silver, dissolved in methyl amine and alcohol. This coating was exposed by contact through a positive transparency to light from a Kodatron flash lamp (high intensity electronic flash of duration about 0.0001 second) at 2 feet. It was then given a general exposure to a 40 watt incandescent .bulb at 5 feet for 20 seconds. 20 seconds in a developer of the following compositio and a positive copy resulted. l
- Example 4 A series of coatings was made as in Example 1, containing the indicated amounts of the following sensitizing dyes per mole of silver halide. When exposed and processed as in Example 1, the following results were obtained:
- the emulsions which I have prepared, while intended to produce a positive reproduction of the subject by means of the Clayden effect as des-cibed in the above examples, may also be used to produce a negative image by exposure either to the high intensity light source or to a low intensity light source but not both, and development in the customary manner.
- the composition of the developing solution is not critical (as long as the emulsion has the required properties, that is, is Clayden desensitizable) and my results may even be obtained with color developers containing the customary coupling or color-forming components.
- the method of obtaining a direct-positive image in a silver halide emulsion layer which comprises imagewise exposing to a high intensity short duration flash of suflicient intensity and sufficiently short duration to produce a Clayden desensitization a silver halide emulsion which when exposed under a step tablet having 28 steps starting with approximately zero density and increasing in intervals of 0.3 density, to a light from a high intensity flash lamp having 18,000 lumen seconds output in .0005 second, two feet from the emulsion, and again exposed with the step tablet rotated 90, to low intensity light from a 1000 watt tungsten lamp 2 feet from the emulsion for 2 minutes, shows at least 0.10 log E decrease in density between an area receiving only low intensity exposure and an area receiving the same level of low intensity exposure plus some level of high intensity exposure, when developed for 2% minutes at.68 F. in a developer of the following composition:
- X representsthe atoms necessary to complete a nucleus selected from the class consisting of thiazole, thiazoline, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole and quinoline
- R is selected from the class consisting of hydrogen and'alkyl radicals
- R is an alkyl radical
- Y represents the atoms necessary to complete a nucleus selected from the class consisting of rhodanine, thiohydantoin and 2-thio-oxaz0lidinedione nuclei, then uniformly exposing said emulsion layer to a light source of sufiiciently low intensity and for a sufiiciently long time to produce a developable density in regions of said emulsion that received no high intensity exposure, and developing a positive image in said emulsion layer with a silver halide developing agent.
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Plural Heterocyclic Compounds (AREA)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE539345D BE539345A (cg-RX-API-DMAC10.html) | 1954-06-29 | ||
| US440283A US2828203A (en) | 1954-06-29 | 1954-06-29 | Method of increasing clayden desensitization of photographic emulsions |
| GB17105/55A GB773388A (en) | 1954-06-29 | 1955-06-14 | Method of obtaining a direct-positive image in a silver halide emulsion layer |
| DEE10923A DE1022090B (de) | 1954-06-29 | 1955-06-27 | Verfahren zur Erzeugung eines Direktpositivbildes in einer Halogensilberemulsion unter Ausnuetzung des Clayden-Desensibilisierungseffektes |
| FR1126802D FR1126802A (fr) | 1954-06-29 | 1955-06-29 | Procédé pour l'obtention directe d'images photographiques positives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US440283A US2828203A (en) | 1954-06-29 | 1954-06-29 | Method of increasing clayden desensitization of photographic emulsions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2828203A true US2828203A (en) | 1958-03-25 |
Family
ID=23748162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US440283A Expired - Lifetime US2828203A (en) | 1954-06-29 | 1954-06-29 | Method of increasing clayden desensitization of photographic emulsions |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US2828203A (cg-RX-API-DMAC10.html) |
| BE (1) | BE539345A (cg-RX-API-DMAC10.html) |
| DE (1) | DE1022090B (cg-RX-API-DMAC10.html) |
| FR (1) | FR1126802A (cg-RX-API-DMAC10.html) |
| GB (1) | GB773388A (cg-RX-API-DMAC10.html) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3063350A (en) * | 1958-08-11 | 1962-11-13 | Honeywell Regulator Co | Recorder |
| US3765900A (en) * | 1970-02-17 | 1973-10-16 | Agfa Gevaert Nv | Spectrally sensitized silver halide emulsions |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2078233A (en) * | 1934-09-14 | 1937-04-27 | Eastman Kodak Co | Photographic emulsion |
| US2263757A (en) * | 1937-12-16 | 1941-11-25 | Eastman Kodak Co | Ketone dye and process for preparing it |
| US2282116A (en) * | 1939-04-14 | 1942-05-05 | Eastman Kodak Co | Photographic element |
-
0
- BE BE539345D patent/BE539345A/xx unknown
-
1954
- 1954-06-29 US US440283A patent/US2828203A/en not_active Expired - Lifetime
-
1955
- 1955-06-14 GB GB17105/55A patent/GB773388A/en not_active Expired
- 1955-06-27 DE DEE10923A patent/DE1022090B/de active Pending
- 1955-06-29 FR FR1126802D patent/FR1126802A/fr not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2078233A (en) * | 1934-09-14 | 1937-04-27 | Eastman Kodak Co | Photographic emulsion |
| US2263757A (en) * | 1937-12-16 | 1941-11-25 | Eastman Kodak Co | Ketone dye and process for preparing it |
| US2282116A (en) * | 1939-04-14 | 1942-05-05 | Eastman Kodak Co | Photographic element |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3063350A (en) * | 1958-08-11 | 1962-11-13 | Honeywell Regulator Co | Recorder |
| US3765900A (en) * | 1970-02-17 | 1973-10-16 | Agfa Gevaert Nv | Spectrally sensitized silver halide emulsions |
Also Published As
| Publication number | Publication date |
|---|---|
| GB773388A (en) | 1957-04-24 |
| BE539345A (cg-RX-API-DMAC10.html) | |
| FR1126802A (fr) | 1956-12-03 |
| DE1022090B (de) | 1958-01-02 |
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