US2828203A - Method of increasing clayden desensitization of photographic emulsions - Google Patents

Method of increasing clayden desensitization of photographic emulsions Download PDF

Info

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
Application number
US440283A
Other languages
English (en)
Inventor
Edgar A Macwilliam
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to BE539345D priority Critical patent/BE539345A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US440283A priority patent/US2828203A/en
Priority to GB17105/55A priority patent/GB773388A/en
Priority to DEE10923A priority patent/DE1022090B/de
Priority to FR1126802D priority patent/FR1126802A/fr
Application granted granted Critical
Publication of US2828203A publication Critical patent/US2828203A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/36Desensitisers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08Sensitivity-increasing substances
    • G03C1/10Organic substances
    • G03C1/12Methine and polymethine dyes
    • G03C1/22Methine and polymethine dyes with an even number of CH groups
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/485Direct positive emulsions
    • G03C1/48592Positive image obtained by various effects other than photohole bleaching or internal image desensitisation, e.g. Sabatier, Clayden effect
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/141Direct 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)
US440283A 1954-06-29 1954-06-29 Method of increasing clayden desensitization of photographic emulsions Expired - Lifetime US2828203A (en)

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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Similar Documents

Publication Publication Date Title
US3384485A (en) Silver halide emulsions photosolubilized with optical sensitizing dyes and silver mercaptides
US2497875A (en) Direct positive photographs using aerial fogging developer
US3033682A (en) Radiation-sensitive emulsions, elements, and processes for making same
JPS6061752A (ja) 感光性平版印刷版
US3733198A (en) Direct positive processes utilizing silver halide internal latent image emulsions containing high concentration of heterocyclic thione antifoggants
US2756148A (en) Photographic emulsion having clayden effect susceptibility
US2828203A (en) Method of increasing clayden desensitization of photographic emulsions
US3446619A (en) Radiation sensitive silver-dye complexes
US3594172A (en) Light developable,direct-writing,silver halide emulsions containing gold and iodine
US2710256A (en) Photographic print-out process
US3156564A (en) Production of photographic images making use of the intensity-reversal effect
US3782957A (en) Fogged,direct-positive silver halide emulsion layer containing a cyanine dye and a compound containing a metal of group viii of the periodic table
US1582050A (en) Photographic print-out paper and prints made therefrom
US2244304A (en) Photographic process
US3364032A (en) Light-developable halide emulsions
US2414839A (en) Light sensitized lead printing compounds and process of reproduction
US3627534A (en) Direct positive photographic emulsion stabilized against development stain
US3508921A (en) Light-developable photographic material and recording process
GB1372204A (en) Method of making a positive image and photographic materials therefor
US3413122A (en) Process for forming images and elements therefor
US4045227A (en) Method for stabilizing silver halide photographic material
US2263002A (en) Desensitization of photographic emulsions
US3241961A (en) Process for forming images
US3323917A (en) Photomechanical bleachout color process
US3278307A (en) Photographic process for producing prints stabilized against print-out