US2592368A - Gelatine silver halide emulsion layer containing a dihydroxy diphenyl tanning developing agent - Google Patents

Gelatine silver halide emulsion layer containing a dihydroxy diphenyl tanning developing agent Download PDF

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US2592368A
US2592368A US783912A US78391247A US2592368A US 2592368 A US2592368 A US 2592368A US 783912 A US783912 A US 783912A US 78391247 A US78391247 A US 78391247A US 2592368 A US2592368 A US 2592368A
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developing agent
silver halide
emulsion
dihydroxy diphenyl
emulsion layer
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US783912A
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Edward C Yackel
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/06—Silver salts
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B15/00—Special procedures for taking photographs; Apparatus therefor
    • 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
    • G03C5/315—Tanning development
    • 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
    • Y10S101/00—Printing
    • Y10S101/29—Printing involving a color-forming phenomenon

Definitions

  • This invention relates to light-sensitive photographic materials and particularly to improved types of sensitized materials suitable for making images in tanned colloid vehicle.
  • a tanning developing agent into a photographic emulsion on a support such as tracing cloth and after exposure and development to form relief images by washing the unexposed emulsion away with water.
  • veloping agent such as pyrocatechol or hydro- .quinone is used, because of solubility, vapor pressure, etc., the developing agent does not remain in the emulsion layer during long periods of keeping. Instead, it wanders throughout the gelatin and waterproofing layer of a material such as tracing cloth and from one piece of material to another when the two are in close contact. This Wandering of the developing agent results in undesirable stain, poor developability, etc.
  • a light-sensitive silver'salt emulsion layer containing a substantially water insoluble tanning developing agent is prepared.
  • a support such as'tracing cloth, a cellulose ester film baseglass, or paper.
  • Fine-grain gelatino-silver bromide emulsions are preferably used but silverchloride or other silver halide emulsions may be used in gelatin or other vehicles such as polyvinyl alcohol, which can be differentially tanned with tanning developing agents.
  • the developing agent may be any substantially water-insoluble developing agent which tans the gelatin or other carrier, for the silver halide, upon development in an alkaline solution.
  • tanning developing agents specially useful because of their non-wandering characteristics, high rate of development, high tanning efliciency, and solubility in the preferred range, are those having a solubility of from about .005 to 1.0 gram per hundredcc. of a phosphate citric acid buffer solution of pH 5.0 prepared from a 1.5 per cent solution of sodium dihydrogenphosphate and sufficient citric acid to bring the pH to 5.0.
  • the preferred developing agent has the solubility of from about .01 to 0.2 gram per hundred cc. of buffer solution.
  • Developing agents following within the above classification arepfor example, 3,4-dihydroxy diphenyl; 2,5-dihydroxy diphenyl; 2,3-dihydroxy diphenyl; and 5,6,'7,8-tetrahydro napthohydroquinone.
  • Compounds like 2-hydroxy-5-amino-diphenyl or 3,4-diaminodipheny1 are not especially useful because of their poor stability characteristics or failure to differentially tan the emulsion vehicle.
  • the developing agents are substantially water-insoluble this is defined as meaning tanning developing agents having solubility within the above range of buffer solution.
  • the emulsion vehicle is substantially unhardened this is defined as meaning not harder than would be the case with gelatin containing 0.25 ounce of formaldehyde (40 per cent solution diluted 1 to 3 with water) per pound, when freshly coated, or 0.1 ounce of the solution per pound for a sample aged three to six months.
  • Emulsion layers appreciably harder are not very satisfactory for use in my process or that of the above oopending application. 7
  • the emulsion layer prepared as above is exposed in the usual manner under a line drawing and is "developed by immersion in an aqueous solution of an alkali such as sodium or potassium carbonate, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, or ammonium hydroxide, or an amine.
  • an alkali such as sodium or potassium carbonate
  • an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, or ammonium hydroxide, or an amine.
  • the addition to the alkaline solution, of other materials, is also helpful in obtaining a satisfactory relief image.
  • the addition of sodium hydroxide to a sodium carbonate solution improves the sensitometric characteristics of the material as well as the relief properties.
  • reducing agents such as ascorbic acid, hydrazine hydrochloride, sodium sulfite, in small quantities, sodium bicarbonate and urea, are also advantageous.
  • warm water I mean water at a temperature of about 90 F. to 100 F. or higher
  • Example I while stirring the latter over a period of about 10 minutes; Solution B preferably not being allowed to run in faster than C. Thereafter, 150 grams of gelatin in 1500 cc. of water at 40 C. are added. The emulsion is then adjusted to pH of 5.0. If desired, the emulsion may then be chilled, set, and washed in the usual manner. It is then remelted and 25 grams of 3,4-dihydroxy diphenyl dissolved in 250 cc. of methyl alcohol is slowly added to the above emulsion with stirring. As a result the developing agent becomes dispersed in the emulsion in minute crystals. Preparatory to coating an emulsion layer, in case a gelatin having poor physical properties has been used, 2 cc. of 10% formaldehyde may be added and this composition is coated on a prepared tracing cloth support over an area of about 500 square feet and dried.
  • 2 cc. of 10% formaldehyde may be added and this composition is coated on a prepared tracing cloth support
  • Example II Another emulsion suitable for use in my invention is made from the following solutions-(A) 25 grams gelatin in 1 liter water at 40 C.; (B) grams silver nitrate dissolved in 500 cc. water at 20 C.; (C) '72 grams potassium bromide in 500 cc. water at 20 C. Solutions B and C are simultaneously run into Solution A with stirring and afterwards a solution of 200 grams gelatin in 2 liter water at 40 C. is added. A suitable surface-active agent may then be added and the pH adjusted to 5.0. Thereafter a solution of 25 grams of 4-phenyl catechol in 250 cc. of methyl alcohol is added with stirring. Preparatory to coating the emulsion on a support as tracing cloth, a small quantity of hardener may be added as in Example I following which the emulsion is coated over an area of about 300 square feet.
  • the concentration of developing agent in the emulsion is dependent in part on the result desired but can be of the order of 350 grams per kg. of silver nitrate, converted to silver halide. used in making the emulsion, to obtain good density, or about 250 grams per kg. of silver nitrate to obtain adequate density and an emulsion having optimum keeping properties.
  • a typical tracing cloth at various stages in my process.
  • a support ill of sized tracing cloth is coated with a gelatinosilver halide emulsion II containing a substantially water insoluble tanning developing agent.
  • This material is exposed and developed by immersion in an alkaline solution to form images of silver and hardened gelatin as shown at I 2 in Fig. 2.
  • the remaining unhardened gelatin and silver halide I3 in Fig. 2 is then washed off by treatment of the tracing cloth with warm water to leave images ll of hardened gelatin on the support III as shown in Fig. 3.
  • a photographic emulsion layer comprising a substantially unhardened gelatin vehicle and dispersed in said vehicle a silver halide and a tanning developing agent of the class consisting of 2,3-dihydroxy diphenyl, 2,5-dihydroxy diphenyl, and 3,4-dihydroxy diphenyl.
  • a photographic emulsion layer comprising Number gelatin, silver halide, and 2,3-dihydroxy diphenyl. 1,535,700 3.
  • a photographic emulsion layer comprising 1,709,569 gelatin, silver halide, and 2,5-dihydroxy diphenyl. 1,812,981 4.
  • a photographic emulsion layer comprising 5 2,039,730 gelatin, silver halide, and 3,4-dihydroxy diphenyl. 2,090,484

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Paper (AREA)
  • Laminated Bodies (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

Apnl 8, 1952 c, YACKEL 2,592,368
GELATINE SILVER HALIDE EMULSION LAYER CONTAINING A DIHYDROXY DIPHENYL TANNING DEVELOPING AGENT Filed Nov. 4, 1947 FIG l /6/L VER HAL/DE EMULSION CONTAIN/N6 INSOLUBLE TANN/NG DEVELOPING AGE/V7 J0 TRA C/NG' C'LOTH 67L VER lMAGE IN TANNED COLLOID J3 A EMULSION DEVELOPED 10 ALKAL/ SOLUTION UNTANNED EMULSION WASHED OFF 10 EDWARD C YACKEL INVENTOR W.M BY fiaw ewf ATTORNEYS Patented Apr. 8, 1952 OFFICE GELATINE SILVER HALIDE EMULSION LAYER CONTAINING A, DIHYDROXY DIPHENYL T A N N I N G DEVELOPING AGENT Edward C. Yackel, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application November 4, 1947, Serial No. 783,912
4 Claims.
This invention relates to light-sensitive photographic materials and particularly to improved types of sensitized materials suitable for making images in tanned colloid vehicle.
In the sensitized photographic tracing cloth at present available a silver halide emulsion is coated on a subbed tracing cloth which has generally been waterproofed. This material sometimes has the. disadvantage that the processed cloth shows a bad tendency to curl which interferes with its every-day use and with filing of the finished drawing. Another disadvantage is that erasures and corrections on the processed sheet are diflicult because of the presence of gelatin. In another type of tracing cloth in which bichromated'gelatin is used the photographic speed of the material is extremely low and the unexposed or unprocessed material has poor keeping properties.
I have found that it is possible to incorporate a. tanning developing agent into a photographic emulsion on a support such as tracing cloth and after exposure and development to form relief images by washing the unexposed emulsion away with water. veloping agent such as pyrocatechol or hydro- .quinone is used, because of solubility, vapor pressure, etc., the developing agent does not remain in the emulsion layer during long periods of keeping. Instead, it wanders throughout the gelatin and waterproofing layer of a material such as tracing cloth and from one piece of material to another when the two are in close contact. This Wandering of the developing agent results in undesirable stain, poor developability, etc. ever, if a substantially water-insoluble tanning developing agent is used inthe emulsion layer the objections to a more soluble type of developing agent are overcome. In addition, when emulsion layers are compounded with the substantially water-insoluble tanning developing agents according to my invention such emulsion layersare eminently suitable for use in a process of the type described and claimed, in Yutzy and Yackel U. S. patent application, Serial No. 783,914 filed concurrently herewith.
It is therefore an object of the present invention to provide light-sensitive photographic emulsion layers containing substantially water-insoluble tanning developing agents. A further object is to provide a sensitized tracing cloth having improved properties. Other objects will appear from the following description of my invention.
These objects are accomplished in part by incorporating a substantially water-insoluble tan- However, if a soluble tanning de- Howning developing agent-in a light-sensitive photographic emulsion layer, and further, by coating such an emulsion layer ona tracing cloth or other support and after exposure and development in analkali solution, treating the element with warm water'to wash away the undevelopedsilver. halide with its vehicle. This leaves-a tanned colloid relief image on the tracing cloth or other support and providesan image carrying materia1 which is substantially free from curl and on which erasures or corrections can be madeandwhich has good keeping properties.
In the accompanying drawings, the three figures are enlarged cross-sectional views of the tracing cloth at various stages in my process.
According to my invention a light-sensitive silver'salt emulsion layer containing a substantially water insoluble tanning developing agent is prepared. According to my method of using such an emulsion layer it is coated on a support such as'tracing cloth, a cellulose ester film baseglass, or paper. Fine-grain gelatino-silver bromide emulsions are preferably used but silverchloride or other silver halide emulsions may be used in gelatin or other vehicles such as polyvinyl alcohol, which can be differentially tanned with tanning developing agents.
The developing agent may be any substantially water-insoluble developing agent which tans the gelatin or other carrier, for the silver halide, upon development in an alkaline solution. Examples of tanning developing agents specially useful because of their non-wandering characteristics, high rate of development, high tanning efliciency, and solubility in the preferred range, are those having a solubility of from about .005 to 1.0 gram per hundredcc. of a phosphate citric acid buffer solution of pH 5.0 prepared from a 1.5 per cent solution of sodium dihydrogenphosphate and sufficient citric acid to bring the pH to 5.0. The preferred developing agent has the solubility of from about .01 to 0.2 gram per hundred cc. of buffer solution. Developing agents following within the above classification arepfor example, 3,4-dihydroxy diphenyl; 2,5-dihydroxy diphenyl; 2,3-dihydroxy diphenyl; and 5,6,'7,8-tetrahydro napthohydroquinone. Compounds like 2-hydroxy-5-amino-diphenyl or 3,4-diaminodipheny1 are not especially useful because of their poor stability characteristics or failure to differentially tan the emulsion vehicle.
Here and in the appended claims wherein it is stated that the developing agents are substantially water-insoluble this is defined as meaning tanning developing agents having solubility within the above range of buffer solution.
Here and in the appended claims wherein it is stated that the emulsion vehicle is substantially unhardened this is defined as meaning not harder than would be the case with gelatin containing 0.25 ounce of formaldehyde (40 per cent solution diluted 1 to 3 with water) per pound, when freshly coated, or 0.1 ounce of the solution per pound for a sample aged three to six months. Emulsion layers appreciably harder are not very satisfactory for use in my process or that of the above oopending application. 7
In general, when utilizing the usual type of photographic gelatin useful results are obtained without addition of hardener to the emulsion. In case the gelatin in use has poor physical properties then a small amount of hardener such as formaldehyde may be used.
The emulsion layer prepared as above is exposed in the usual manner under a line drawing and is "developed by immersion in an aqueous solution of an alkali such as sodium or potassium carbonate, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, or ammonium hydroxide, or an amine. The addition to the alkaline solution, of other materials, is also helpful in obtaining a satisfactory relief image. For example, the addition of sodium hydroxide to a sodium carbonate solution improves the sensitometric characteristics of the material as well as the relief properties. The addition of reducing agents such as ascorbic acid, hydrazine hydrochloride, sodium sulfite, in small quantities, sodium bicarbonate and urea, are also advantageous.
After development of the exposed material in the alkaline solution the element is washed with warm water to remove the unexposed and undeveloped colloid and silver halide and then dried. By warm water I mean water at a temperature of about 90 F. to 100 F. or higher My invention will be further understood by reference to the following examples which are illustrative only.
Example I while stirring the latter over a period of about 10 minutes; Solution B preferably not being allowed to run in faster than C. Thereafter, 150 grams of gelatin in 1500 cc. of water at 40 C. are added. The emulsion is then adjusted to pH of 5.0. If desired, the emulsion may then be chilled, set, and washed in the usual manner. It is then remelted and 25 grams of 3,4-dihydroxy diphenyl dissolved in 250 cc. of methyl alcohol is slowly added to the above emulsion with stirring. As a result the developing agent becomes dispersed in the emulsion in minute crystals. Preparatory to coating an emulsion layer, in case a gelatin having poor physical properties has been used, 2 cc. of 10% formaldehyde may be added and this composition is coated on a prepared tracing cloth support over an area of about 500 square feet and dried. The
dried product is exposed to a suitable negative and developed in a 4 percent sodium carbonate solution. The developed element is then washed with water at 35 C. to remove the unexposed, undeveloped and untanned emulsion, is then rinsed and dried. A positive relief image in gelatin is thus obtained with no gelatin remaining in the unexposed area. Erasures and redrawing of lines were as satisfactory on the print as on the uncoated tracing cloth. Curl was greatly diminished and was approximately equivalent to that of the uncoated tracing cloth, after having been processed through the same baths.
Example II Another emulsion suitable for use in my invention is made from the following solutions-(A) 25 grams gelatin in 1 liter water at 40 C.; (B) grams silver nitrate dissolved in 500 cc. water at 20 C.; (C) '72 grams potassium bromide in 500 cc. water at 20 C. Solutions B and C are simultaneously run into Solution A with stirring and afterwards a solution of 200 grams gelatin in 2 liter water at 40 C. is added. A suitable surface-active agent may then be added and the pH adjusted to 5.0. Thereafter a solution of 25 grams of 4-phenyl catechol in 250 cc. of methyl alcohol is added with stirring. Preparatory to coating the emulsion on a support as tracing cloth, a small quantity of hardener may be added as in Example I following which the emulsion is coated over an area of about 300 square feet.
The concentration of developing agent in the emulsion is dependent in part on the result desired but can be of the order of 350 grams per kg. of silver nitrate, converted to silver halide. used in making the emulsion, to obtain good density, or about 250 grams per kg. of silver nitrate to obtain adequate density and an emulsion having optimum keeping properties.
In the accompanying drawings, I have shown a typical tracing cloth at various stages in my process. As shown in Fig. 1, a support ill of sized tracing cloth is coated with a gelatinosilver halide emulsion II containing a substantially water insoluble tanning developing agent. This material is exposed and developed by immersion in an alkaline solution to form images of silver and hardened gelatin as shown at I 2 in Fig. 2. The remaining unhardened gelatin and silver halide I3 in Fig. 2 is then washed off by treatment of the tracing cloth with warm water to leave images ll of hardened gelatin on the support III as shown in Fig. 3.
I am aware that the incorporation of organic developing agents in emulsions to form self-developing emulsions is well known and that the use of hardening developers in solution to form hardened gelatin images for use in the production of relief images, is also known. However, I am not aware that substantially waterinsoluble hardening developing agents of the type specified above have been incorporated in light-sensitive silver salt emulsions and the resulting emulsions used to form tanned images.
My invention having been described, I would have it understood that the disclosure herein is by way of example and included in the invention are all modifications and equivalents falling within the scope of the appended claims.
What I claim is:
l. A photographic emulsion layer comprising a substantially unhardened gelatin vehicle and dispersed in said vehicle a silver halide and a tanning developing agent of the class consisting of 2,3-dihydroxy diphenyl, 2,5-dihydroxy diphenyl, and 3,4-dihydroxy diphenyl.
- 5 2. A photographic emulsion layer comprising Number gelatin, silver halide, and 2,3-dihydroxy diphenyl. 1,535,700 3. A photographic emulsion layer comprising 1,709,569 gelatin, silver halide, and 2,5-dihydroxy diphenyl. 1,812,981 4. A photographic emulsion layer comprising 5 2,039,730 gelatin, silver halide, and 3,4-dihydroxy diphenyl. 2,090,484
EDWARD C. YACKEL. 2,126,899
2,315,966 REFERENCES CITED 2,334 215 The following references are of record in the 10 213501124 file of this patent: 2,409,959
UNITED STATES PATENTS Number Name Date Number 742,405 Eichengrun Oct. 27, 1903 23,251 1,102,028 Fischer June 30, 1914 581,479 1,472,048 Christensen Oct. 30, 1923 6 Name Date Troland Apr. 25, 1925 Procoudine-Gorsky Apr. 16, 1929 Procoudine-Gorsky July 7, 1931 Mannes et a1. May 5, 1936 Ostromislensky Aug. 17, 1937 Lieber- Aug. 16, 1938 Knott Apr. 6, 1943 Nadeau et a1. Nov. 16, 1943 Nadeau et a1 May 30, 1944 Ryan Oct. 22, 1946 FOREIGN PATENTS Country Date Great Britain Dec. 16, 1892 Great Britain Oct. 14, 1946

Claims (1)

1. A PHOTOGRAPHIC EMULSION LAYER COMPRISING A SUBSTANTIALLY UNHARDENED GELATIN VEHICLE AND DISPERSED IN SAID VEHICLE A SILVER HALIDE AND A TANNING DEVELOPING AGENT OF THE CLASS CONSISTING OF 2,3-DIHYDROXY DIPHENYL, 2,5-DIHYDROXY DIPHENYL, AND 3,4-DIHYDROXY DIPHENYL.
US783912A 1947-11-04 1947-11-04 Gelatine silver halide emulsion layer containing a dihydroxy diphenyl tanning developing agent Expired - Lifetime US2592368A (en)

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US783914A US2596756A (en) 1947-11-04 1947-11-04 Photomechanical copy method
US783912A US2592368A (en) 1947-11-04 1947-11-04 Gelatine silver halide emulsion layer containing a dihydroxy diphenyl tanning developing agent
US267446A US2675313A (en) 1947-11-04 1952-01-21 Photographic reproduction process
US267482A US2763553A (en) 1947-11-04 1952-01-21 Lithographic offset printing process

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US783914A Expired - Lifetime US2596756A (en) 1947-11-04 1947-11-04 Photomechanical copy method
US267446A Expired - Lifetime US2675313A (en) 1947-11-04 1952-01-21 Photographic reproduction process
US267482A Expired - Lifetime US2763553A (en) 1947-11-04 1952-01-21 Lithographic offset printing process

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US267446A Expired - Lifetime US2675313A (en) 1947-11-04 1952-01-21 Photographic reproduction process
US267482A Expired - Lifetime US2763553A (en) 1947-11-04 1952-01-21 Lithographic offset printing process

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US2716059A (en) * 1952-01-21 1955-08-23 Eastman Kodak Co Photographic transfer process
US2740717A (en) * 1952-05-03 1956-04-03 Eastman Kodak Co Photographic transfer process
US2843485A (en) * 1952-05-03 1958-07-15 Eastman Kodak Co Transfer process of photographic printing
US3146104A (en) * 1959-12-21 1964-08-25 Eastman Kodak Co Silver halide sensitized lithographic printing plate
US3287129A (en) * 1963-01-16 1966-11-22 Eastman Kodak Co Light-sensitive photographic elements containing developing agent precursors
US3312550A (en) * 1959-04-10 1967-04-04 Eastman Kodak Co Processing photographic elements containing developing agent
US3345170A (en) * 1964-06-05 1967-10-03 Eastman Kodak Co Light sensitive photographic elements containing developing agent precursors
US4283479A (en) * 1979-02-26 1981-08-11 Fuji Photo Film Co., Ltd. Silver halide photographic materials and a process forming relief images
US4299909A (en) * 1979-08-07 1981-11-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US5037734A (en) * 1989-12-28 1991-08-06 Eastman Kodak Company Stabilized photographic element containing infrared sensitizing dye

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US2739890A (en) * 1952-01-21 1956-03-27 Eastman Kodak Co Photographic reproduction process
NL94963C (en) * 1952-05-13
US2704712A (en) * 1952-09-18 1955-03-22 Eastman Kodak Co Photographic copying process
US2710820A (en) * 1952-09-18 1955-06-14 Eastman Kodak Co Formation of laminates using contact resins
US2795504A (en) * 1952-10-25 1957-06-11 Dick Co Ab Compositions for use in the manufacture of elements in reproduction
US3010389A (en) * 1953-03-09 1961-11-28 Buskes Willem Marie Photographic transfer printing plates
US2747999A (en) * 1953-03-16 1956-05-29 Eastman Kodak Co Photographic reproduction process
DE954391C (en) * 1953-06-05 1956-12-13 Agfa Ag Fuer Photofabrikation Halogen silver layers containing developer substances
US2969015A (en) * 1953-07-14 1961-01-24 Dick Co Ab Method of producing a spirit master from a positive and a duplicating process with same
US2914404A (en) * 1953-07-31 1959-11-24 Blaupunkt Werke Gmbh Method of producing two-dimensional circuits or circuit elements on supporting bases
US2756143A (en) * 1953-12-24 1956-07-24 Eastman Kodak Co Photographic reproduction process
US3010390A (en) * 1954-06-29 1961-11-28 Buskes Willem Marie Planographic printing plates
US3010391A (en) * 1954-06-29 1961-11-28 Grinten Chem L V D Light-sensitive sheets and process for producing transfer images
US2903964A (en) * 1955-01-24 1959-09-15 Eastman Kodak Co Photographic spirit duplicating process
US3029727A (en) * 1956-07-13 1962-04-17 Polychrome Corp Method and composition for fixing transfer image
US3278958A (en) * 1955-03-31 1966-10-18 Dick Co Ab Method of imaging a photolithographic plate and elements for use in the preparation of same
BE546664A (en) * 1955-04-05
US2942975A (en) * 1955-05-05 1960-06-28 Keuffel & Esser Co Photosensitive material
US2873671A (en) * 1955-05-11 1959-02-17 Dick Co Ab Copy process and materials for use in same
US2834676A (en) * 1955-07-19 1958-05-13 Sperry Rand Corp Photographic diffusion transfer process for producing multiple direct positive copies
US3220837A (en) * 1955-07-22 1965-11-30 Polaroid Corp Diffusion transfer to stratum of a silver image inked and used in printing
US2865745A (en) * 1955-08-25 1958-12-23 Eastman Kodak Co Photographic reproduction process
BE555103A (en) * 1956-02-18
BE555263A (en) * 1956-02-25
US2856283A (en) * 1956-05-07 1958-10-14 Eastman Kodak Co Photographic emulsion
DE1200134B (en) * 1957-05-09 1965-09-02 Wilhelm Ritzerfeld Printing form foil with a light-sensitive direct positive halogen silver layer and a translucent carrier
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FR1092963A (en) 1955-04-28
BE517064A (en) 1954-11-26
FR980399A (en) 1951-05-11
FR980401A (en) 1951-05-11
FR1089934A (en) 1955-03-24
BE517066A (en) 1954-11-26
BE485611A (en) 1948-11-13
BE485609A (en) 1942-11-12
US2596756A (en) 1952-05-13
US2675313A (en) 1954-04-13
GB725667A (en) 1955-03-09
GB655273A (en) 1951-07-18
GB726543A (en) 1955-03-23
GB655274A (en) 1951-07-18
US2763553A (en) 1956-09-18
DE927307C (en) 1955-05-23
DE874704C (en) 1953-04-27

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