US3384490A - Vacuum deposited silver halide photographic element - Google Patents
Vacuum deposited silver halide photographic element Download PDFInfo
- Publication number
- US3384490A US3384490A US421725A US42172564A US3384490A US 3384490 A US3384490 A US 3384490A US 421725 A US421725 A US 421725A US 42172564 A US42172564 A US 42172564A US 3384490 A US3384490 A US 3384490A
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- United States
- Prior art keywords
- silver halide
- fog
- sodium
- layer
- salts
- Prior art date
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- Expired - Lifetime
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- -1 silver halide Chemical class 0.000 title description 50
- 229910052709 silver Inorganic materials 0.000 title description 45
- 239000004332 silver Substances 0.000 title description 45
- 239000000126 substance Substances 0.000 description 27
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 15
- 229910052700 potassium Inorganic materials 0.000 description 15
- 239000011591 potassium Substances 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910052751 metal Chemical class 0.000 description 8
- 239000002184 metal Chemical class 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000001235 sensitizing effect Effects 0.000 description 7
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 7
- 235000019345 sodium thiosulphate Nutrition 0.000 description 7
- 150000003567 thiocyanates Chemical class 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 150000002343 gold Chemical class 0.000 description 6
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 6
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical class [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 150000003378 silver Chemical class 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 2
- 238000003287 bathing Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- HDGMAACKJSBLMW-UHFFFAOYSA-N 4-amino-2-methylphenol Chemical compound CC1=CC(N)=CC=C1O HDGMAACKJSBLMW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229910003767 Gold(III) bromide Inorganic materials 0.000 description 1
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- YNQQQPFWPHIOAF-UHFFFAOYSA-N S=C(N)NCC=C.[Au] Chemical class S=C(N)NCC=C.[Au] YNQQQPFWPHIOAF-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
- 235000016720 allyl isothiocyanate Nutrition 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical class [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- OVWPJGBVJCTEBJ-UHFFFAOYSA-K gold tribromide Chemical compound Br[Au](Br)Br OVWPJGBVJCTEBJ-UHFFFAOYSA-K 0.000 description 1
- YVIYNOINIIHOCG-UHFFFAOYSA-N gold(1+);sulfide Chemical compound [S-2].[Au+].[Au+] YVIYNOINIIHOCG-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 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
- G03C1/08—Sensitivity-increasing substances
- G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
-
- 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
- G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
- G03C1/496—Binder-free compositions, e.g. evaporated
- G03C1/4965—Binder-free compositions, e.g. evaporated evaporated
-
- 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
- Y10S430/133—Binder-free emulsion
Definitions
- This invention relates to the chemical sensitization of photographic elements having as a light sensitive layer an essentially binder-free deposit of silver halide.
- photographic elements having a light sensitive layer of binder-free silver halide may be prepared, for example, by vacuum deposition of silver halide on a suitable support. These elements have advantages in rapid processing, good acutance and ease and economy of preparation.
- one disadvantage of such elements is their relatively low sensitivity as compared to conventional silver halide emulsions. It has been found that good increases in sensitivity of the present elements may be realized by various chemical sensitizers, but that many of these sensitizers cause an undesirable increase in fog. it would be highly desirable if photographic elements having as a light sensitive layer a binder-free deposit of silver halide could be sensitized with chemical sensitizers, without inducing fog.
- One object of this invention is to provide novel photographic elements having a chemically sensitized lightsensitive layer of silver halide that is substantially free from binder, which sensitized elements exhibit low fog.
- a further object of this invention is the sensitization of photographic elements having a light sensitive, binderfree layer of silver halide, with the combination of a chemical sensitizer and a substance which coacts with the chemical sensitizer to substantially reduce fog
- Another object of this invention is to provide a novel method of sensilizing photographic elements having a light sensitive, binder-free layer of silver halide, which features employing certain chemical sensitizers in combination with a substance which reduces fog.
- Still another object of this invention is to provide novel sensitization of photographic elements having a light sensitive, vacuum deposited silver halide layer, with sensitizers in combination with certain substances which function to reduce fog.
- photographic elements having a light sensitive binder-free deposit of silver halide coated on a support are chemically sensitized with a chemical sensitizer in combination with a suitable compound which coacts with the chemical sensitizer to reduce fog.
- a photographic element having a binder-free deposit of silver halide is chemically sensitized with a gold salt, a silver salt, or a salt of a Group VIII metal having an atomic weight in excess of 100, in combination with a sulfur-containing ice compound which coacts with the chemical sensitizer to substantially reduce or eliminate fog.
- photographic elements having a vacuum deposited layer of light sensitive silver halide are sensitized with a gold salt in combination with a thiosulfate and a thiocyanate salt, such as the alkali metal or ammonium salts thereof. It has been found that when vacuum deposited silver halide layers are sensitized in accordance with this procedure, a substantial increase in the sensitivity of the element is realized without the appearance of undesirably high fog.
- the photographic element is bathed in a solution containing a combination of chemical sensitizer and a substance which coacts with the chemical sensitizer to reduce fog.
- the photographic element may be first bathed in the fog-reducing compound, and then in a solution containing the chemical sensitizer.
- the photographic element may be bathed first in a solution containing a chemical sensitizer, and then in a solution containing fog reducer. In the latter case, it is highly desirable to bathe the element in the solution containing the fog reducing agent substantially immediately after bathing it in the solution containing the chemical sensitizer in order to etfectively control fog.
- the photographic element is provided with an arrangement wherein the light sensitive layer has a contiguous hydrophilic coating containing the combination of chemical sensitizer and iog-reducing agent.
- a support is provided having thereon a binder-free light sensitive silver halide layer, and has coated thereover a hydrophilic substance containing the combination of chemical sensitizer and fog-reducing agent.
- EXAMPLE 1 A series of paper supports had vacuum deposited thereon silver bromide at a thickness of about 0.1 to 5.0 microns, and the silver bromide layer was then overcoated with a thin layer of hardened gelatin. One film strip was then bathed for 5 minutes at 68 F. in Solution 1 consisting of 4 mg. potassium chloroaurate in 200 cc. distilled water, the pAg being adjusted to 8.5 with dilute potassium bromide. Another film strip was bathed for 5 minutes at 68 F. in Solution 2 which consisted of 4 mg. potassium chloroaurate and 10 mg. sodium thiocyanate in 200 cc. distilled water. A third film strip was bathed for 5 minutes at 68 F. in Solution 3, which was the same as Solution 2 except that 2 mg. of sodium thiosulfate were added. The film strips were then exposed to room lights for 10 seconds through a step wedge and developed for 10 seconds in the following developer:
- exemplary of latter groups of salts are the water-soluble metal compounds represented by the following general formula:
- R represents a hydrogen atom, an :alkali metal atom or an ammonium radical
- M represents a metal atom selected from Group VIII of the periodic arrangement of the elements having an atomic weight greater than 100, i.e., ruthenium, rhodium, palladium, osmium, iridium and platinum
- X represents a halogen atom, e.g., a chlorine or bromine atom.
- Still other metal compounds which we employ in practicing our invention are those which are represented by the following general formula:
- R represents a hydrogen atom, an alkali metal atom or an ammonium radical
- M represents a palladium or a platinum atom
- X represents a halogen atom.
- metal compounds are ammonium and potassium chloropalladate, ammonium, sodium and potassium chloroplatinate, ammonium, potassium and sodium bromoplatinate, ammonium chlororhodate, ammonium chlororuthenate, ammonium chloroiridate; ammonium, potassium and sodium chloroplatinite, ammonium, potassium and sodium chloropalladite, etc.
- a particularly useful class of sensitizers in accordance with the invention are the soluble gold compounds, such as the gold halides, e.g., auric chloride, or complex gold halides such as potassium auric chloride, sodium aun'c chloride, potassium or sodium auric bromide, potassium or sodium auric iodide, complex gold salts such as auric sulfate, alkali metal aurous thiosulfates, alkali metal aurous sulfites, complex salts formed by interaction of thiourea and auric chloride, and complex salts such as gold thiosinamine complexes, etc.
- the gold halides e.g., auric chloride
- complex gold halides such as potassium auric chloride, sodium aun'c chloride, potassium or sodium auric bromide, potassium or sodium auric iodide
- complex gold salts such as auric sulfate, alkali metal aurous thiosulfates, alkali metal au
- An especially useful group of gold sensitizers are the salts which contain both gold and sulfur atoms, such as sodium aurous thiosulfate, potassium aurithiocyanate, 2 aurosulfobenzathiazole methochloride, and aurous sulfide, etc.
- Such salts show reduced tendency to cause background fog although it is desirable to have, in addition to such gold salts, a substance which coacts therewith to further reduce fogging.
- the substance which we employ in combination with the chemical sensitizers preferably is a sulfur containing compound.
- metal and ammonium thiocyanates e.g., potassium, sodium, ammonium, cadmium or calcuim thiocyanates; cystine, ,B-ethyl xanthate propionic acid, and the like.
- the chemical sensitizer and fog reducing compound employed in this invention may be incorporated in a layer contiguous to the binder-free silver halide layer, such as a colloid layer composed of a hydrophilic substance such as gelatin, polyvinyl alcohol, a far hydrolyzed cellulose ester, such as water soluble cellulose acetate, and other hydrophilic substances such as those referred to in US. Patent 3,039,873, column 13.
- a colloid layer composed of a hydrophilic substance such as gelatin, polyvinyl alcohol, a far hydrolyzed cellulose ester, such as water soluble cellulose acetate, and other hydrophilic substances such as those referred to in US. Patent 3,039,873, column 13.
- the photographic elements of this invention may be spectrally sensitized in any convenient manner, such as by bathing in suitable solutions of a sensitizing dye such as the cyanine or merocyanine dyes.
- the binder-free silver halide photographic elements of this invention are preferably prepared by vacuum deposition of a suitable silver halide or silver halides onto a support, for example, by the method described by De Boer et al., U.S. Patent 1,970,496 or Manfeld US. Patent 2,945,771.
- the evaporated silver halide layer may be provided with a contiguous, vacuum deposited alkali metal salt layer to increase the speed as described in Rasch and Hodges, U.S. patent application Ser. No. 361,243, filed Mar. 20, 1964.
- This invention provides a highly convenient method of sensitizing light sensitive deposits of binder-free silver halide. In using the same sensitizers in conventional silver halide emulsions, it is necessary to digest the emulsions at elevated temperatures. No digestion is required in sensitizing the photographic elements of this invention.
- sulfur compounds such as sodium thiosulfate and sodium thiocyanate
- sensitizers function as sensitizers and actually may cause fogging unless careful control is exercised.
- present activity of such compounds as antifoggants was completely unexpected.
- a photographic element having a light-sensitive binder-free vacuum-deposited layer of silver halide coated on a support, said silver halide being chemically sensitized with a compound selected from the group consisting of silver salts, gold salts and salts of a Group VIII metal having an atomic weight in excess of 100, and containing an effective quantity of a thiosulfate salt and a thiocyanate salt to substantially reduce fog.
- a photographic element comprising a support having vacuum deposited thereon a light-sensitive silver halide coating, said silver halide being chemically sensi tized with a gold salt and containing an effective quantity of a thiosulfate salt and a thiocyanate salt to substantially reduce fog.
- a photographic element comprising a support having vacuum deposited thereon a light-sensitive silver halide coating, said silver halide being chemically sensitized with potassium chloroaurate and containing an effective quantity of sodium thiosulfate and sodium thiocyanate to substantially reduce fog.
- a photographic element comprising a support hav ing a light-sensitive vacuum-deposited silver halide coating thereon, and having contiguous to said silver halide coating a hydrophilic colloid layer containing (1) a metallic salt selected from the group consisting of silver salts, gold salts and salts of a Group VIII metal having an atomic weight in excess of 100, said metallic salt being present in a concentration sufficient to chemically sensitize the silver halide, and (2) an effective quantity of a thiocyanate salt and a thiosulfate salt to reduce fog.
- a photographic element comprising a support having a light-sensitive vacuum-deposited silver halide coating thereon, and having contiguous to said silver halide coating a hydrophilic colloid layer containing (1) a sufficient quantity of potassium chloroaurate to effectively sensitize the silver halide, and (2) an effective quantity of sodium thiocyanate and sodium thiosulfate to reduce fog.
- the method of reducing fog in a chemically sensitized photographic element having a light-sensitive vacuum-deposited layer of silver halide coated on a support which comprises contacting the silver halide with a solution containing (1) a metallic salt selected from the group consisting of silver salts, gold salts and salts of a Group VIII metal having an atomic Weight in excess of 100, said metallic salt being present in a concentration sufiicient to chemically sensitize the silver halide, and (2) an effective quantity of a thiocyanate salt and a thiosulfate salt to reduce fog.
- the method of reducing fog in a chemically sensitized photographic element having a light-sensitive vacuum-deposited layer of silver halide coated on a support which comprises contacting the silver halide with a solution containing (1) a sufficient quantity of potassium chloroaurate to effectively sensitize the silver halide, and (2) an effective quantity of sodium thiocyanate and sodium thiosulfate to reduce background fog.
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Description
United States Patent 3,384,490 VACUUM DEPOSITED SILVER HALIDE PHOTOGRAPHZC ELEMENT William W. Rees, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New .lersey No Drawing. Filed Dec. 28, 1964, Ser. No. 421,725 7 Claims. (Cl. 96-410) ABSTRACT OF THE DISCLOSURE Photographic elements, incorporating a binderless layer of vacuum-deposited silver halide as the light-sensitive component, can be chemically sensitized with gold and other metal salts without an increase in fog by including the combination of a thiosulfate salt and a thiocyanate salt as an antifoggant.
This invention relates to the chemical sensitization of photographic elements having as a light sensitive layer an essentially binder-free deposit of silver halide.
It is known to provide photographic elements having a light sensitive layer of binder-free silver halide. Such elements may be prepared, for example, by vacuum deposition of silver halide on a suitable support. These elements have advantages in rapid processing, good acutance and ease and economy of preparation. However, one disadvantage of such elements is their relatively low sensitivity as compared to conventional silver halide emulsions. It has been found that good increases in sensitivity of the present elements may be realized by various chemical sensitizers, but that many of these sensitizers cause an undesirable increase in fog. it would be highly desirable if photographic elements having as a light sensitive layer a binder-free deposit of silver halide could be sensitized with chemical sensitizers, without inducing fog.
One object of this invention is to provide novel photographic elements having a chemically sensitized lightsensitive layer of silver halide that is substantially free from binder, which sensitized elements exhibit low fog. A further object of this invention is the sensitization of photographic elements having a light sensitive, binderfree layer of silver halide, with the combination of a chemical sensitizer and a substance which coacts with the chemical sensitizer to substantially reduce fog Another object of this invention is to provide a novel method of sensilizing photographic elements having a light sensitive, binder-free layer of silver halide, which features employing certain chemical sensitizers in combination with a substance which reduces fog. Still another object of this invention is to provide novel sensitization of photographic elements having a light sensitive, vacuum deposited silver halide layer, with sensitizers in combination with certain substances which function to reduce fog. Other objects of the invention will appear herein.
In accordance with this invention, photographic elements having a light sensitive binder-free deposit of silver halide coated on a support are chemically sensitized with a chemical sensitizer in combination with a suitable compound which coacts with the chemical sensitizer to reduce fog.
In one embodiment of the invention, a photographic element having a binder-free deposit of silver halide is chemically sensitized with a gold salt, a silver salt, or a salt of a Group VIII metal having an atomic weight in excess of 100, in combination with a sulfur-containing ice compound which coacts with the chemical sensitizer to substantially reduce or eliminate fog.
In a preferred embodiment of the invention, photographic elements having a vacuum deposited layer of light sensitive silver halide are sensitized with a gold salt in combination with a thiosulfate and a thiocyanate salt, such as the alkali metal or ammonium salts thereof. It has been found that when vacuum deposited silver halide layers are sensitized in accordance with this procedure, a substantial increase in the sensitivity of the element is realized without the appearance of undesirably high fog.
In one method of sensitizing photographic elements having a binder-free deposit of silver halide in accordance with the invention, the photographic element is bathed in a solution containing a combination of chemical sensitizer and a substance which coacts with the chemical sensitizer to reduce fog. If desired, the photographic element may be first bathed in the fog-reducing compound, and then in a solution containing the chemical sensitizer. Alternatively, the photographic element may be bathed first in a solution containing a chemical sensitizer, and then in a solution containing fog reducer. In the latter case, it is highly desirable to bathe the element in the solution containing the fog reducing agent substantially immediately after bathing it in the solution containing the chemical sensitizer in order to etfectively control fog.
In another method of sensitizing photographic elements having a binder-free silver halide layer in accordance with the invention, the photographic element is provided with an arrangement wherein the light sensitive layer has a contiguous hydrophilic coating containing the combination of chemical sensitizer and iog-reducing agent. Preferably, in sensitizing in accordance with this method of the invention, a support is provided having thereon a binder-free light sensitive silver halide layer, and has coated thereover a hydrophilic substance containing the combination of chemical sensitizer and fog-reducing agent.
Our invention will be further illustrated in the following example.
EXAMPLE 1 A series of paper supports had vacuum deposited thereon silver bromide at a thickness of about 0.1 to 5.0 microns, and the silver bromide layer was then overcoated with a thin layer of hardened gelatin. One film strip was then bathed for 5 minutes at 68 F. in Solution 1 consisting of 4 mg. potassium chloroaurate in 200 cc. distilled water, the pAg being adjusted to 8.5 with dilute potassium bromide. Another film strip was bathed for 5 minutes at 68 F. in Solution 2 which consisted of 4 mg. potassium chloroaurate and 10 mg. sodium thiocyanate in 200 cc. distilled water. A third film strip was bathed for 5 minutes at 68 F. in Solution 3, which was the same as Solution 2 except that 2 mg. of sodium thiosulfate were added. The film strips were then exposed to room lights for 10 seconds through a step wedge and developed for 10 seconds in the following developer:
Grams Methyl p-aminophenol 3.1 Sodium sulfite, des. 45.0 Hydroquinone 12.0 Sodium carbonate 67.5 Potassium bromide 1.9 Sodium thiosulfate 2.5
' Water to make 1 liter.
The strips were all then stopped, fixed and washed in the usual manner. Comparison of the three strips which had been bathed in the solution containing gold salt showed approximately four times as great a speed :as that of the control, which had not been treated in any bath. The fog in each of the strips was determined and is shown in the following table:
Table 1 Treatment: Fog Control 0.04 Solution 1 heavily fogged Solution 2 0.32 Solution 3 0.07
It may be seen in Table 1 that the sensitizing combination of the invention drastically reduces fog. The combination of sodium thiosulfate and sodium thiocyanate demonstrates unexpected coaction in providing a very low fog level.
In accordance with the invention, a large variety of silver or gold salts or salts of metals of Group VIII which have an atomic weight over 100, may be employed as sensitizer. Exemplary of latter groups of salts are the water-soluble metal compounds represented by the following general formula:
wherein R represents a hydrogen atom, an :alkali metal atom or an ammonium radical, M represents a metal atom selected from Group VIII of the periodic arrangement of the elements having an atomic weight greater than 100, i.e., ruthenium, rhodium, palladium, osmium, iridium and platinum, and X represents a halogen atom, e.g., a chlorine or bromine atom. Still other metal compounds which we employ in practicing our invention are those which are represented by the following general formula:
R M'XC,
wherein R represents a hydrogen atom, an alkali metal atom or an ammonium radical, M represents a palladium or a platinum atom, and X represents a halogen atom. Examples of such metal compounds are ammonium and potassium chloropalladate, ammonium, sodium and potassium chloroplatinate, ammonium, potassium and sodium bromoplatinate, ammonium chlororhodate, ammonium chlororuthenate, ammonium chloroiridate; ammonium, potassium and sodium chloroplatinite, ammonium, potassium and sodium chloropalladite, etc.
A particularly useful class of sensitizers in accordance with the invention are the soluble gold compounds, such as the gold halides, e.g., auric chloride, or complex gold halides such as potassium auric chloride, sodium aun'c chloride, potassium or sodium auric bromide, potassium or sodium auric iodide, complex gold salts such as auric sulfate, alkali metal aurous thiosulfates, alkali metal aurous sulfites, complex salts formed by interaction of thiourea and auric chloride, and complex salts such as gold thiosinamine complexes, etc. An especially useful group of gold sensitizers are the salts which contain both gold and sulfur atoms, such as sodium aurous thiosulfate, potassium aurithiocyanate, 2 aurosulfobenzathiazole methochloride, and aurous sulfide, etc. Such salts show reduced tendency to cause background fog although it is desirable to have, in addition to such gold salts, a substance which coacts therewith to further reduce fogging.
The substance which we employ in combination with the chemical sensitizers preferably is a sulfur containing compound. Typical sulfur compounds which may be employed are sulfur compounds containing C=S or S-S-- groups, such as thiourea, allyl isothiocyanate, thiosinamine, etc. Also useful are metal and ammonium thiocyanates, e.g., potassium, sodium, ammonium, cadmium or calcuim thiocyanates; cystine, ,B-ethyl xanthate propionic acid, and the like.
If desired, the chemical sensitizer and fog reducing compound employed in this invention may be incorporated in a layer contiguous to the binder-free silver halide layer, such as a colloid layer composed of a hydrophilic substance such as gelatin, polyvinyl alcohol, a far hydrolyzed cellulose ester, such as water soluble cellulose acetate, and other hydrophilic substances such as those referred to in US. Patent 3,039,873, column 13.
The photographic elements of this invention may be spectrally sensitized in any convenient manner, such as by bathing in suitable solutions of a sensitizing dye such as the cyanine or merocyanine dyes.
The binder-free silver halide photographic elements of this invention are preferably prepared by vacuum deposition of a suitable silver halide or silver halides onto a support, for example, by the method described by De Boer et al., U.S. Patent 1,970,496 or Manfeld US. Patent 2,945,771. If desired, the evaporated silver halide layer may be provided with a contiguous, vacuum deposited alkali metal salt layer to increase the speed as described in Rasch and Hodges, U.S. patent application Ser. No. 361,243, filed Mar. 20, 1964.
This invention provides a highly convenient method of sensitizing light sensitive deposits of binder-free silver halide. In using the same sensitizers in conventional silver halide emulsions, it is necessary to digest the emulsions at elevated temperatures. No digestion is required in sensitizing the photographic elements of this invention.
In conventional emulsions, sulfur compounds, such as sodium thiosulfate and sodium thiocyanate, function as sensitizers and actually may cause fogging unless careful control is exercised. Thus, the present activity of such compounds as antifoggants was completely unexpected.
The invention has been described in detail with particular reference to preferred embodiments thereof but it will be understood that variations and modifications can be effected within the spirit and scope of the in- Vention as described hereinabove and as defined in the appended claims.
I claim:
1. A photographic element having a light-sensitive binder-free vacuum-deposited layer of silver halide coated on a support, said silver halide being chemically sensitized with a compound selected from the group consisting of silver salts, gold salts and salts of a Group VIII metal having an atomic weight in excess of 100, and containing an effective quantity of a thiosulfate salt and a thiocyanate salt to substantially reduce fog.
2. A photographic element comprising a support having vacuum deposited thereon a light-sensitive silver halide coating, said silver halide being chemically sensi tized with a gold salt and containing an effective quantity of a thiosulfate salt and a thiocyanate salt to substantially reduce fog.
3. A photographic element comprising a support having vacuum deposited thereon a light-sensitive silver halide coating, said silver halide being chemically sensitized with potassium chloroaurate and containing an effective quantity of sodium thiosulfate and sodium thiocyanate to substantially reduce fog.
4. A photographic element comprising a support hav ing a light-sensitive vacuum-deposited silver halide coating thereon, and having contiguous to said silver halide coating a hydrophilic colloid layer containing (1) a metallic salt selected from the group consisting of silver salts, gold salts and salts of a Group VIII metal having an atomic weight in excess of 100, said metallic salt being present in a concentration sufficient to chemically sensitize the silver halide, and (2) an effective quantity of a thiocyanate salt and a thiosulfate salt to reduce fog.
5. A photographic element comprising a support having a light-sensitive vacuum-deposited silver halide coating thereon, and having contiguous to said silver halide coating a hydrophilic colloid layer containing (1) a sufficient quantity of potassium chloroaurate to effectively sensitize the silver halide, and (2) an effective quantity of sodium thiocyanate and sodium thiosulfate to reduce fog.
6. The method of reducing fog in a chemically sensitized photographic element having a light-sensitive vacuum-deposited layer of silver halide coated on a support which comprises contacting the silver halide with a solution containing (1) a metallic salt selected from the group consisting of silver salts, gold salts and salts of a Group VIII metal having an atomic Weight in excess of 100, said metallic salt being present in a concentration sufiicient to chemically sensitize the silver halide, and (2) an effective quantity of a thiocyanate salt and a thiosulfate salt to reduce fog.
7. The method of reducing fog in a chemically sensitized photographic element having a light-sensitive vacuum-deposited layer of silver halide coated on a support which comprises contacting the silver halide with a solution containing (1) a sufficient quantity of potassium chloroaurate to effectively sensitize the silver halide, and (2) an effective quantity of sodium thiocyanate and sodium thiosulfate to reduce background fog.
References Cited UNITED STATES PATENTS 2,448,857 9/1948 Brice 96-110 2,597,915 5/1952 Yutzy et al 96--110 3,219,450 11/1965 Goldberg 96--94 OTHER REFERENCES Lu Valle et al.: AD Report 220,728, pp. l-4, 7-11 and 15 14, July 1959.
J. TRAVIS BROWN, Primary Examiner.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US421725A US3384490A (en) | 1964-12-28 | 1964-12-28 | Vacuum deposited silver halide photographic element |
| DE19651472878 DE1472878A1 (en) | 1964-12-28 | 1965-12-10 | Photographic material |
| GB54249/65A GB1134007A (en) | 1964-12-28 | 1965-12-22 | Silver halide photographic materials |
| FR43903A FR1461967A (en) | 1964-12-28 | 1965-12-28 | New binder-free silver halide photographic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US421725A US3384490A (en) | 1964-12-28 | 1964-12-28 | Vacuum deposited silver halide photographic element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3384490A true US3384490A (en) | 1968-05-21 |
Family
ID=23671783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US421725A Expired - Lifetime US3384490A (en) | 1964-12-28 | 1964-12-28 | Vacuum deposited silver halide photographic element |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3384490A (en) |
| DE (1) | DE1472878A1 (en) |
| FR (1) | FR1461967A (en) |
| GB (1) | GB1134007A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4288535A (en) * | 1979-06-16 | 1981-09-08 | Konishiroku Photo Industry Co., Ltd. | Process for preparing silver halide photographic emulsions |
| US5110719A (en) * | 1988-09-06 | 1992-05-05 | Fuji Photo Film Co., Ltd. | Process for preparing a direct positive photographic material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2448857A (en) * | 1945-10-25 | 1948-09-07 | Eastman Kodak Co | Stabilization of photographic emulsions |
| US2597915A (en) * | 1949-09-24 | 1952-05-27 | Eastman Kodak Co | Stabilization of photographic emulsions sensitized with gold compounds |
| US3219450A (en) * | 1962-12-11 | 1965-11-23 | Technical Operations Inc | Photographic media including a photosensitive binder-free silver halide layer and method for producing same |
-
1964
- 1964-12-28 US US421725A patent/US3384490A/en not_active Expired - Lifetime
-
1965
- 1965-12-10 DE DE19651472878 patent/DE1472878A1/en active Pending
- 1965-12-22 GB GB54249/65A patent/GB1134007A/en not_active Expired
- 1965-12-28 FR FR43903A patent/FR1461967A/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2448857A (en) * | 1945-10-25 | 1948-09-07 | Eastman Kodak Co | Stabilization of photographic emulsions |
| US2597915A (en) * | 1949-09-24 | 1952-05-27 | Eastman Kodak Co | Stabilization of photographic emulsions sensitized with gold compounds |
| US3219450A (en) * | 1962-12-11 | 1965-11-23 | Technical Operations Inc | Photographic media including a photosensitive binder-free silver halide layer and method for producing same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4288535A (en) * | 1979-06-16 | 1981-09-08 | Konishiroku Photo Industry Co., Ltd. | Process for preparing silver halide photographic emulsions |
| US5110719A (en) * | 1988-09-06 | 1992-05-05 | Fuji Photo Film Co., Ltd. | Process for preparing a direct positive photographic material |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1461967A (en) | 1966-12-09 |
| DE1472878A1 (en) | 1969-01-09 |
| GB1134007A (en) | 1968-11-20 |
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