US2981622A - Photographic process - Google Patents
Photographic process Download PDFInfo
- Publication number
- US2981622A US2981622A US826407A US82640759A US2981622A US 2981622 A US2981622 A US 2981622A US 826407 A US826407 A US 826407A US 82640759 A US82640759 A US 82640759A US 2981622 A US2981622 A US 2981622A
- Authority
- US
- United States
- Prior art keywords
- acid
- latent image
- sensitized
- solution
- image
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 25
- 239000000463 material Substances 0.000 claims description 25
- 239000011964 heteropoly acid Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000000975 dye Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- 239000001018 xanthene dye Substances 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 19
- 239000002253 acid Substances 0.000 description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical class [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Chemical class 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- -1 hydrogen ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- KQEIJFWAXDQUPR-UHFFFAOYSA-N 2,4-diaminophenol;hydron;dichloride Chemical compound Cl.Cl.NC1=CC=C(O)C(N)=C1 KQEIJFWAXDQUPR-UHFFFAOYSA-N 0.000 description 1
- CMWPUDHQIUJSCD-UHFFFAOYSA-N 4-benzhydryl-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 CMWPUDHQIUJSCD-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 241000206672 Gelidium Species 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 241001208007 Procas Species 0.000 description 1
- 241001168730 Simo Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 244000010375 Talinum crassifolium Species 0.000 description 1
- 235000015055 Talinum crassifolium Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229920002494 Zein Polymers 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002508 contact lithography Methods 0.000 description 1
- FYGDTMLNYKFZSV-MRCIVHHJSA-N dextrin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)OC1O[C@@H]1[C@@H](CO)OC(O[C@@H]2[C@H](O[C@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-MRCIVHHJSA-N 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229920000591 gum Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 150000003732 xanthenes Chemical class 0.000 description 1
- 239000005019 zein Substances 0.000 description 1
- 229940093612 zein Drugs 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
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/725—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing inorganic compounds
-
- 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
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
- G03C1/732—Leuco dyes
Definitions
- This invention relates to a photographic process, and more particularly to a process in which a latent image is formed upon a material sensitized with a heteropolyacid of tungsten or molybdenum and subsequently developedfinto a visible image.
- Another advantage lies in extended shelf life of photographic materials that can be prepared with the new sens'itizers. This factor is of increasing importance because of the rising level of radioactivity not only in thebackground radiation but in natural products from which paper and other materials for the packing and preservation of photographic fillms and papers are made.
- the latent image of a silver sensitized material builds up under the continuous exposure to penetrating radiatioh into a fog that limits the shelf life.
- materials sensitized with the heteropolyacids while sensitive to ionizing radiation, can be prepared so that tlielatent image produced by exposure to penetrating radiation retrogresses and does not build up into an objectionable fog.
- Such materlals have an indefinite shelf life in spite er the increased background radiation and radioactivity of packing materials.
- proloh ed shelf life alsoec'ts the nwprocess apart from latent image processes built upon the use of such sensitizers as diazo compounds, mercury salts, lead salts, etc.
- the process is useful for the conventional photo: graphic purposes of making negatives-andpositive prints from negatives.
- the heteropolyacids may be sensitized to longer wave lengths extending through the visible spectrum by derivatives of Xanthene dyes, and thus the procas may" utilize orthochrcmatic materials.
- the process yields images with very fine grain, and thus is suitable for high resolution work.
- the process also is useful tor/routine reproduction of drawings and documents, recording ininstruments using mirror galvanometers, etc.
- heteropolyacids may be used singly or in admixture with each other.
- heteropolyacid is here used generically and includes both free acids and their salts in which one or more of the hydrogen ions shown in the formulae above have been replaced by another cation, usually an alkali metal ion. These salts are themselves acid in solution.
- Carbonaceous reducing agents suitable from use in the process are illustrated by the following:
- Polyhydric alcohols exemplified by: ethylene glycol, propylene glycol, glycerine, Z-ethylhexanediol- 1,3, sucrose, lactose, dextrine, starch, gum arab-ic, agar-agar, polyvinyl alcohol, triethanol amine, sorbitol.
- Polyethers exemplified by ethylene glycol diethyl ether, diethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, benzyl cellulose, acetal.
- l-olyamids exemplified by nylon
- albumen casein
- gelatin glue
- silk silk
- wool zein
- Aldehydes exemplified by formaldehyde, acetaldehyde, n-butyraldehyde, benzaldehyde.
- triphenylmethane dyes exemplified by 4 climethylamino triphenylmethane, 4,4 bis dimethylarnino triphenylmethane, 4,4,4"-tris-dimethylamino triphenylmethane, 4,4-bis-diethylan1ino triphenylmethane.
- Leucobases of Xanthene dyes exemplified by 3,6-bisdimethylamino Xanthene, 3,6 bis dimethylamino 9- two or more of the chemical functions.
- Suitable carbonaceous reducing agents may combine Examples are, polyethylene glycol of average molecular weight 300, polyethylene glycol of average molecular weight 400, polyethylene glycol of average molecular weight 1500, polyethylene glycol of average molecular weight 4000, which combine the polyether and polyhydric alcohol functions; and glucose, which combines the polyhydric alchol and aldehyde functions. 7
- the materials have their maximum sensitivity at wave lengths shorter than about 4500 ,A.
- Materials containing salts of the xanthene dye leucobases and of 4-dimethylamino-triphenylmethane are also sensitive to the longer wave lengths absorbed by the dyes corresponding to the leuco bases.
- the photographic materials may be exposed by usual photographic methods.
- the exposed sensitized material is developed preferably by a physical developer.
- Physical developers have long been known. Those employing salts of silver and mercury are most generally used, although others, such as palladium and gold developers, may be employed.
- Materials sensitized with the heterop-olytungstic acids should preferably be developed within a few days after exposure because the latent image retrogresses on these materials.
- Materials sensitized with heteropolymolybdic acids may-be stored for some time after exposure and before development because on storage there is little retrogression of the latent image.
- the retrogression of the latent image may be arrested by treatment of the exposed material with a solution of a salt of a precious metal, such as silver, and washing.
- the photograph may then be stored for some time before development.
- Example 1 Water leaf paper is wet with an aqueous solution containing 2.5% of phosphotungstic acid, mrw o iin o, and 2.5% of glucose, and dried and stored in the dark. This paper is printed for 20 seconds at an intensity of 280 microwatts per square centimeter of 3650 A. U. radiation from a hot mercury arc lamp. No visible image is formed by this exposure. Immediately after printing the image is developed in red light by the following sequence of treatments: N/ 20 silver nitrate solution for minutes, rinse in water for 3 minutes, bathe in a solution of 1.1 g. potassium iodide and 2.7 g. of sodium sulfite in water to 100 ml.
- Example 2 Paper is coated with a thorough mixture of equal volumes of a 10% solution of high viscosity, completely hydrolyzed polyvinyl alcohol (such as Elvanol 72-51) brought to an acidity of pH 1.5 with (sulfuric acid, and a 2% solution of phosphotungstomolybdic acid,
- HgPWeMOsOs and dried. Contact prints to form a latent image are made upon this by the light from a hot mercury lamp. Before development the paper is treated for 1 hour at C. with 10% silver nitrate solution and rinsed with distilled water. The print then is developed for 10 minutes at 25 C. in a freshly mixed solution of 3 volumes of 5% silver nitrate and 10 volumes of a solution containing 1% of hydroquinone and 0.6% of citric acid; fixed in 35% sodium thiosulfate solution, washed and dried.
- Example 3 Paper is coated with a thorough mixture of equal volumes of a 10% solution of high viscosity, completely hydrolyzed polyvinyl alcohol, brought to an acidity of pH 1.5 with sulfuric acid; and a 1.2% solution of phospho-lZ-molybdic acid, and dried. Contact printing is done upon this by the light from a hot mercury lamp to form a latent image. Before development the paper is treated for 1 hour at 25 C. with 10% silver nitrate solution, rinsed with distilled Water and developed and fixed as in Example 2.
- Example 4 Paper is coated with a solution containing 5% of high viscosity, completely hydrolyzed polyvinyl alcohol, such as Elvanol 72-51, and 1.5% of silico-lZ-tungstic acid, the acidity having been adjusted with sulfuric acid to pH 3.
- Printing is done by a carbon arc lamp, and the latent image developed promptly for 10 minutes at 25 C. in a solution freshly mixed from 3 volumes of 5% silver nitrate and 10 volumes of a solution containing 1% of hydroquinone and 0.6% of citric acid.
- the developed print is fixed in 35% sodium thiosulfate to remove all silver salts, washed and dried.
- Example 5 Paper is coated with a solution containing 5% of high viscosity, completely hydrolyzed polyvinyl alcohol and 1% of phospho-lZ-tungstic acid, the reaction having been Paper sensitized and printed as in Example 3 is developed for minutes at 25 C. in a solution com posed of 1 volume of 10% aqueous oxalic acid and 1 volume of. 0.1 of 1% chloroauric acid, washed in running water and dried. The image is purple, in contrast with r the silver developed images, which are black.
- the photographic process comprising the steps of irradiating a photosensitive photographic material sensitized with a combination of a heteropolyacid ofa metal chosen from the group of molybdenum and tungsten and a carbonaceous reducing agent chosen from the group consisting of polyhydric alcohol, polyether, polyamid,
- aldehyde leucobase of a triphenylmethane dye, leucobase of a xauthe'ne dye to form a latent image and developing the irradiated photographic material to produce a visible image.
- the photographic process comprising the steps of irradiating a photosensitive photographic material sensitized with a combination of a heteropolyacid of a metal chosen from the group consisting of molybdenum and tungsten and a carbonaceous reducing agent chosen from the group consisting of polyhydric alcohol, polyether, polyamid, aldehyde, leucobase of a triphenylmethane dye, leucobase of a xanthene dye to form a latent image and developing the latent image into a visible image by physical development which deposits from a solution containing a metallic salt a light absorbing metallic substance upon the irradiated portions of the photosensitive photographic material.
- a heteropolyacid of a metal chosen from the group consisting of molybdenum and tungsten
- a carbonaceous reducing agent chosen from the group consisting of polyhydric alcohol, polyether, polyamid, aldehyde, leucobase of a triphenylmethane dye, leu
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Description
PHOTOGRAPHIC PRUCESS Lyman Chalkley, Prince Georges County, Md. (5320 Middleton Lane, Washington 22, B13.)
This invention relates to a photographic process, and more particularly to a process in which a latent image is formed upon a material sensitized with a heteropolyacid of tungsten or molybdenum and subsequently developedfinto a visible image.
In my copending application Serial No. 448,990, now U.S. Patent No. 2,895,892, issued July 21, 1959, of which this is a continuation in part, it was shown that photographic processes could be built upon photosensitive systems composed of a heteropolytungstic acid and a carbonaceous reducing agent. The claims in that application relatedto a printing out process in which a visible image was formed by exposure alone. The present application relates to a process in which a latent image formed upon a heteropolyacid sensitized material is subsequently developed.
The formation and development of latent images, especially upon silver sensitized materials, has long been known. The replacement of silver as the photosensitive material by compounds of tungsten and molybdenum hasa number of advantages. The first and most obvious advantage is a reduction in cost because molybdenum and tungsten are much cheaper elements than silver.
Another advantage lies in extended shelf life of photographic materials that can be prepared with the new sens'itizers. This factor is of increasing importance because of the rising level of radioactivity not only in thebackground radiation but in natural products from which paper and other materials for the packing and preservation of photographic fillms and papers are made.
The latent image of a silver sensitized material builds up under the continuous exposure to penetrating radiatioh into a fog that limits the shelf life. On the other hand, materials sensitized with the heteropolyacids, while sensitive to ionizing radiation, can be prepared so that tlielatent image produced by exposure to penetrating radiation retrogresses and does not build up into an objectionable fog. Such materlalshave an indefinite shelf life in spite er the increased background radiation and radioactivity of packing materials.
The advantage of proloh ed shelf life alsoec'ts the nwprocess apart from latent image processes built upon the use of such sensitizers as diazo compounds, mercury salts, lead salts, etc.
The process is useful for the conventional photo: graphic purposes of making negatives-andpositive prints from negatives. As already disclosed in US. Patent No. 2,895,892,.the heteropolyacids may be sensitized to longer wave lengths extending through the visible spectrum by derivatives of Xanthene dyes, and thus the procas may" utilize orthochrcmatic materials. The process yields images with very fine grain, and thus is suitable for high resolution work. The process also is useful tor/routine reproduction of drawings and documents, recording ininstruments using mirror galvanometers, etc.
"Other uses and advantages will appear from thefollowing more detailed disclosure.
ttes arm 2,981,522 Fatented Apr. 25, 1961 12-tungstic acid, H BW O phospho-lZ-tungstic acid,
l-I PW O phospho-9-tungstic acid, H PW O phospho-12-rnolybdic acid, H PMo O., silic-o-12-molybdic 0 acid, H SiMo O phospho-lZ-tungstomolybdic acids,
H PW Mo O where x plus y equal 12. The heteropolyacids may be used singly or in admixture with each other. The term heteropolyacid" is here used generically and includes both free acids and their salts in which one or more of the hydrogen ions shown in the formulae above have been replaced by another cation, usually an alkali metal ion. These salts are themselves acid in solution.
Carbonaceous reducing agents suitable from use in the process are illustrated by the following:
Polyhydric alcohols, exemplified by: ethylene glycol, propylene glycol, glycerine, Z-ethylhexanediol- 1,3, sucrose, lactose, dextrine, starch, gum arab-ic, agar-agar, polyvinyl alcohol, triethanol amine, sorbitol.
Polyethers, exemplified by ethylene glycol diethyl ether, diethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, benzyl cellulose, acetal.
l-olyamids, exemplified by nylon," albumen, casein, gelatin, glue, silk, wool, zein.
Aldehydes, exemplified by formaldehyde, acetaldehyde, n-butyraldehyde, benzaldehyde.
Leucobases of triphenylmethane dyes, exemplified by 4 climethylamino triphenylmethane, 4,4 bis dimethylarnino triphenylmethane, 4,4,4"-tris-dimethylamino triphenylmethane, 4,4-bis-diethylan1ino triphenylmethane.
Leucobases of Xanthene dyes exemplified by 3,6-bisdimethylamino Xanthene, 3,6 bis dimethylamino 9- two or more of the chemical functions.
(Z-carboxyethyl) xanthene, 3,6-bis-diethylamino-9- (2-carboxyphenyl) xanthene, 3,6-bis-monethylamino-9- (Z-carboxyphenyl) xanthene ethyl ester.
Suitable carbonaceous reducing agents may combine Examples are, polyethylene glycol of average molecular weight 300, polyethylene glycol of average molecular weight 400, polyethylene glycol of average molecular weight 1500, polyethylene glycol of average molecular weight 4000, which combine the polyether and polyhydric alcohol functions; and glucose, which combines the polyhydric alchol and aldehyde functions. 7
Without optical sensitizers the materials have their maximum sensitivity at wave lengths shorter than about 4500 ,A. Materials containing salts of the xanthene dye leucobases and of 4-dimethylamino-triphenylmethane are also sensitive to the longer wave lengths absorbed by the dyes corresponding to the leuco bases.
The photographic materials may be exposed by usual photographic methods.
The exposed sensitized material is developed preferably by a physical developer. Physical developers have long been known. Those employing salts of silver and mercury are most generally used, although others, such as palladium and gold developers, may be employed.
Materials sensitized with the heterop-olytungstic acids should preferably be developed within a few days after exposure because the latent image retrogresses on these materials. Materials sensitized with heteropolymolybdic acids may-be stored for some time after exposure and before development because on storage there is little retrogression of the latent image.
, If it is desired. to delay the development of a heteropolytungstic acid sensitized material for some time after exposure, the retrogression of the latent image may be arrested by treatment of the exposed material with a solution of a salt of a precious metal, such as silver, and washing. The photograph may then be stored for some time before development. J
The following examples will make clearer the operation of the process.
Example 1 Water leaf paper is wet with an aqueous solution containing 2.5% of phosphotungstic acid, mrw o iin o, and 2.5% of glucose, and dried and stored in the dark. This paper is printed for 20 seconds at an intensity of 280 microwatts per square centimeter of 3650 A. U. radiation from a hot mercury arc lamp. No visible image is formed by this exposure. Immediately after printing the image is developed in red light by the following sequence of treatments: N/ 20 silver nitrate solution for minutes, rinse in water for 3 minutes, bathe in a solution of 1.1 g. potassium iodide and 2.7 g. of sodium sulfite in water to 100 ml. for 3 minutes, rinse in water for 1 minute, develop for 1 hour at 20 C. in a solution of 2 g. sodium sulfite, 0.33 g. silver nitrate, 3.2 g. sodium thiosulfate and 0.16 g. of 2,4-diaminophenol dihydrochloride in water to 100 ml., rinse for 1 minute, fix for minutes in sodium thiosulfate, wash for 10 minutes and dry. A permanent silver image is obtained.
Example 2 Paper is coated with a thorough mixture of equal volumes of a 10% solution of high viscosity, completely hydrolyzed polyvinyl alcohol (such as Elvanol 72-51) brought to an acidity of pH 1.5 with (sulfuric acid, and a 2% solution of phosphotungstomolybdic acid,
HgPWeMOsOs and dried. Contact prints to form a latent image are made upon this by the light from a hot mercury lamp. Before development the paper is treated for 1 hour at C. with 10% silver nitrate solution and rinsed with distilled water. The print then is developed for 10 minutes at 25 C. in a freshly mixed solution of 3 volumes of 5% silver nitrate and 10 volumes of a solution containing 1% of hydroquinone and 0.6% of citric acid; fixed in 35% sodium thiosulfate solution, washed and dried.
- Example 3 Paper is coated with a thorough mixture of equal volumes of a 10% solution of high viscosity, completely hydrolyzed polyvinyl alcohol, brought to an acidity of pH 1.5 with sulfuric acid; and a 1.2% solution of phospho-lZ-molybdic acid, and dried. Contact printing is done upon this by the light from a hot mercury lamp to form a latent image. Before development the paper is treated for 1 hour at 25 C. with 10% silver nitrate solution, rinsed with distilled Water and developed and fixed as in Example 2.
Example 4 Paper is coated with a solution containing 5% of high viscosity, completely hydrolyzed polyvinyl alcohol, such as Elvanol 72-51, and 1.5% of silico-lZ-tungstic acid, the acidity having been adjusted with sulfuric acid to pH 3. Printing is done by a carbon arc lamp, and the latent image developed promptly for 10 minutes at 25 C. in a solution freshly mixed from 3 volumes of 5% silver nitrate and 10 volumes of a solution containing 1% of hydroquinone and 0.6% of citric acid. The developed print is fixed in 35% sodium thiosulfate to remove all silver salts, washed and dried.
Example 5 Paper is coated with a solution containing 5% of high viscosity, completely hydrolyzed polyvinyl alcohol and 1% of phospho-lZ-tungstic acid, the reaction having been Paper sensitized and printed as in Example 3 is developed for minutes at 25 C. in a solution com posed of 1 volume of 10% aqueous oxalic acid and 1 volume of. 0.1 of 1% chloroauric acid, washed in running water and dried. The image is purple, in contrast with r the silver developed images, which are black.
The above examples illustrate the practice of the process. Many other applications will occur to those skilled in the art, and it is obvious that various changes may be made in the specific details of the invention without departing from the spirit and scope thereof.
I claim:
1. The photographic process comprising the steps of irradiating a photosensitive photographic material sensitized with a combination of a heteropolyacid ofa metal chosen from the group of molybdenum and tungsten and a carbonaceous reducing agent chosen from the group consisting of polyhydric alcohol, polyether, polyamid,
. aldehyde, leucobase of a triphenylmethane dye, leucobase of a xauthe'ne dye to form a latent image and developing the irradiated photographic material to produce a visible image.
2. The process of claim 1 wherein said heteropolyacid is phosphotungstic acid.
3. The process of claim 1 wherein said heteropolyacid is phosphomolybdic acid.
4. The process of claim 1 wherein said heteropolyacid is phosphotungstomolybdic acid.
5. The process of claim 1 wherein said heteropolyacid is silicotungstic acid.
6. The process of claim 1 wherein said heteropolyacid is silicomolybdic acid.
7. The photographic process comprising the steps of irradiating a photosensitive photographic material sensitized with a combination of a heteropolyacid of a metal chosen from the group consisting of molybdenum and tungsten and a carbonaceous reducing agent chosen from the group consisting of polyhydric alcohol, polyether, polyamid, aldehyde, leucobase of a triphenylmethane dye, leucobase of a xanthene dye to form a latent image and developing the latent image into a visible image by physical development which deposits from a solution containing a metallic salt a light absorbing metallic substance upon the irradiated portions of the photosensitive photographic material.
8. The process of claim 7 wherein said physical developer contains the salt of a noble metal and deposits such metal to form the image.
9. The process of claim 7 wherein said physical developer contains a salt of silver and deposits metallic silver to form the image.
10. The process of claim 7 wherein said physical developer contains a salt of gold and deposits metallic gold to form the image.
References Cited in the file of this patent UNITED STATES PATENTS
Claims (1)
- 7. THE PHOTOGRAPHIC PROCESS COMPRISING THE STEPS OF IRRADIATING A PHOTOSENSITIVE PHOTOGRAPHIC MATERIAL SENSITIZED WITH A COMBINATION OF A HETEROPOLYACID OF A METAL CHOSEN FROM THE GROUP CONSISTING OF MOLYBDENUM AND TUNGSTEN AND A CARBONACEOUS REDUCING AGENT CHOSEN FROM THE GROUP CONSISTING OF POLYHYDRIC ALCOHOL, POLYETHER, POLYUAMID, ALDEHYDE, LEUCOBASE OF A TRIPHENYLMETHANE DYE, LEUCOBASE OF A XANTHENE DYE TO FORM A LATENT IMAGE AND DEVELOPING THE LATENT IMAGE INTO A VISIBLE IMAGE BY PHYSICAL DEVELOPMENT WHICH DEPOSITS FROM A SOLUTION CONTAINING A METALLIC SALT A LIGHT ABSORBING METALLIC SUBSTANCE UPON THE IRRADIATED PORTIONS OF THE PHOTOSENSITIVE PHOTOGRAPHIC MATERIAL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US826407A US2981622A (en) | 1959-07-13 | 1959-07-13 | Photographic process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US826407A US2981622A (en) | 1959-07-13 | 1959-07-13 | Photographic process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2981622A true US2981622A (en) | 1961-04-25 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US826407A Expired - Lifetime US2981622A (en) | 1959-07-13 | 1959-07-13 | Photographic process |
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| US (1) | US2981622A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3272635A (en) * | 1963-04-17 | 1966-09-13 | Horizons Inc | Compositions containing leuco xanthene dyes and suitable activators |
| US3284205A (en) * | 1963-09-17 | 1966-11-08 | Horizons Inc | Benzotriazole and heterocyclic ketimide activators for leuco compounds |
| US3285150A (en) * | 1961-05-16 | 1966-11-15 | Wunder Phot Inc | Combined photographic and development apparatus |
| US3285746A (en) * | 1964-07-23 | 1966-11-15 | Alvin M Marks | Irreversible photothermotropic compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB190713726A (en) * | 1907-06-13 | 1908-05-07 | Chester Eben Albright | Improvements in Machines for Crimping and Clamping or Shaping Leather or the like in the Manufacture of Purse Bodies and similar Articles. |
| US1934451A (en) * | 1931-04-13 | 1933-11-07 | Easman Kedak Company | Ultra-violet sensitive layer |
| US2084420A (en) * | 1933-07-25 | 1937-06-22 | Agfa Ansco Corp | Manufacture of photographic pictures |
| US2427443A (en) * | 1943-06-04 | 1947-09-16 | Dick Co Ab | Light-sensitive layer and processes of making and exposing it |
| GB670883A (en) * | 1949-06-21 | 1952-04-30 | Gevaert Photo Prod Nv | Improvements in or relating to the production of photographic images |
| US2895892A (en) * | 1954-08-10 | 1959-07-21 | Chalkley Lyman | Photochemical process |
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1959
- 1959-07-13 US US826407A patent/US2981622A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB190713726A (en) * | 1907-06-13 | 1908-05-07 | Chester Eben Albright | Improvements in Machines for Crimping and Clamping or Shaping Leather or the like in the Manufacture of Purse Bodies and similar Articles. |
| US1934451A (en) * | 1931-04-13 | 1933-11-07 | Easman Kedak Company | Ultra-violet sensitive layer |
| US2084420A (en) * | 1933-07-25 | 1937-06-22 | Agfa Ansco Corp | Manufacture of photographic pictures |
| US2427443A (en) * | 1943-06-04 | 1947-09-16 | Dick Co Ab | Light-sensitive layer and processes of making and exposing it |
| GB670883A (en) * | 1949-06-21 | 1952-04-30 | Gevaert Photo Prod Nv | Improvements in or relating to the production of photographic images |
| US2895892A (en) * | 1954-08-10 | 1959-07-21 | Chalkley Lyman | Photochemical process |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3285150A (en) * | 1961-05-16 | 1966-11-15 | Wunder Phot Inc | Combined photographic and development apparatus |
| US3272635A (en) * | 1963-04-17 | 1966-09-13 | Horizons Inc | Compositions containing leuco xanthene dyes and suitable activators |
| US3284205A (en) * | 1963-09-17 | 1966-11-08 | Horizons Inc | Benzotriazole and heterocyclic ketimide activators for leuco compounds |
| US3285746A (en) * | 1964-07-23 | 1966-11-15 | Alvin M Marks | Irreversible photothermotropic compositions |
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