US2502529A - Photographically sensitive X-ray film elements - Google Patents
Photographically sensitive X-ray film elements Download PDFInfo
- Publication number
- US2502529A US2502529A US697829A US69782946A US2502529A US 2502529 A US2502529 A US 2502529A US 697829 A US697829 A US 697829A US 69782946 A US69782946 A US 69782946A US 2502529 A US2502529 A US 2502529A
- Authority
- US
- United States
- Prior art keywords
- fluorescent
- water
- silver halide
- ray film
- halide emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000839 emulsion Substances 0.000 claims description 25
- 229910052709 silver Inorganic materials 0.000 claims description 16
- 239000004332 silver Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 14
- 239000000049 pigment Substances 0.000 claims description 14
- 150000001241 acetals Chemical class 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 8
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 3
- 230000003381 solubilizing effect Effects 0.000 claims description 2
- -1 SILVER HALIDE Chemical class 0.000 description 16
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 11
- 239000000084 colloidal system Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229920002301 cellulose acetate Polymers 0.000 description 4
- 239000000463 material Substances 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
- 239000002904 solvent Substances 0.000 description 4
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- IQXNHMVROFUCTR-UHFFFAOYSA-N 2-formylbenzenesulfonic acid;sodium Chemical compound [Na].OS(=O)(=O)C1=CC=CC=C1C=O IQXNHMVROFUCTR-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HQWKKEIVHQXCPI-UHFFFAOYSA-L disodium;phthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C([O-])=O HQWKKEIVHQXCPI-UHFFFAOYSA-L 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical class [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- UFMBEBVGXVUTHP-UHFFFAOYSA-M sodium;acetic acid;2-carboxybenzoate Chemical compound [Na+].CC(O)=O.OC(=O)C1=CC=CC=C1C([O-])=O UFMBEBVGXVUTHP-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/16—X-ray, infrared, or ultraviolet ray processes
- G03C5/17—X-ray, infrared, or ultraviolet ray processes using screens to intensify X-ray images
-
- 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
- Y10S430/167—X-ray
Definitions
- This invention relates to photographic elements which have a light-sensitive layer and a coactive, removable, fluorescent layer. More particularly it relates to X-ray film elements which have a light-sensitive silver halide emulsion layer and a contiguous, removable, fluorescent layer.
- An object of this invention is to provide improved radiographic elements.
- a further object is to provide X-ray films and papers with removable coatings.
- a related object is to provide such elements with removable coatings which do not come off in a developer solution.
- a still further object is to provide such elements with fluorescent coatings which are readily removable in water. Still other objects will be apparent from the following description.
- the above objects are attained and commercially practical radiation-sensitive elements provided by coating the hydrophilic colloid silver I halide emulsions of photographic elements with a solution of a water-soluble, aqueous-alkalinedeveloper-insoluble colloid in a water-soluble, volatile solvent having no solvent action on the colloid binding agent of the emulsion and especially a volatile alcohol, for example, methanol or ethanol containing less than of water, said solutions having a fluorescent pigment which is activated by X-rays.
- the solvent is allowed .to evaporate.
- Other useful solvents include dioxane and acetone and mixtures ,contain'- ing not more than 10% of water.
- a satisfactory X-ray fihn element can be made by coating a transparent film base with a colloid, e. g., gelatino-silver halide emulsion, and allowing it to dry.
- a colloid e. g., gelatino-silver halide emulsion
- One of the silver halide emulsion coatings is then coated with a dispersion of a fluorescent pigment in a methanol orethanol solution of a water-Soluble, aqueous-alkalinedeveloper-insoluble colloid and allowed to dry.
- the element is exposed by means of X-rays and developed in any conventional X-ray film developing bath.
- the element is then washed in wa ter which removes the coating of fluorescentpigment. It is then fixed and again washed with water and finally dried.
- the resulting radiograph is free from haze due to pigment particles and has a clear surface.
- the developer solution is free from contamination with the colloid and fluorescent pigment.
- the washing step after development can be eliminated if desired.
- X-ray films which have a hydrophilic colloid silver halide emulsion layer on each surface need only have one of the emulsion layers coated with the novel fluorescent layers hereof. Both surfaces may be coated in order to increase the strength of the fluorescent radiation, however.
- the water-soluble polyvinyl acetals of aromatic monoaldehydes having sulfonic acid or carboxylic acid groups and alkali metal salts thereof there is used as the water-soluble, aqueous-alkalinedeveloper -insoluble colloid.
- Suitable acetals of this type can be prepared from polyvinyl alcohols and substantially completely hydrolyzed polyvinyl esters and aldehyde carboxylic or sulfonic acids, such as ortho-, meta-, and parabenzaldehyde sulfonic acid, acetaldehyde disulfonic acid, naphthaldehyde sulfonic acids, e.
- Fig. 1 is a cross-section of the film of Example I.
- Fig. 2 is a cross-section of the film of Exam ple II.
- Fig. 3 is a cross-section of the film of Exam ple III.
- Fig. 4 is a cross-section of the film of Exam ple IV.
- Example I Asshown in Fig. 1 of the drawing cellulose acetate film base I is provided with a thin gelatin phenol sublayer 2 over which is coated a gelatinosilver bromide emulsion of an X-ray type at a temperature of about F. to a weight of about mg. of silver bromide per square decimeter of surface and dried whereby layer 3 is formed;
- a dispersion of the following composition is prepared by admixing the components with stirring:
- the fluorescent mixed crystals of lead and barium sulfate contain 80% of the latter and 20% of the former and are obtainable as disclosed in United States Patent 2,289,997.
- the resulting solution is coated on the gelatino-silver halide emulsion layer to a Weight of 60 mg. per square decimeter forming layer 4.
- the element is dried. All operations are carried out in the absence of actinic radiations.
- the resulting element is given an unscreened exposure by means of X-rays and developed in a bath of the composition:
- the developed element is washed thoroughly in water whereby the fluorescent coating is removed.
- the developed and washed element is then fixed ina solution of the composition:
- Example II A similar element is made by substituting ,for the polyvinyl acetal of Example I, five grams of sodium alginate and is shown in Fig. 2 of the drawing. The water was increased to 150 cc. and the ethanol reduced to 150 cc. The fluorescent coating was readily removed by washing after exposure and development after the manner set forth in Example I.
- Example III A similar element shown in Fig. 3 of the drawing is made by substituting for the polyvinyl acetal of Example I, 15 grams of cellulose acetateacid phthalate sodium salt and one gram of gelatin resulting in layer 6. The water-alcohol ratio was changed to a 60-40 mixture. It gives similar results upon exposure-and processing as described in Example I.
- Example IV A similar element, shown in Fig. 4 of the drawing is made by substituting for the polyvinyl acetal of Example I, 2.0 grams of a mixture of 20
- the colloid silver halide emulsion layers may contain in addition to the light-sensitive silver halide, e. g., silver chlorides, silver-chloride-broinide, silver-iodobromide, etc., various sensitizing dyes and other materials which are common in emulsion layers. Such additional materials include fog inhibiting agents, emulsion hardeners, emulsion preservatives, etc.
- Suitable additional agents include calcium tungstate, fired lead sulfate, and fired barium sulfate, as described in United States Patents 2,289,384 and. 2,336,815, and zinc sulfide. These materials emit under such rays light in the ultra-violet and blue regions of the spectrum. Agents which prevent after-glow can be added if desired so that the intensification will not be prolonged after X-ray exposure has ceased.
- the radiation-sensitive layers can be deposited on various supports, e. g., paper, transparentized paper, cellulose derivatives, e. g., cellulose acetate, cellulose nitrate, superpolymers, e. g., styrene, methyl methacrylate, nylon, glass, etc.
- supports e. g., paper, transparentized paper, cellulose derivatives, e. g., cellulose acetate, cellulose nitrate, superpolymers, e. g., styrene, methyl methacrylate, nylon, glass, etc.
- the fluorescent coatings have the advantage that they form satisfactory anti-abrasion layers. Their advantage is that they are simple, economical, and do not contaminate the developer. The major advantage is that these layers eliminate the need for screens and yield films which are easily handled in industrial work.
- An X-ray film element comprising a transparent film support, a hydrophilic colloid-silver halide emulsion layer on the support and a contiguous fluorescent coating comprising a pigment which exhibits fluoresence when irradiated by X-rays dispersed in a water-soluble, aqueousalkaline-developer-insoluble polyvinyl acetal of an aromatic aldehyde containing a solubilizing group taken from the class consisting of free carboxylic acid and free sulfonic acid groups and their water-soluble salts.
- An X-ray film element comprising a transparent film support, a hydrophilic colloid-silver halide emulsion layer on the support and a contiguous fluorescent coating comprising a pigment which exhibits fluorescence when irradiated by X-rays dispersed in a water-soluble, aqueous-alkaline-developer-insoluble polyvinyl acetal of an aromatic aldehyde containing an alkali metal sulfonate group.
- An X-ray film element comprising a transparent film support, a hydrophilic colloid-silver halide emulsion layer on the support and a contiguous fluorescent coating comprising a pigment which exhibits fluoresence when irradiated by X rays dispersed in a Water-soluble, aqueous-alkaline-developer-insoluble sodium-o-sulfobenzaldehyde acetal of polyvinyl alcohol.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
April 4, 1950 o. w. MURRAY 2,502,529
PHOTOGRAPHICALLY SENSITIVE X-RAY FILM ELEMENTS Filed Sept. 18, 1946 FIG.1.
FLUORESCENT LEAD AND BARIUM SULFATE AND SODIUM-0'SULFOBENZALDEHYDE POLYVINYL ACETAL GELATINO SILVER HALIDE EMULSION GELATlN-PHENOL SUBLAYER CELLULOSE ACETATE BASE FLUORESCENT LEAD AND BARIUM SULFATE AND GELATIN- CELLULOSE ACETATE-PHTHALATE-SODIUMSALT GELATINO SILVER HALIDE EMULSION GELATIN-PHENOL SUBLAYER CELLULOSE ACETATE BASE FLUORESCENT LEAD AND BARIUM SULFATE AND SODIUM CASElNATE-GELATIN GELATINO SILVER HALIDE EMULSION GELATlN-PHENOL SUB'LAYER GELLULOSE ACETATE BASE WMIIIIIM'IIA INVENTOR.
Ofi's Willard Murray BY A T TORNE Y Patented Apr. 4, 1950 UNITED I STATES PHOTOGRAPHICALIJY SENSITIVE X-RA FILM ELEMENTS Otis Willard Murray, Fords, N. J., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware Application September 18, 1946, Serial No. 697,829
3 Claims.
This invention relates to photographic elements which have a light-sensitive layer and a coactive, removable, fluorescent layer. More particularly it relates to X-ray film elements which have a light-sensitive silver halide emulsion layer and a contiguous, removable, fluorescent layer. An object of this invention is to provide improved radiographic elements. A further object is to provide X-ray films and papers with removable coatings. A related object is to provide such elements with removable coatings which do not come off in a developer solution. A still further object is to provide such elements with fluorescent coatings which are readily removable in water. Still other objects will be apparent from the following description.
The above objects are attained and commercially practical radiation-sensitive elements provided by coating the hydrophilic colloid silver I halide emulsions of photographic elements with a solution of a water-soluble, aqueous-alkalinedeveloper-insoluble colloid in a water-soluble, volatile solvent having no solvent action on the colloid binding agent of the emulsion and especially a volatile alcohol, for example, methanol or ethanol containing less than of water, said solutions having a fluorescent pigment which is activated by X-rays. The solvent is allowed .to evaporate. Other useful solventsinclude dioxane and acetone and mixtures ,contain'- ing not more than 10% of water.
The use of such solvents or mixtures has the advantage that it does not adversely affect the fluorescent properties of the fluorescent pigment nor-embed the pigment in the emulsion layers. When solutions of the colloids in water alone are used with aqueous dispersions of fluorescent pig-. ments, the hydrophilic colloids of the emulsion layer swell under the influence of the overcoating and the pigments become embedded in the silver halide emulsion layers. The resulting emulsion layers are permanently endowed with an undesirable haze which complicates the reading of the finished radiographs The fluorescent pigment layers formed in accordance with the present invention are completely removed and no pigment haze is left in the emulsion layer.
A satisfactory X-ray fihn element can be made by coating a transparent film base with a colloid, e. g., gelatino-silver halide emulsion, and allowing it to dry. One of the silver halide emulsion coatings is then coated with a dispersion of a fluorescent pigment in a methanol orethanol solution of a water-Soluble, aqueous-alkalinedeveloper-insoluble colloid and allowed to dry. The element is exposed by means of X-rays and developed in any conventional X-ray film developing bath. The element is then washed in wa ter which removes the coating of fluorescentpigment. It is then fixed and again washed with water and finally dried. The resulting radiograph is free from haze due to pigment particles and has a clear surface. In addition, the developer solution is free from contamination with the colloid and fluorescent pigment. The washing step after development can be eliminated if desired. X-ray films which have a hydrophilic colloid silver halide emulsion layer on each surface need only have one of the emulsion layers coated with the novel fluorescent layers hereof. Both surfaces may be coated in order to increase the strength of the fluorescent radiation, however.
In the preferred aspect of the invention, there is used as the water-soluble, aqueous-alkalinedeveloper -insoluble colloid, the water-soluble polyvinyl acetals of aromatic monoaldehydes having sulfonic acid or carboxylic acid groups and alkali metal salts thereof. Suitable acetals of this type can be prepared from polyvinyl alcohols and substantially completely hydrolyzed polyvinyl esters and aldehyde carboxylic or sulfonic acids, such as ortho-, meta-, and parabenzaldehyde sulfonic acid, acetaldehyde disulfonic acid, naphthaldehyde sulfonic acids, e. g., 1-naphthaldehyde-2-sulfonic acid, l-naphthaldehydel-sulfonic acid, 2-naphthaldehyde-5-sulfonic acid, and the corresponding carboxylic acids, by condensation in the presence of mineral acids or acid salts after the manner described in German Patent 643,650. Such acetals are insoluble in aqueous alkaline photographic developer solutions containing 2% or more by weight of dissolved inorganic salts. The condensation should be carried out until the vinyl. alcohol groups have been acetalized.
The invention will be further illustrated by the following examples and in the drawin wherein: I
Fig. 1 is a cross-section of the film of Example I.
Fig. 2 is a cross-section of the film of Exam ple II. v
Fig. 3 is a cross-section of the film of Exam ple III. Fig. 4 is a cross-section of the film of Exam ple IV.
Example I Asshown in Fig. 1 of the drawing cellulose acetate film base I is provided with a thin gelatin phenol sublayer 2 over which is coated a gelatinosilver bromide emulsion of an X-ray type at a temperature of about F. to a weight of about mg. of silver bromide per square decimeter of surface and dried whereby layer 3 is formed; A dispersion of the following composition is prepared by admixing the components with stirring:
Sodium-o-sulfobenzaldehyde polyvinyl ace- The fluorescent mixed crystals of lead and barium sulfate contain 80% of the latter and 20% of the former and are obtainable as disclosed in United States Patent 2,289,997. The resulting solution is coated on the gelatino-silver halide emulsion layer to a Weight of 60 mg. per square decimeter forming layer 4. The element is dried. All operations are carried out in the absence of actinic radiations. The resulting element is given an unscreened exposure by means of X-rays and developed in a bath of the composition:
N-methyl-p-aminophenol sulfate grams 2.5 Sodium sulfite (anhydrous) do 75.0 Hydroquinone do 3.0 Borax do 5.0 Water liter 1.0
The developed element is washed thoroughly in water whereby the fluorescent coating is removed. The developed and washed element is then fixed ina solution of the composition:
Sodium thiosulfate grams 240 Sodium sulfite do 6 Boric acid do 6 Potassium alum do 12 Acetic acid (28%) ..cc 35 Water to liter 1 The finished radiograph, after washing, is free from surface stain and haze, being substantially free from any fluorescent leador barium sulfates.
Example II A similar element is made by substituting ,for the polyvinyl acetal of Example I, five grams of sodium alginate and is shown in Fig. 2 of the drawing. The water was increased to 150 cc. and the ethanol reduced to 150 cc. The fluorescent coating was readily removed by washing after exposure and development after the manner set forth in Example I.
Example III A similar element shown in Fig. 3 of the drawing is made by substituting for the polyvinyl acetal of Example I, 15 grams of cellulose acetateacid phthalate sodium salt and one gram of gelatin resulting in layer 6. The water-alcohol ratio was changed to a 60-40 mixture. It gives similar results upon exposure-and processing as described in Example I.
Example IV A similar element, shown in Fig. 4 of the drawing is made by substituting for the polyvinyl acetal of Example I, 2.0 grams of a mixture of 20 The colloid silver halide emulsion layers may contain in addition to the light-sensitive silver halide, e. g., silver chlorides, silver-chloride-broinide, silver-iodobromide, etc., various sensitizing dyes and other materials which are common in emulsion layers. Such additional materials include fog inhibiting agents, emulsion hardeners, emulsion preservatives, etc.
In place of the specific fluorescent pigments of the above examples, there can be substituted other such materials which exhibit fluoresence under the influence of X-rays. Suitable additional agents include calcium tungstate, fired lead sulfate, and fired barium sulfate, as described in United States Patents 2,289,384 and. 2,336,815, and zinc sulfide. These materials emit under such rays light in the ultra-violet and blue regions of the spectrum. Agents which prevent after-glow can be added if desired so that the intensification will not be prolonged after X-ray exposure has ceased.
The radiation-sensitive layers can be deposited on various supports, e. g., paper, transparentized paper, cellulose derivatives, e. g., cellulose acetate, cellulose nitrate, superpolymers, e. g., styrene, methyl methacrylate, nylon, glass, etc.
The fluorescent coatings have the advantage that they form satisfactory anti-abrasion layers. Their advantage is that they are simple, economical, and do not contaminate the developer. The major advantage is that these layers eliminate the need for screens and yield films which are easily handled in industrial work.
As many widely different embodiments of this invention can be made without departing from the spirit and scope thereof, it is to be understood that the invention is .not to be limited except as defined by the claims.
What is claimed is:
1. An X-ray film element comprising a transparent film support, a hydrophilic colloid-silver halide emulsion layer on the support and a contiguous fluorescent coating comprising a pigment which exhibits fluoresence when irradiated by X-rays dispersed in a water-soluble, aqueousalkaline-developer-insoluble polyvinyl acetal of an aromatic aldehyde containing a solubilizing group taken from the class consisting of free carboxylic acid and free sulfonic acid groups and their water-soluble salts.
2. An X-ray film element comprising a transparent film support, a hydrophilic colloid-silver halide emulsion layer on the support and a contiguous fluorescent coating comprising a pigment which exhibits fluorescence when irradiated by X-rays dispersed in a water-soluble, aqueous-alkaline-developer-insoluble polyvinyl acetal of an aromatic aldehyde containing an alkali metal sulfonate group.
'3. An X-ray film element comprising a transparent film support, a hydrophilic colloid-silver halide emulsion layer on the support and a contiguous fluorescent coating comprising a pigment which exhibits fluoresence when irradiated by X rays dispersed in a Water-soluble, aqueous-alkaline-developer-insoluble sodium-o-sulfobenzaldehyde acetal of polyvinyl alcohol.
OTIS WILLARD MURRAY.
REFEEENCES CITED The following references are of record in. th file of this patent:
UNITED STATES PATENTS Number Name Date 1,954,337 Staud Apr. 10, 1934 2,245,218 Murray et al June 10, 1941 2,303,917 Dietz Dec. 1, 19.42 2,319,080 Nadeau et al. May 11,1943 2,319,102 Albers et al. May 11,1943
Claims (1)
1. AN X-RAY FILM ELEMENT COMPRISING A TRANSPARENT FILM SUPPORT, A HYDROPHILIC COLLOID-SILVER HALIDE EMULSION LAYER ON THE SUPPORT AND A CONTIGUOUS FLUORESCENT COATING COMPRISING A PIGMENT WHICH EXHIBITS FLUORESENCE WHEN IRRADIATED BY X-RAYS DISPERSED IN A WATER-SOLUBLE, AQUEOUSALKALINE-DEVELOPER-INSOLUBLE POLYVINYL ACETAL OF AN AROMATIC ALDEHYDE CONTAINING A SOLUBILIZING
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US697829A US2502529A (en) | 1946-09-18 | 1946-09-18 | Photographically sensitive X-ray film elements |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US697829A US2502529A (en) | 1946-09-18 | 1946-09-18 | Photographically sensitive X-ray film elements |
Publications (1)
Publication Number | Publication Date |
---|---|
US2502529A true US2502529A (en) | 1950-04-04 |
Family
ID=24802744
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US697829A Expired - Lifetime US2502529A (en) | 1946-09-18 | 1946-09-18 | Photographically sensitive X-ray film elements |
Country Status (1)
Country | Link |
---|---|
US (1) | US2502529A (en) |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3275828A (en) * | 1962-04-02 | 1966-09-27 | Georg S Mittelstaedt | Radiographic intensifying means |
US3753714A (en) * | 1969-11-21 | 1973-08-21 | Fuji Photo Film Co Ltd | Image formation by radiation and intensification |
US5401971A (en) * | 1993-11-24 | 1995-03-28 | Eastman Kodak Company | Overcoated radiation image storage panel and method for preparing radiation image storage panel |
US5427868A (en) * | 1993-11-24 | 1995-06-27 | Eastman Kodak Company | Radiographic phosphor panel having binder compatible oxosulfur stabilizer and method for preparing phosphor panel |
US5464568A (en) * | 1993-11-24 | 1995-11-07 | Eastman Kodak Company | Alkaline earth metal fluorobromoiodide storage phosphor, and radiation image storage panel, and method |
US5507976A (en) * | 1993-11-24 | 1996-04-16 | Eastman Kodak Company | Stabilized phosphor intermediates, storage phosphors, radiation image storage panels, and preparation methods |
US5523558A (en) * | 1995-04-24 | 1996-06-04 | Eastman Kodak Company | Radiographic phosphor panel having metal hydride stabilizing compound |
US5549844A (en) * | 1995-03-24 | 1996-08-27 | Eastman Kodak Company | Radiographic phosphor panel, phosphor and phosphor modification method |
US5549843A (en) * | 1991-11-21 | 1996-08-27 | Eastman Kodak Company | Annealed alkaline earth metal fluorohalide storage phosphor, preparation method, and radiation image storage panel |
US5641583A (en) * | 1993-11-24 | 1997-06-24 | Eastman Kodak Company | Radiographic phosphor panel having both binder compatible oxosulfur stabilizer and oxosulfur pigment and method for preparing phosphor panel |
US5641967A (en) * | 1995-05-31 | 1997-06-24 | Eastman Kodak Company | Radiographic phosphor panel having oxosulfur functionalized polymer reducing agents |
US5650626A (en) * | 1996-07-16 | 1997-07-22 | Eastman Kodak Company | X-ray imaging detector with thickness and composition limited substrate |
US5753921A (en) * | 1996-07-16 | 1998-05-19 | Eastman Kodak Company | X-ray imaging detector with limited substrate and converter |
US5830629A (en) * | 1995-11-01 | 1998-11-03 | Eastman Kodak Company | Autoradiography assemblage using transparent screen |
US6346707B1 (en) * | 1996-05-23 | 2002-02-12 | Eastman Kodak Company | Electronic imaging system for autoradiography |
US6802991B2 (en) | 1999-07-02 | 2004-10-12 | Symyx Technologies, Inc. | Method for preparing a CsX photostimulable phosphor and phosphor screens therefrom |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1954337A (en) * | 1932-10-01 | 1934-04-10 | Eastman Kodak Co | Superficial coating for photographic elements |
US2245218A (en) * | 1938-07-27 | 1941-06-10 | Eastman Kodak Co | Water-soluble photographic coating |
US2303917A (en) * | 1942-04-01 | 1942-12-01 | Eastman Kodak Co | Luminescent material |
US2319080A (en) * | 1939-04-14 | 1943-05-11 | Eastman Kodak Co | Antihalation backing for photographic film |
US2319102A (en) * | 1938-06-10 | 1943-05-11 | Gen Aniline & Film Corp | Adhesive |
-
1946
- 1946-09-18 US US697829A patent/US2502529A/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1954337A (en) * | 1932-10-01 | 1934-04-10 | Eastman Kodak Co | Superficial coating for photographic elements |
US2319102A (en) * | 1938-06-10 | 1943-05-11 | Gen Aniline & Film Corp | Adhesive |
US2245218A (en) * | 1938-07-27 | 1941-06-10 | Eastman Kodak Co | Water-soluble photographic coating |
US2319080A (en) * | 1939-04-14 | 1943-05-11 | Eastman Kodak Co | Antihalation backing for photographic film |
US2303917A (en) * | 1942-04-01 | 1942-12-01 | Eastman Kodak Co | Luminescent material |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3275828A (en) * | 1962-04-02 | 1966-09-27 | Georg S Mittelstaedt | Radiographic intensifying means |
US3753714A (en) * | 1969-11-21 | 1973-08-21 | Fuji Photo Film Co Ltd | Image formation by radiation and intensification |
US5549843A (en) * | 1991-11-21 | 1996-08-27 | Eastman Kodak Company | Annealed alkaline earth metal fluorohalide storage phosphor, preparation method, and radiation image storage panel |
US5464568A (en) * | 1993-11-24 | 1995-11-07 | Eastman Kodak Company | Alkaline earth metal fluorobromoiodide storage phosphor, and radiation image storage panel, and method |
US5427868A (en) * | 1993-11-24 | 1995-06-27 | Eastman Kodak Company | Radiographic phosphor panel having binder compatible oxosulfur stabilizer and method for preparing phosphor panel |
US5507976A (en) * | 1993-11-24 | 1996-04-16 | Eastman Kodak Company | Stabilized phosphor intermediates, storage phosphors, radiation image storage panels, and preparation methods |
US5401971A (en) * | 1993-11-24 | 1995-03-28 | Eastman Kodak Company | Overcoated radiation image storage panel and method for preparing radiation image storage panel |
US5641583A (en) * | 1993-11-24 | 1997-06-24 | Eastman Kodak Company | Radiographic phosphor panel having both binder compatible oxosulfur stabilizer and oxosulfur pigment and method for preparing phosphor panel |
US5549844A (en) * | 1995-03-24 | 1996-08-27 | Eastman Kodak Company | Radiographic phosphor panel, phosphor and phosphor modification method |
US5523558A (en) * | 1995-04-24 | 1996-06-04 | Eastman Kodak Company | Radiographic phosphor panel having metal hydride stabilizing compound |
US5641967A (en) * | 1995-05-31 | 1997-06-24 | Eastman Kodak Company | Radiographic phosphor panel having oxosulfur functionalized polymer reducing agents |
US5830629A (en) * | 1995-11-01 | 1998-11-03 | Eastman Kodak Company | Autoradiography assemblage using transparent screen |
US6346707B1 (en) * | 1996-05-23 | 2002-02-12 | Eastman Kodak Company | Electronic imaging system for autoradiography |
US5650626A (en) * | 1996-07-16 | 1997-07-22 | Eastman Kodak Company | X-ray imaging detector with thickness and composition limited substrate |
US5753921A (en) * | 1996-07-16 | 1998-05-19 | Eastman Kodak Company | X-ray imaging detector with limited substrate and converter |
US6802991B2 (en) | 1999-07-02 | 2004-10-12 | Symyx Technologies, Inc. | Method for preparing a CsX photostimulable phosphor and phosphor screens therefrom |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2502529A (en) | Photographically sensitive X-ray film elements | |
US2887379A (en) | Photographic elements | |
US3155514A (en) | Photographic compositions and elements | |
US4891306A (en) | Photographic light-sensitive silver halide material containing an antistatic block copolymer | |
US4130429A (en) | Combination of photosensitive elements suited for use in radiography | |
US4130428A (en) | Combination of photosensitive elements suited for use in radiography | |
US3033682A (en) | Radiation-sensitive emulsions, elements, and processes for making same | |
US3615548A (en) | Photographic elements bearing light-absorbing layers containing an oxazole styryl dye and a metal chelate of a fuchsone dye | |
EP0211273B1 (en) | Light-sensitive elements for radiographic use and process for the formation of an x-ray image | |
US3359102A (en) | Optical brightening of photographic materials | |
US2628167A (en) | Method of making colloid silver halide emulsions containing thallium | |
US3377169A (en) | Copper thallium and lead halide and pseudohalides photosoluble crystals | |
US2332038A (en) | Photographic element | |
US2462534A (en) | Light-sensitive photographic elements | |
US3607278A (en) | Photographic elements containing fogged and unfogged silver halide grains and a slow silver halide emulsion layer | |
US3409437A (en) | Silver halide emulsions containing antibronzing agents | |
US5811229A (en) | Radiographic image forming film-screen system with blue pigment | |
US3652280A (en) | Light-sensitive silver halide emulsion with high resolving power | |
DE2128296B2 (en) | Spectrally sensitized silver halide photographic emulsion | |
US2649375A (en) | Light-sensitive photographic element | |
JPH07502132A (en) | Arylidene sensitizing dyes for tabular grains | |
US3249440A (en) | Radiation-sensitive elements and their preparation | |
DE2051262A1 (en) | Radiographic recording element | |
US3189456A (en) | Radiation-sensitive emulsions and elements and their preparation | |
US2843486A (en) | Photographic filter and anti-halation layers |