# US 4,394,439 A · Non-silver X-ray recording process > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,394,439 A - Document ID: US4394439A - Status: Granted - Kind: A - Application number: 06/267,685 - Filed: 1981-05-28 - Granted: 1983-07-19 - Earliest claimed: 1981-05-28 - Inventors: Jean J. Robillard - Web page: https://patentgrep.com/patent/US4394439A ## CPC - G03C 5/16: X-ray, infrared, or ultraviolet ray processes - G03C 1/675: Compositions containing polyhalogenated compounds as photosensitive substances (for photopolymerisable or photocrosslinkable compositions G03F7/028, covered by G03C1/72) - G03C 1/733: {with macromolecular compounds as photosensitive substances, e.g. photochromic (photodegradable or photocrosslinkable compositions G03F7/004)} - Y10S 430/117: Free radical - Y10S 430/168: X-ray exposure process - G03C: PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES (for photomechanical purposes G03F); PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY (photographic processes characterised by the use or manipulation of apparatus classifiable per se in subclass G03B, see G03B; photomechanical production of textured or patterned surfaces G03F; electrophotography, magnetography G03G) - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract Permanent records of X rays or radiations of shorter wavelengths are formed on a film substrate by direct exposure to the radiation and heat development. The process is not sensitive to visible radiation and can therefore be carried on in daylight. An X ray photosensitive film containing a halogenated photodegradable polymer and an aryl dye promoter reacting to free radicals is exposed to an X ray image and then heated under conditions which allow the free radical generated by the photodegradation of the polymer to migrate and react with the aryl dye promoter to provide the imaging dye. The X ray photosensitive layer of the X ray photosensitive film or paper includes, in addition to the photodegradable polymer and the aryl dye promoter, a heat activable complexing agent and an organic binder. The process can be carried out using currently available X ray equipment with the advantage of handling the film in daylight and eliminating chemical development. ## Claims ### Claim 1 A process for forming a permanent record of an X ray image onto a transparent substrate which comprises (A) providing a photosensitive film comprising (1) a film substrate made of a photodegradable halogenated polymer, and (2) an image forming layer on said film substrate, said image forming layer comprising (a) an halogenated free radical sensitive dye former, and (b) a complexing agent, which is an organic metal salt said (a) and (b) being uniformly dispersed in an organic binder; (B) photographically, imagewise exposing the photosensitive film to an X ray image to imagewise photodegrade the polymer and selectively generate halogenated free radicals; and (C) heating the exposed photosensitive film to allow the imagewise generated halogenated free radicals to react with the dye former to thereby form a dye image and complex the dye with the complexing agent to finally provide a dye complex image. ### Claim 2 (depends on 1) The process according to claim 1 wherein said photosensitive film comprises (1) a film substrate made of a photodegradable polymer selected from the group consisting of polyhexafluoropropylene, the copolymer of vinylidene fluoride and hexafluoropropylene, the copolymer of tetrafluoroethylene and nitrosofluoromethane, the copolymer of tetrafluoroethylene and nitrosochlormethane, the copolymer of tetrafluoroethylene and nitrosobromomethane, the coordinated complex of polyaminoquinone with copper II copolymerized with one of these halogenated polymers and the coordinated complex of poly 1,4 phenylenebis (dithiocarbamic acid) with copper I copolymerized with one of these halogenated polymers; and (2) an image forming layer on said film substrate, said image forming layer made of an image forming composition comprising (a) at least one halogenated free radical sensitive dye former selected from the group consisting of arylamines, arylaldehydes, arylindolizines, spiropyrans, crystal violet lactone, 4-(p-dimethylaminostyryl) quinolines, leuco triphenylmethane, leuco-p-diaminostyryl bases, leucocyanine bases, leuco xanthine bases, leuco dyes with N-vinylcarbazol and leucomerocyanine with N-vinylcarbazol; and (b) at least one complexing agent which is an organic metal salt selected from the group consisting of metal salts of behenic acid, naphthenic acid and stearic acid and said image forming layer being uniformly dispersed in an organic binder which softens at the temperature of the heating step (C) and in the range of about 100.degree. C. to 150.degree. C. ### Claim 3 (depends on 2) The process of claim 2 wherein said film substrate has a thickness in the range of from about 0.05 to 3 mm. ### Claim 4 (depends on 2) The process of claim 2 wherein said image forming layer comprises from 0.01 to 1 g per square meter of (a) and from 0.1 to 2 g per square meter of (b) and the amount of the organic binder is sufficient to form an image forming layer having a thickness in the range of from about 1 to 10 microns. ### Claim 5 (depends on 1) The process of claim 1 wherein step (C) comprises heating the exposed photosensitive film to a temperature in the range of from about 100.degree. C. to about 150.degree. C. for a time varying between 0.5 to 10 sec. ### Claim 6 (depends on 1) The process of claim 1 wherein in said image forming layer said (a) halogenated free radical sensitive dye former is a mixture of 1-methyl-2-phenylindolizine with either 4-aminodiphenylamine or 4-dimethylaminobenzaldehyde, and said (b) complexing agent is lead naphthenate or nickel stearate. ### Claim 7 (depends on 1) The process of claim 1 wherein in said image forming layer said (a) halogenated free radical sensitive dye former is 3-ethylthio-4-carbocyanine and said (b) complexing agent is cobalt naphthenate or a mixture of cobalt naphthenate with lead polyacrylate. ### Claim 8 (depends on 1) The process of claim 1 wherein in said image forming layer said (a) halogenated free radical sensitive dye former is 3'-methyl-spiro (2'H,1'-benzopyran-2,2'(2H,1-benzopyran)), and said (b) complexing agent is ferric stearate. ### Claim 9 (depends on 1) The process of claim 1 wherein in said image forming layer said (a) halogenated free radical sensitive dye former is 4-dimethylaminodiphenylamine, and said (b) complexing agent is copper naphthenate or lead polymethacrylate. ### Claim 10 (depends on 2) The process of claim 2 wherein said complexing agent which is an organic metal salt is selected from the group consisting of lead, zinc, barium copper and cobalt behenates, naphthenates, and stearates.