US2462534A - Light-sensitive photographic elements - Google Patents

Light-sensitive photographic elements Download PDF

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US2462534A
US2462534A US658224A US65822446A US2462534A US 2462534 A US2462534 A US 2462534A US 658224 A US658224 A US 658224A US 65822446 A US65822446 A US 65822446A US 2462534 A US2462534 A US 2462534A
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Murray Otis Willard
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • 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

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  • This invention relates to novel photographic elements which have the photosensitive layer or layers thereof protected from exposure to visible light. More particularly it relates to such elements which are useful for obtaining X-ray photographs or radiograms. Still more particularly it relates to X-ray films which can be safely handled under conditions of ordinary room illumination without exposure of the photosensitive layers thereof and yield developed radiographs free from coloring matter.
  • Photographic elements with various types of antihalation layers have been proposed and manufactured commercially.
  • they comprise a support, a light-sensitive layer, and an antihalation layer composed of a removable natural or synthetic material which has dispersed therethrough an antihalation or light-absorbing dye or pigment.
  • the light-sensitive layer is placed on one side of the base and the antihalation layer on the other.
  • Various water-soluble cellulose derivatives and synthetic resins are among the substances which have been proposed. Materials which are soluble in dilute alcohol solutions or in alkaline developer solutions have also been advocated but they require special conditions for manufacturing or processing.
  • Photographic elements for obtaining X-ray photographs which are provided with an opaque protecting medium for the sensitive layer are known.
  • the previous protective layers were not entirely satisfactory for X-ray films because the layers were diflicult to remove after exposure to X-rays and the light-blocking material is not uniformly distributed throughout the layer.
  • Murray United States Patent No. 2,379,373 relates to photographic elements and, more particularly, to X-ray film elements comprising a base, a light-sensitive emulsion layer, a lightblocking outer antihalation layer disposed on each side of said element composed of casein and gelatin in the proportion of to parts of the former per part of the latter having intimately and uniformly dispersed therethrough finely divided carbon particles.
  • These elements while commercially practical, sometimes have the disadvantage that complete removal of the finely divided carbon is diflicult. A small amount of carbon particles sometimes becomes anchored to the photographic emulsion layer at the fusion point between the emulsion layer and the protective, layer.
  • This invention has for an object a photographic element for X-rays which can be handled under daylight conditions without exposure.
  • a further object is such an element which is provided with antihalation layers which can be removed easily and completely in aqueous baths.
  • a still further object is to provide such an element wherein the antihalation layer is photographically inert and the light-blocking material is non-diffusing and uniformly dispersed throughout the layers.
  • a still further object is to improve the photographic elements of the aforesaid United States patent.
  • novel photographic elements or X-ray elements of this invention comprise a base having superposed thereon at least one photosensitive emulsion layer, two outer light-absorbing protective layers disposed on the outersurfaces of the elements, and a removable water-soluble colloid layer intercalated between any emulsion layer and said protective layer.
  • the elements comprise a film base or support having a photographic emulsion layer coated on each side of the base and a protective layer coated on each photographic emulsion layer which contains a non-difiusing, lightabsorbing material.
  • the protective light-blocking or antihalation layers consist of an aqueous dispersion of a mixture of casein and gelatin and a black inert pigment such as colloidal carbon or finely divided' carbon black which is uniformly distributed therethrough.
  • the casein and gelatin are present in the amount of 10 to 20 parts of the former per part of the latter.
  • the amount of the black inert pigment particles may vary over a fairly wide range but should be present in sufficient amount that thin layers prevent visible light from penetrating therethrough and exposing the photographic layers.
  • a particle size of 10 to 100 mu represents a practical range and 30 to mu a preferred range for aforesaid pigments.
  • the coating mixtures can be made in the form of an aqueous dispersion or paste and coated in a mannersimilar to that in which gelatin-silver halide emulsions are coated. They can be made by dispersing the colloidal silver or carbon black in an aqueous dispersion of gelatin and casein.
  • Various wetting and dispersing agents can be used in aiding the dispersions such as sodium alkyl sulfates of 10 to 18 carbon atoms, lower alkyl naphthalene sulfonic acid alkali metal salts wherein the alkyl groups have 1 to 4 carbon atoms, e. g., tri-isopropyl naphthalene sulfonic acid sodium salt, sodium or potassium alkane sulfonic acid salts having 10 to 18 carbon atoms, etc. Coating may be accomplished by spreading,
  • Suitable colloids include water-soluble cellulose derivatives, e. g., low substituted cellulose ethers, such as methyl cellu lose, ethyl cellulose, and benzyl cellulose, cellulose esters having solubilizing acid salt groups, e. g., sodium, potassium, and ammonium salts of cellulose acid phthalate, cellulose ether acids, e. g., sodium cellulose glycollate, casein gelatin mixtures, water-soluble synthetic resins, e. g., polyvinyl alcohol, and esters.
  • water-soluble cellulose derivatives e. g., low substituted cellulose ethers, such as methyl cellu lose, ethyl cellulose, and benzyl cellulose
  • cellulose esters having solubilizing acid salt groups e. g., sodium, potassium, and ammonium salts of cellulose acid phthalate
  • cellulose ether acids e. g., sodium cellulose glycollate
  • a preferred type of water-soluble layer is composed of a macromolecular water-soluble acetal of a vinyl alcohol polymer with an aldehyde containing a free sulfonic acid or free carboxylic acid group or an alkali metal, ammonium or amine salt of such acids.
  • An element containing this preferred type of water-soluble layer is shown in Fig.
  • a base l is provided on each surface with a silver halide emulsion layer 2 and 2, a remov- -ablelayer 3 and 3' composed of a macromolecular Water-soluble acetal of a vinyl alcohol polymer with an aldehyde containing a free sulfonic acid or carboxylic acid group, or a water-soluble salt thereof is deposited on'each emulsion layer and an antihalation layer 4 and 4 composed of gelatin and casein in the proportion of 10 to 20 parts :of the former per part of the latter which has finely-divided carbon uniformly dispersed therethrough on removable layers 3 and.
  • the water-soluble colloids can be coated from an aqueous solution or solvent mixtures which do not have a deleterious effect on the light-sensitivity of the emulsion layers.
  • Aqueous solutions containing 5 to 45% by weight of a water-soluble alcohol, e. g., ethanol or methanol, and a small amount, e. g., 0.05 to 2% by weight of a wetting agent are preferred. From 5 to 20 grams of colloid per 100 cc. of solution constitutes a practical range.
  • the coating may be applied by any of the methods useful in coating gelatin emulsions on supports includingthose referred to above.
  • EXAMPLE I A cellulose acetate film base was suitably subbed with gelatin and coated on each side with a gelatin-silver halide emulsion of the X-ray type. Each emulsion surface was coated at 75 F. with ;the following solution:
  • a dispersion of the following composition was prepared by mixing Solution B with Solution A and then adding Solution C with Vigorous stirring.
  • Solution A Water cubic centimeters 9100 Casein grams 1000 Sodium carbonate (10% aqueous solution) cubic centimeters 340 7 Solution B C'olloidal carbon (particle size 50 mu) grams 1000 Water cubic centimeters 2000 Sodium dodecyl sulfate (10% solution) do 20 7 Solution C Gelatin grams 100 Water cubic centimeter 1250 Sodium dodecyl sulfate (10% aqueous solution) do 100 Saponin (5% aqueous solution) do 100 The mixture was coated onto each methyl cellulose layer at about F. to form a layer approximately 30 microns thick. The above coating operations were carried out in the absence of actinic radiations. The resulting layer, after drying, had a density greater than 4.0.
  • the film element as described above was exposed in the usual manner to X-ray radiations in ordinary room illumination without the use of a cassette.
  • the film was processed as follows:
  • a photographic paper composed of an interfelted white paper stock and a black pigmented paper stock forming a photographically'opaque black outer stratum is provided with a baryta Casein g rams 20.0 Water. cubic centimeters 100.0 NM2CO3 (20%) d0 6.8 Gelatin grams 1.0 Mannitan monolaurate 10 cubic centimeters.-- 5.0 Water do 50.0
  • a thin layer (e. g., 10 mu.) from a dispersion made by mixing thev following solutions with stirring.
  • Solution A Water cubic centimeters 10,000 Casein grams 2,000 Sodium carbonate aqueous solution) cubic centimeters 680
  • Solution B was added to Solution A slowly and then Solution C was added and the resulting solution filtered.
  • the composition was then 40 coated in darkness onto each of the emulsion layers of aforesaid film element to a thickness of microns,
  • the resulting element had a density of greater than 4 on either side.
  • the layer was easilyremoved in the developing solu- 5 tion by a gentle swabbing with cotton.
  • the element can be safely handled in daylight or under ordinary artificial illumination without exposure of the light-sensitive stratum.
  • the outer layers Upon exposure and development as in Example I the outer layerswere readily removed without leaving any residual deposit of the light-blocking layer on the film.
  • the resulting element had: properties similar to those of Example I.
  • the hydrophilic macromolecular acetal described in Example V can be made by the reacti. n-of atvinyl alcohol polymer, including inter polymers, with an aldehyde containing a sulfonic acid or carboxylic acid group or an alkali metal, annnonium, or amine-salt of such acids, under acetal-forming conditions.
  • the acetalization may be conveniently carried out in solution or suspension in water or an organic solvent or diluent using a catalyst such as phosphoric acid, sulfuric acid, hydrochloric acid, etc.
  • a catalyst such as phosphoric acid, sulfuric acid, hydrochloric acid, etc.
  • the free acid groups can be converted into salt groups by a simple neutralization.
  • Partially and completely hydrolyzed polyvinyl alcoholscf low, intermediate, and high viscosity, having a, molecular weight of 5,000 to 50,000 and hydrolyzed interpolymers of vinyl esters with one or less equivalent of a terminally unsaturated interpolymerizable organic compounds can be used, in preparing, the vinyl alcohol acetals of aldehydes containing carboxylic or sulfonic acid Y In general, such polymer having for each 100 carbon atoms between 20, and 5.0 free non-phenolic hydroxyl groups are useful.
  • acetalizationirom polyvinyl alcohol of high molecular weight (viscosity of 4% aqeuous solution at 20 C., 40 to 60 centipoises) (2) polyvinyl alcohol of medium molecular weight (viscosity of 4% aqueous solution at 20 C., 15 to 30 centipoises) which may be substituted on 40 to 60% of the hydroxyl groups with acetate, propionate,
  • the preferred polyvinyl acetals have the above properties and, in addition, are colorless or substantially colorless and are free from color former nuclei.
  • the preparation of suitable such acetals for the removable layers is also more fully described in copending application Serial No. 651,996 filed March 5, 1946.
  • colloidal carbon or carbon black which have a very fine particle size, for instance, from 10 to 100 millimicrons, including mixtures Of particles having sizes within these ranges can be substituted for those de scribed in the above examples.
  • Small amounts (e. g., 0.5 to 2% of the gelatin) of the cellulose derivatives described in such patents may also be present.
  • the black inert pigments can be used in a wide range of proportions, e. g., one part by weight of pigment to 20 parts of combined casein and gelatin to two parts of pigment to one part of combined gelatin and casein.
  • Additional useful wetting agents include a1- kali metal ,alkyl sulfates of 8 to 20 carbon atoms, .e. g., sodium octyl sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate, ammonium octadecyl sulfate, oleyl sulfate, sodium n-hexadecanesulfonic acid, tri-isopropyl-napththalene sulfonic acid, the condensation products of ethylol cyanimides with lauric, stearic, palmitic, etc., acids.
  • a1- kali metal ,alkyl sulfates of 8 to 20 carbon atoms, .e. g., sodium octyl sulfate, sodium tetradecyl sulfate, sodium hexadecy
  • casein By varying the proportion of casein to the photographic gelatin it is possible to modify the properties of the light absorptive layers somewhat.
  • the higher proportions, e. g., 20 to 25, of casein make the layers removable in a water rinse before development, whereas somewhat lower proportions render the layers soluble in alkaline developer solution. Proportions near the lower limits render the layers removable at the end of normal development with gentle swabbing. Water rinses after development remove all traces of the products.
  • the antihalation elements of this invention as described above have all the desirable characteristics of a commercially practical element. Their, prepartion does not present any coating difficulties.
  • the two outer layers are soluble in aqueous treating baths and may be readily removed from the film by treatment in such baths. They are photographically inert and hence do not adversely affect the radiation sensitive layers.
  • the light-blocking pigments are non-diffusing and are uniformly dispersed throughout the combination' colloid layer.
  • the invention provides a novel X-ray film which can be handled safely in diffused daylight or under ordinary room illumination but yet can be easily processed to X-ray photographs. They may be processed in ordinary illumination if so desired. They eliminate the use of cassettes and enable the technicians to exercise much greater latitude and attain more speed in roentgenology.
  • the layers are abrasion resistant, have good anti-static properties, are not affected by usual changes in humidity, and have good aging properties.
  • Aphotogr'aphic'elemeht comprising a base, a light-sensitive emulsion layer, an outer antihalation layer disposed on each side of said base composed of casein and gelatin in the proportion of 10 to 20 parts of the former per part of the latter, having intimately and uniformly dispersed therethrough finely divided carbon particles and a water-soluble acetal of a vinyl alcohol polymer containing a group taken from the class consisting of free sulfonic acid groups, free carboxylic acid groups, and their water-soluble salts intercalated between said emulsion layer and antihalation layer.
  • a photographic element comprising a base, a light-sensitive emulsion layer, an outer antihalation layer disposed on each side of said base composed of casein and gelatin in the proportion of 10 to 20 parts of the former per part of the latter, having intimately and uniformly dispersed therethrough finely divided carbon particles and a water-soluble sodium-o-sulfobenzaldehyde acetal of polyvinyl alcohol intercalated between said emulsion layer and anti-halation layer.

Description

o. w. MURRAY 2,462,534
LIGHT-SENSITIVE PHOTOGRAPHIC ELEMENT Feb. 22, 1949.
Filed March 29, 1946 INVENTOR.
OTIS WILLA RD MURRAY BY A TTORNEY RATIO CONTAINING CARBON PARTICLES.
Patented Feb. 22, 1949 LIGHT-SENSITIVE PHOTOGRAPHI C ELEMENTS Otis Willard Murray, Fords, N. J assignor to E. I. & Company, Wilmington, Delaware Application March 29, 1946, Serial No. 658,224
du Pont de Nemours Del, a corporation of 2 Claims.
This invention relates to novel photographic elements which have the photosensitive layer or layers thereof protected from exposure to visible light. More particularly it relates to such elements which are useful for obtaining X-ray photographs or radiograms. Still more particularly it relates to X-ray films which can be safely handled under conditions of ordinary room illumination without exposure of the photosensitive layers thereof and yield developed radiographs free from coloring matter.
Photographic elements with various types of antihalation layers have been proposed and manufactured commercially. In general they comprise a support, a light-sensitive layer, and an antihalation layer composed of a removable natural or synthetic material which has dispersed therethrough an antihalation or light-absorbing dye or pigment. The light-sensitive layer is placed on one side of the base and the antihalation layer on the other. Various water-soluble cellulose derivatives and synthetic resins are among the substances which have been proposed. Materials which are soluble in dilute alcohol solutions or in alkaline developer solutions have also been advocated but they require special conditions for manufacturing or processing.
Photographic elements for obtaining X-ray photographs which are provided with an opaque protecting medium for the sensitive layer are known. The previous protective layers, however, were not entirely satisfactory for X-ray films because the layers were diflicult to remove after exposure to X-rays and the light-blocking material is not uniformly distributed throughout the layer.
Murray United States Patent No. 2,379,373 relates to photographic elements and, more particularly, to X-ray film elements comprising a base, a light-sensitive emulsion layer, a lightblocking outer antihalation layer disposed on each side of said element composed of casein and gelatin in the proportion of to parts of the former per part of the latter having intimately and uniformly dispersed therethrough finely divided carbon particles. These elements, while commercially practical, sometimes have the disadvantage that complete removal of the finely divided carbon is diflicult. A small amount of carbon particles sometimes becomes anchored to the photographic emulsion layer at the fusion point between the emulsion layer and the protective, layer.
This invention has for an object a photographic element for X-rays which can be handled under daylight conditions without exposure. A further object is such an element which is provided with antihalation layers which can be removed easily and completely in aqueous baths. A still further object is to provide such an element wherein the antihalation layer is photographically inert and the light-blocking material is non-diffusing and uniformly dispersed throughout the layers. A still further object is to improve the photographic elements of the aforesaid United States patent.
The novel photographic elements or X-ray elements of this invention comprise a base having superposed thereon at least one photosensitive emulsion layer, two outer light-absorbing protective layers disposed on the outersurfaces of the elements, and a removable water-soluble colloid layer intercalated between any emulsion layer and said protective layer. In the case of duplicoated X-ray film, the elements comprise a film base or support having a photographic emulsion layer coated on each side of the base and a protective layer coated on each photographic emulsion layer which contains a non-difiusing, lightabsorbing material.
The protective light-blocking or antihalation layers consist of an aqueous dispersion of a mixture of casein and gelatin and a black inert pigment such as colloidal carbon or finely divided' carbon black which is uniformly distributed therethrough. The casein and gelatin are present in the amount of 10 to 20 parts of the former per part of the latter. The amount of the black inert pigment particles may vary over a fairly wide range but should be present in sufficient amount that thin layers prevent visible light from penetrating therethrough and exposing the photographic layers. A particle size of 10 to 100 mu represents a practical range and 30 to mu a preferred range for aforesaid pigments.
The coating mixtures can be made in the form of an aqueous dispersion or paste and coated in a mannersimilar to that in which gelatin-silver halide emulsions are coated. They can be made by dispersing the colloidal silver or carbon black in an aqueous dispersion of gelatin and casein. Various wetting and dispersing agents can be used in aiding the dispersions such as sodium alkyl sulfates of 10 to 18 carbon atoms, lower alkyl naphthalene sulfonic acid alkali metal salts wherein the alkyl groups have 1 to 4 carbon atoms, e. g., tri-isopropyl naphthalene sulfonic acid sodium salt, sodium or potassium alkane sulfonic acid salts having 10 to 18 carbon atoms, etc. Coating may be accomplished by spreading,
has a marked solubility in water at 20 C.) of
natural or synthetic type. Suitable colloids include water-soluble cellulose derivatives, e. g., low substituted cellulose ethers, such as methyl cellu lose, ethyl cellulose, and benzyl cellulose, cellulose esters having solubilizing acid salt groups, e. g., sodium, potassium, and ammonium salts of cellulose acid phthalate, cellulose ether acids, e. g., sodium cellulose glycollate, casein gelatin mixtures, water-soluble synthetic resins, e. g., polyvinyl alcohol, and esters.
A preferred type of water-soluble layer is composed of a macromolecular water-soluble acetal of a vinyl alcohol polymer with an aldehyde containing a free sulfonic acid or free carboxylic acid group or an alkali metal, ammonium or amine salt of such acids. An element containing this preferred type of water-soluble layer is shown in Fig. 1 of the accompanying drawing wherein a base l is provided on each surface with a silver halide emulsion layer 2 and 2, a remov- -ablelayer 3 and 3' composed of a macromolecular Water-soluble acetal of a vinyl alcohol polymer with an aldehyde containing a free sulfonic acid or carboxylic acid group, or a water-soluble salt thereof is deposited on'each emulsion layer and an antihalation layer 4 and 4 composed of gelatin and casein in the proportion of 10 to 20 parts :of the former per part of the latter which has finely-divided carbon uniformly dispersed therethrough on removable layers 3 and. 3.
V The water-soluble colloids can be coated from an aqueous solution or solvent mixtures which do not have a deleterious effect on the light-sensitivity of the emulsion layers. Aqueous solutions containing 5 to 45% by weight of a water-soluble alcohol, e. g., ethanol or methanol, and a small amount, e. g., 0.05 to 2% by weight of a wetting agent are preferred. From 5 to 20 grams of colloid per 100 cc. of solution constitutes a practical range. The coating may be applied by any of the methods useful in coating gelatin emulsions on supports includingthose referred to above.
The invention will be further illustrated but is not intended to be limited by the following examples.
EXAMPLE I A cellulose acetate film base was suitably subbed with gelatin and coated on each side with a gelatin-silver halide emulsion of the X-ray type. Each emulsion surface was coated at 75 F. with ;the following solution:
A dispersion of the following composition was prepared by mixing Solution B with Solution A and then adding Solution C with Vigorous stirring.
Solution A Water cubic centimeters 9100 Casein grams 1000 Sodium carbonate (10% aqueous solution) cubic centimeters 340 7 Solution B C'olloidal carbon (particle size 50 mu) grams 1000 Water cubic centimeters 2000 Sodium dodecyl sulfate (10% solution) do 20 7 Solution C Gelatin grams 100 Water cubic centimeter 1250 Sodium dodecyl sulfate (10% aqueous solution) do 100 Saponin (5% aqueous solution) do 100 The mixture was coated onto each methyl cellulose layer at about F. to form a layer approximately 30 microns thick. The above coating operations were carried out in the absence of actinic radiations. The resulting layer, after drying, had a density greater than 4.0. No visible fog was produced after a 20 minute exposure in a normally lighted room but a'slight edge fog developed, e. g., about inch around the periphery of the film. The black antihalation layers and the contiguous water-soluble colloid layers were removed easily after a three minute soak in water by gentle swabbing with cotton.
The film element as described above was exposed in the usual manner to X-ray radiations in ordinary room illumination without the use of a cassette. The film was processed as follows:
1. Developed for four minutes in a solution made by admixing the following components:
Hydroquinone grams 7.5 p-N-ethyl-aminophenol sulfate do 5.0 Sodium sulfite (anhydrous) do 60.0 Sodium carbonate (anhydrous) do 50.0 Potassium bromide do 15.0 Water ton. liters 1.0 2. Treated for one minute in a stop bath of the composition Volumes Acetic acid (28%) 1 Water 20 3. The outer black layers were then removed in water by gentle swabbing.
4. Fixed for five minutes in a solution of the composition:
Sodium thiosulfate crystals grams 240.0 Sodium sulfite (anhydrous) do 6.0 Boric acid do 6.0 Potassium alum do 12.0 Acetic acid (28%) oubic centimeters 35.0 Water to liters 1.0
A photographic paper composed of an interfelted white paper stock and a black pigmented paper stock forming a photographically'opaque black outer stratum is provided with a baryta Casein g rams 20.0 Water. cubic centimeters 100.0 NM2CO3 (20%) d0 6.8 Gelatin grams 1.0 Mannitan monolaurate 10 cubic centimeters.-- 5.0 Water do 50.0
On the surface of the casein gelatin layer was coated a thin layer (e. g., 10 mu.) from a dispersion made by mixing thev following solutions with stirring.
Solution A Water cubic centimeters 10,000 Casein grams 2,000 Sodium carbonate aqueous solution) cubic centimeters 680 Solution B or Colloidal carbon (particle size 60 mu) grams 600 ater cubic centimeters 3000 Condensationproduct of ethylol cyanamide 'with lauric acid (1% solution) do 2 Solution 0 Gelatin grams 100 Water cubic centimeters 3000 Sodium dodecyl sulfate (10% solution-- aqueous) do 25 Saponin (5% solution-aqueous) do 75 Solution B was added to Solution A slowly and then Solution C was added and the resulting solution filtered. The composition was then 40 coated in darkness onto each of the emulsion layers of aforesaid film element to a thickness of microns, The resulting element had a density of greater than 4 on either side. The layer was easilyremoved in the developing solu- 5 tion by a gentle swabbing with cotton. The element can be safely handled in daylight or under ordinary artificial illumination without exposure of the light-sensitive stratum. Upon exposure and development as in Example I the outer layerswere readily removed without leaving any residual deposit of the light-blocking layer on the film.
EXAMPLE III In place of the methyl cellulose solution of Example I was used the following:
Corn dextrine grams 10 Water cubic centimeters 100 Ethanol do 20 Saponin solution do 10 Aerosol CEL (10%) do 2 The resulting element had properties similar to those of Example I.
EXAMPLE IV In place of the gelatin-casein coating solution of Example II was substituted:
Cellulose acetate-acid phthalate grams 5 10% NazCOa oubic centimeters 10 Water do 150 Ethanol do 50 Gelatin grams 5 Water -cubic centimeters- 100 r groups.
The resulting element had: properties similar to those of Example I.
ExAMrLE V In place of the gelatin-casein coating solution of Example II there was substituted the following solution:
Sodium-o-sulfobenzaldehyde acetal of poly- The resulting complete element when processed after the manner described in Example I gave similar results.
"The hydrophilic macromolecular acetal described in Example V can be made by the reacti. n-of atvinyl alcohol polymer, including inter polymers, with an aldehyde containing a sulfonic acid or carboxylic acid group or an alkali metal, annnonium, or amine-salt of such acids, under acetal-forming conditions. For example, the acetalization may be conveniently carried out in solution or suspension in water or an organic solvent or diluent using a catalyst such as phosphoric acid, sulfuric acid, hydrochloric acid, etc. Suitable procedures and aldehydes 'are described in United States Patent 2,310,943 and in German Patent No. 643,650. The free acid groups can be converted into salt groups by a simple neutralization.
Partially and completely hydrolyzed polyvinyl alcoholscf low, intermediate, and high viscosity, having a, molecular weight of 5,000 to 50,000 and hydrolyzed interpolymers of vinyl esters with one or less equivalent of a terminally unsaturated interpolymerizable organic compounds can be used, in preparing, the vinyl alcohol acetals of aldehydes containing carboxylic or sulfonic acid Y In general, such polymer having for each 100 carbon atoms between 20, and 5.0 free non-phenolic hydroxyl groups are useful.
'Water-soluble, macromolecular, neutralized acetals of vinyl alcohol polymers useful in accordance with this invention are prepared by acetalizationirom (1) polyvinyl alcohol of high molecular weight (viscosity of 4% aqeuous solution at 20 C., 40 to 60 centipoises) (2) polyvinyl alcohol of medium molecular weight (viscosity of 4% aqueous solution at 20 C., 15 to 30 centipoises) which may be substituted on 40 to 60% of the hydroxyl groups with acetate, propionate,
acetal, propional, and butyral groups, and (3) to hydrolyzed interpolymers of vinyl acetate with 0.05 to 0.5 mol equivalents of terminally unsaturated mono-oleflns, e. g., ethylene, such as described in Roland United States Patent No. 2,386,347, and (4) completely hydrolyzed interpolymers of vinyl acetate with minor portions (less than 50%) 0f polymerizable vinyl or vinylidene compounds, for example, vinyl chloride, Vinyl cyanide, alkyl methacrylates, e. g., methyl and ethyl methacrylate, etc., with an aldehyde containing carboxylic or a sulfonic acid group.
The preferred polyvinyl acetals have the above properties and, in addition, are colorless or substantially colorless and are free from color former nuclei. The preparation of suitable such acetals for the removable layers is also more fully described in copending application Serial No. 651,996 filed March 5, 1946.
Various commercial forms of colloidal carbon or carbon black which have a very fine particle size, for instance, from 10 to 100 millimicrons, including mixtures Of particles having sizes within these ranges can be substituted for those de scribed in the above examples. Small amounts (e. g., 0.5 to 2% of the gelatin) of the cellulose derivatives described in such patents may also be present. The black inert pigments can be used in a wide range of proportions, e. g., one part by weight of pigment to 20 parts of combined casein and gelatin to two parts of pigment to one part of combined gelatin and casein.
Additional useful wetting agents include a1- kali metal ,alkyl sulfates of 8 to 20 carbon atoms, .e. g., sodium octyl sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate, ammonium octadecyl sulfate, oleyl sulfate, sodium n-hexadecanesulfonic acid, tri-isopropyl-napththalene sulfonic acid, the condensation products of ethylol cyanimides with lauric, stearic, palmitic, etc., acids.
By varying the proportion of casein to the photographic gelatin it is possible to modify the properties of the light absorptive layers somewhat. The higher proportions, e. g., 20 to 25, of casein make the layers removable in a water rinse before development, whereas somewhat lower proportions render the layers soluble in alkaline developer solution. Proportions near the lower limits render the layers removable at the end of normal development with gentle swabbing. Water rinses after development remove all traces of the products.
The antihalation elements of this invention as described above have all the desirable characteristics of a commercially practical element. Their, prepartion does not present any coating difficulties. The two outer layers are soluble in aqueous treating baths and may be readily removed from the film by treatment in such baths. They are photographically inert and hence do not adversely affect the radiation sensitive layers. The light-blocking pigments are non-diffusing and are uniformly dispersed throughout the combination' colloid layer.
The invention provides a novel X-ray film which can be handled safely in diffused daylight or under ordinary room illumination but yet can be easily processed to X-ray photographs. They may be processed in ordinary illumination if so desired. They eliminate the use of cassettes and enable the technicians to exercise much greater latitude and attain more speed in roentgenology. In addition, the layers are abrasion resistant, have good anti-static properties, are not affected by usual changes in humidity, and have good aging properties.
'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. Aphotogr'aphic'elemeht comprising a base, a light-sensitive emulsion layer, an outer antihalation layer disposed on each side of said base composed of casein and gelatin in the proportion of 10 to 20 parts of the former per part of the latter, having intimately and uniformly dispersed therethrough finely divided carbon particles and a water-soluble acetal of a vinyl alcohol polymer containing a group taken from the class consisting of free sulfonic acid groups, free carboxylic acid groups, and their water-soluble salts intercalated between said emulsion layer and antihalation layer.
2. A photographic element comprising a base, a light-sensitive emulsion layer, an outer antihalation layer disposed on each side of said base composed of casein and gelatin in the proportion of 10 to 20 parts of the former per part of the latter, having intimately and uniformly dispersed therethrough finely divided carbon particles and a water-soluble sodium-o-sulfobenzaldehyde acetal of polyvinyl alcohol intercalated between said emulsion layer and anti-halation layer.
QTISWILLARD MURRAY.
REFERENCES CITED The following references are of record in the file of this patent: V
UNITED STATES PATENTS Number Name Date 1,537,939 Dunham May 9, 1925 1,631,421 Lohofer June 7, 1927 1,942,852 Young Jan. 9, 1934 2,271,234 Staud et al Jan. 27, 1942 2,319,080 Nadeau et a1 May 11, 1943 2,379,373 Murray June 26, 1945 FOREIGN PATENTS Number Country Date 163,349 Great Britain May 26, 1921 212,484 Great Britain Mar. 13, 1924 292,990 Great Britain Jan. 10, 1929 322,007 Great Britain Nov. 28, 1929
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3005711A (en) * 1954-11-12 1961-10-24 Agfa Ag Triphenylcarbinol dyestuffs as photographic antihalation material
US3021214A (en) * 1958-03-17 1962-02-13 Eastman Kodak Co Waterproof paper negative
US3269252A (en) * 1961-05-08 1966-08-30 Gevaert Photo Prod Nv Photographic material
US3511660A (en) * 1965-10-19 1970-05-12 Eastman Kodak Co Antihalation backing for photographic silver halide recording elements

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB163349A (en) * 1919-08-22 1921-05-26 Philip Henry Wilfrid Serle Improvements in and relating to the production of casein cements
GB212484A (en) * 1923-03-10 1924-03-13 Actien-Gesellschaft Fuer Anilin-Fabrikation
US1537939A (en) * 1923-03-26 1925-05-19 Casein Mfg Company Casein waterproof glue or cement
US1631421A (en) * 1923-03-09 1927-06-07 Ig Farbenindustrie Ag Photographic film
GB292990A (en) * 1927-06-29 1929-01-10 Ig Farbenindustrie Ag Improvements in the manufacture of photographic anti-halation plates or films
GB322007A (en) * 1928-09-03 1929-11-28 Hermann Weck Improvements relating to photographic process printing
US1942852A (en) * 1931-02-16 1934-01-09 Eastman Kodak Co Nonhalation backing for photographic film
US2271234A (en) * 1940-06-29 1942-01-27 Eastman Kodak Co Colloidal carbon antihalation layer
US2319080A (en) * 1939-04-14 1943-05-11 Eastman Kodak Co Antihalation backing for photographic film
US2379373A (en) * 1944-01-01 1945-06-26 Du Pont Photographic elements

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB163349A (en) * 1919-08-22 1921-05-26 Philip Henry Wilfrid Serle Improvements in and relating to the production of casein cements
US1631421A (en) * 1923-03-09 1927-06-07 Ig Farbenindustrie Ag Photographic film
GB212484A (en) * 1923-03-10 1924-03-13 Actien-Gesellschaft Fuer Anilin-Fabrikation
US1537939A (en) * 1923-03-26 1925-05-19 Casein Mfg Company Casein waterproof glue or cement
GB292990A (en) * 1927-06-29 1929-01-10 Ig Farbenindustrie Ag Improvements in the manufacture of photographic anti-halation plates or films
GB322007A (en) * 1928-09-03 1929-11-28 Hermann Weck Improvements relating to photographic process printing
US1942852A (en) * 1931-02-16 1934-01-09 Eastman Kodak Co Nonhalation backing for photographic film
US2319080A (en) * 1939-04-14 1943-05-11 Eastman Kodak Co Antihalation backing for photographic film
US2271234A (en) * 1940-06-29 1942-01-27 Eastman Kodak Co Colloidal carbon antihalation layer
US2379373A (en) * 1944-01-01 1945-06-26 Du Pont Photographic elements

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3005711A (en) * 1954-11-12 1961-10-24 Agfa Ag Triphenylcarbinol dyestuffs as photographic antihalation material
US3021214A (en) * 1958-03-17 1962-02-13 Eastman Kodak Co Waterproof paper negative
US3269252A (en) * 1961-05-08 1966-08-30 Gevaert Photo Prod Nv Photographic material
US3511660A (en) * 1965-10-19 1970-05-12 Eastman Kodak Co Antihalation backing for photographic silver halide recording elements

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