US2551133A - Photographic light-sensitive diazo element - Google Patents

Photographic light-sensitive diazo element Download PDF

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US2551133A
US2551133A US693802A US69380246A US2551133A US 2551133 A US2551133 A US 2551133A US 693802 A US693802 A US 693802A US 69380246 A US69380246 A US 69380246A US 2551133 A US2551133 A US 2551133A
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light
sensitive
color former
hydrophilic
coating
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US693802A
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Jennings Andrew Bradshaw
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
    • G03C1/52—Compositions containing diazo compounds as photosensitive substances
    • G03C1/58—Coupling substances therefor

Definitions

  • This invention relates to photography and, more particularly, to light-sensitive photographic elements containing light-sensitive diazonium salts and to compositions and preparing the same. Still more particularly it relates to photographic elements comprisinga support bearing a hydrophilic color former layer having intimately dispersed therethrough light-sensitive diazonium salts and to processes for making such layers.
  • An object of this invention is to provide a new type of light-sensitive photographic element.
  • a more specific object is to provide such an element which contains light-sensitive diazonium salts.
  • a further object is to provide such an element which may be processed rapidly to yield reproductions of high contrast with good resolving power and definition.
  • a still further object is to provide a simple and economical method for preparing such elements. Still other objects will be apparent from the following description of the invention.
  • the novel photographic elements of this invention consist of a support which bears at least one water-permeable layer composed of a hydrophilic, polymeric color former which has intimately dispersed therethough light-sensitive diazonium salts.
  • the hydrophilic, polymeric color formers consist of synthetic, organic, polymeric com pounds which contain a polymeric chain nucleus and include in their molecular structure nuclei which are capable of forming azomethine or indophenol dyes on color coupling development of exposed silver halides. These color formers are also capable ofcoupling with diazo compounds to form diazo dyes. Hence when light-sensitive diazonium salts are incorporated with them, the latter compounds couple under the conditions suitable for development of light-sensitive :diazonium salts to form polymeric azo dyes.
  • novel elements consist essentially of two components, namely, the hydrophilic, polymeric color former and the light-sensitive diazonium salt. Hence they are quite simple to fabricate and process.
  • the coating techniques for preparing the emulsions or light-sensitive coatings are simplified by reason of the two-component nature of the final product.
  • the coating solutions may be prepared by dissolving the. hydrophilic, polymeric color former suitable solvent or mixture of solvents, such as methanol, ethanol, diouane, etc, and mixtures of such solvents with water.
  • the hydrophilic, polymeric color former and the light-sensitive dazonium compound may be dissolved in the same solution by adding them separately or simultaneously or they may be separately dissolved in different portions of the same solvent and admixed with stirring.
  • Stabilizing agents for the diazonium salts can be incorporated with the coating solutions if desired.
  • the resulting solutions may then be applied to a support to form a thin layer and dried.
  • the preparation of the solutions and the coating operations should, of course, be carried out in the absence of actinic radiations which would aiiect the light-sensitive diazonium compounds;
  • An alternative method of preparing the lightsensitive coatings or layers is to dissolve the hydrophilic, polymeric color former in a solution and to coat this upon a support to form a layer which is then dried. The dried layer is then impregnated with a solution containing the lightsensitive diazonium compound. The latter solution freely permeates throughout the entire layer and as it dries it deposits the light-sensitive salt uniformly throughout the layer.
  • hydrophilic hydroxyl color formers which consist of a linear polymer chain which has attached, to recurring carbon atoms thereof, a hydroxyl group and, to other recurring carbon atoms, color former nuclei capable of forming azomethine or indophenol dyes through a covalent bond.
  • the color former nuclei may be attached to recurring carbon atoms of the polymer chain through ether or acetal linkages.
  • light-sensitive diazonium compound in a preferred hydrophilic, hydroxyl polymer color formers should have a polymer chain containing more than 200 carbon atoms.
  • acrylic acid acrylic acid allcyl esters, alkyl methacrylates, vinyl chloride, vinyl cyanide, and maleic anhydride, and also the partial esters, ethers, and acetals of such polymers.
  • These polymers may be connected to the color former nuclei by various chemical groupings or linkages, such as, for example, carbonamide, sulionamide, amino groups, acetal, ester, ether linkages, etc.
  • the -CH2- group is usually pres ent between two such groups, for example,
  • the coating solutions described above may be applied to the support by any of the conventional coating procedures, e. g., by dipping, spraying, coating from hoppers by means of beading rollers, etc. They may be applied to practically any type of support, such as metal, plastic, glass, transparent film base, water-prooied paper, cellulose derivatives, superpolymers, e. g., nylon, etc.
  • Example I A 5% solution of meta(lhydroxynaphthalene-2-sulfoamido)benzaldehyde polyvinyl acetal (prepared as described in application Serial Number 667,111, filed May 3, 1946, now U. S. Patent No. 2,433,572) was prepared in a waterethanol solution containing 75 parts of the former and parts of the latter by weight. resulting solution was deposited on a baryta coated paper support at a coating weight of 60 milligrams per square decimeter of said acetal.
  • the resulting layer was dried at a temperature of about l050 C. in a current of air. solution of the zinc double salt of diazotized p-amino-diethylaniline in water was supplied to the layer. The entire operation was carried out in the absence of actinic light.
  • the resulting element after drying, was exposed to a positive transparent image by means of a 500 watt 3200 K. lamp at a distance of three feet for ten minutes. The exposed element was subsequently developed by fuming it with ammonia vapor for a period of ten minutes. A strong, positive image, which was brown in color, was formed.
  • Example II A 5% solution of meta(p-[5-ethylcarbonato-3- methyl l pyrazoyl)benzamidolbenzaldehyde acetal of polyvinyl alcohol (prepared as described in application Serial Number 667,126, filed May 8,1946, now U. S. Patent No. 2,476,988) was substituted for the acetal of Example I. The resulting element was exposed and developed as described in that example whereby a magenta image was formed.
  • Example III A 5% solution of meta(benzoylacetamido)benzaldehyde polyvinyl acetal (prepared as described in application Serial Number 667,126, filed May 3, 1946, now U. S. Patent No. 2,464,597) was sub stituted for the acetal of Example I. The resulting element was exposed and processed as described in that example and a strong, orange image was obtained.
  • Any organic solvent or mixture of solvents may be employed in preparing the solutions as long as they are not reactive with the daizo compounds.
  • ketones such as acetone, methyl ethyl ketone, cyclohexanone, etc.
  • alcohols e. g., methanol, ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, etc; glycols, c. g., ethylene glycol, diethylene glycol, propylene glycol; ethlyene glycol monomethyl and monoethyl ethers; ethylene glycol dimethyl ether; tetrahydroiuran; esters, e.
  • methyl acetate, ethyl acetate, ethyl propionate, ethyl butyrate, ethyl glycolate, ethyl methoxyacetate; hydrocarbons, e. g., hexane, benzene; chlorinated hydrocarbons, e. g., chloroform, carbon tetrachloride, ethylene dichloride, etc., can be used providing that they are solvents for all the constituents of the coating composition.
  • the preferred solvents or solvent solutions are those which are water-miscible to the extent that 10% or more water can be dissolved therein.
  • a small amount of water in the coating composition is desirable and aids in dissolving the diazonium compound and in securing an even lightsensitive coating. Further, it is usually desirable to use those with an appreciable vapor pressure at normal temperatures so that drying times will be as short as possible.
  • portions (e. g., 5 to 25%) of solvent with a higher vapor pressure, e.g., boiling between and 260 C, are advantageous as an aid in securing even flow outs and smooth coatings.
  • an anti-foaming agent e. g., long chain aliphatic alcohol, e. g.,
  • naphthalene l-aminodieth'ylaniline, 4-aminodiaminonapthalene, 4-amino-diphenyl, 4-aminocarboethoxyaniline; methyl, 4 amino-2,5-dimethoxyphenyl urea; phenyl, 4-amino-'2,5-dichlorophenyl urea. f
  • any of the various known sensitizers such as urea, thiourea, allyl thiourea, thiosulfate, etc., and/or compounds which form double salts with diazonium compounds, such as tin," zinc, or cadmium salts, of weak acids, e. g., tartaric, citric, succinic, boric, etc., may be employed in these compositions.
  • weak acids e. g., tartaric, citric, succinic, boric, etc.
  • pigments it is also desirable in some cases to add pigments to the compositions.
  • a pigment is added which is complementary in color to that of the final azo dye produced in the drawing.
  • a white pigment such as titanium dioxide or barium sulfate pigment.
  • the final colors are to be red, a green pigment may be used, or if they are to be blue, a yellow pigment may be used or any other such combination.
  • Suitable diazo stabilizers which prevent decomposition of the light-sensitive diazonium compounds when coated on metal plates, e. g., ferrous metal plates, are metal deactivators and corrosion inhibitors which are unreactive toward diazonium salts.
  • Compounds useful for this purpose include water-soluble metal nitrites, e. g., alkali metal nitrites, alkyl nitrites, e. g., amyl nitrite; alkyl phosphates, e. g., monododecyl phosphate, didodecyl phosphate; and aromatic phosphates, e. g., tricresyl phosphate. These compounds may be used in small amounts, e. g., 0.01 to 0.2% based on the total weight of the hydrophilic, polymeric color former used.
  • Self-supporting foils may be made by coating the hydrophilic, polymeric color former solu- 6 tions onto-a smooth surface, drying the resulting film element, and Stripping it from thecasting surface.
  • the light-sensitive, hydrophilic, polymeric color former coating compositions hereof have the advantage that they form watei' permeable layers which are free from tackiness so that the surface will not stick to other materials, even when stored. in a humid place.
  • the resulting layers have a tough, smooth surface and are not softened by'water sufficiently to cause scratching or marring when handled Wet.
  • compositions of this invention have a wide utility and are generally useful where it is desired to copy a design, drawing,
  • Photographic element comprising a support bearing at least one layer composed of a hydrophilic polymeric color former having light-sensitive diazonium compounds uniformly dispersed therethrough, said color former containing a multiplicity of recurring active groups which have a structure represented by the formula where n is a number taken from the group consisting of 0 and l.
  • Photographic element comprising a support bearing at least one layer composed of a hydrophilic polymeric color former having light-sentitive diazonium salts uniformly dispersed therethrough, said color former containing a multiplicity of recurring active groups which have a structure represented by the formula where n is a number taken from the group consisting of 0 and l. p
  • Photographic element comprising a support bearing at least one layer composed of a hydrophilic hydroxyl polymer color former having light-sensitive diazonium salts uniformly dispersed th rethrough, said color former containing a multiplicity of recurring CH2--CHOH-- groups and a multiplicity of recurring active groups which have a structure represented by the formula where n is a number taken from the group consisting of 0 and 1.
  • Photographic element comprising a support bearing at least one layer composed of a hydrophilic polyvinyl acetal color former which contains a multiplicity of recurring CHzCHOH- groups and a multiplicity of recurring active groups which have a structure represented by the formula .
  • n. is a. number taken from the group con- :former having light-sensitive diazonium compound uniformly dispersed therethrough, said polyvinyl acetal color former containing a multiplicity of recurring extralinear active groups which have a structure represented by the formula where n is a number taken from the group consisting of 0 and. 1.
  • a photographic element comprising a waterproofed paper support bearing a layer composed of m (1-hydroxynaphthalene-2-su1fonamido)r benzaldehyde polyvinyl acetal having a zinc double salt of diazotized p-aminodiethyl aniline uniformly dispersed therethrough.
  • a photographic element comprising a water-proofed paper support bearing a layer composed of m-(p-[5-ethylcarbonato-3-methy1- 1 pyrazoybbenzamido] benzaldehyde polyvinyl acetal having a zinc double salt of diazotized p-aminodiethyl aniline uniformly dispersed therethrough.
  • a photographic element comprising a waterproofed paper support bearing a layer composed of m-(benzoylacetamido) benzaldehyde polyvinyl acetal having a zinc double salt of diazotized p-aminodiethyl aniline uiformly dispersed therethrough.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Printing Methods (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Description

Patented May 1, 1951 Andrew Bradshaw Jennings, New Brunswick, and Otis Willard Murray, Fords, N. J assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No waiting. Application August 29, 1946, Serial No. 693,802
8 Claims.
This invention relates to photography and, more particularly, to light-sensitive photographic elements containing light-sensitive diazonium salts and to compositions and preparing the same. Still more particularly it relates to photographic elements comprisinga support bearing a hydrophilic color former layer having intimately dispersed therethrough light-sensitive diazonium salts and to processes for making such layers.
An object of this invention is to provide a new type of light-sensitive photographic element. A more specific object is to provide such an element which contains light-sensitive diazonium salts. A further object is to provide such an element which may be processed rapidly to yield reproductions of high contrast with good resolving power and definition. A still further object is to provide a simple and economical method for preparing such elements. Still other objects will be apparent from the following description of the invention.
The novel photographic elements of this invention consist of a support which bears at least one water-permeable layer composed of a hydrophilic, polymeric color former which has intimately dispersed therethough light-sensitive diazonium salts. The hydrophilic, polymeric color formers consist of synthetic, organic, polymeric com pounds which contain a polymeric chain nucleus and include in their molecular structure nuclei which are capable of forming azomethine or indophenol dyes on color coupling development of exposed silver halides. These color formers are also capable ofcoupling with diazo compounds to form diazo dyes. Hence when light-sensitive diazonium salts are incorporated with them, the latter compounds couple under the conditions suitable for development of light-sensitive :diazonium salts to form polymeric azo dyes.
The novel elements consist essentially of two components, namely, the hydrophilic, polymeric color former and the light-sensitive diazonium salt. Hence they are quite simple to fabricate and process. The coating techniques for preparing the emulsions or light-sensitive coatings are simplified by reason of the two-component nature of the final product.
The coating solutions may be prepared by dissolving the. hydrophilic, polymeric color former suitable solvent or mixture of solvents, such as methanol, ethanol, diouane, etc, and mixtures of such solvents with water. The hydrophilic, polymeric color former and the light-sensitive dazonium compound may be dissolved in the same solution by adding them separately or simultaneously or they may be separately dissolved in different portions of the same solvent and admixed with stirring. Stabilizing agents for the diazonium salts can be incorporated with the coating solutions if desired. The resulting solutions may then be applied to a support to form a thin layer and dried. The preparation of the solutions and the coating operations should, of course, be carried out in the absence of actinic radiations which would aiiect the light-sensitive diazonium compounds;
An alternative method of preparing the lightsensitive coatings or layers is to dissolve the hydrophilic, polymeric color former in a solution and to coat this upon a support to form a layer which is then dried. The dried layer is then impregnated with a solution containing the lightsensitive diazonium compound. The latter solution freely permeates throughout the entire layer and as it dries it deposits the light-sensitive salt uniformly throughout the layer.
In the preferred form of the invention there are used hydrophilic hydroxyl color formers which consist of a linear polymer chain which has attached, to recurring carbon atoms thereof, a hydroxyl group and, to other recurring carbon atoms, color former nuclei capable of forming azomethine or indophenol dyes through a covalent bond. The color former nuclei may be attached to recurring carbon atoms of the polymer chain through ether or acetal linkages. The
and. light-sensitive diazonium compound in a preferred hydrophilic, hydroxyl polymer color formers, moreover, should have a polymer chain containing more than 200 carbon atoms.
Suitable synthetic hydroxyl polymers that may be connected to color forming nuclei to produce the hydrophilic color forming hydroxyl polymers of the present invention include hydrolyzed polyvinyl esters, i. e., polyvinyl alcohols, hydrolyzed interpolymers of vinyl esters, e. g., vinyl acetate, vinyl propionate, and vinyl butyrate, etc., with olefins, e. g., ethylene, propylene, butene-l, and other vinyl compounds, e. g., acrylic acid, acrylic acid allcyl esters, alkyl methacrylates, vinyl chloride, vinyl cyanide, and maleic anhydride, and also the partial esters, ethers, and acetals of such polymers. These polymers may be connected to the color former nuclei by various chemical groupings or linkages, such as, for example, carbonamide, sulionamide, amino groups, acetal, ester, ether linkages, etc.
The color former nuclei or components of the above synthetic polymers have as active coupling groups a structure which may be represented as i I -o=o, C=N-, CEN
and others. The -CH2- group is usually pres ent between two such groups, for example,
I o o Gino o o CHZCN, -o o oH2o=N in a cylic or acyclic system. In all of the color former nuclei the hydrogen atoms in the coupling position may be replaced by groups which are readily eliminated in the coupling reaction, e. g., halogen, e. g., chlorine and bromine, sulionic acid, carboxylic acid, etc.
Suitable specific color formers of the above type are described in United States Patents 2,310,943, 2,320,422, 2,397,864, and 2,397,865.
The coating solutions described above may be applied to the support by any of the conventional coating procedures, e. g., by dipping, spraying, coating from hoppers by means of beading rollers, etc. They may be applied to practically any type of support, such as metal, plastic, glass, transparent film base, water-prooied paper, cellulose derivatives, superpolymers, e. g., nylon, etc.
The invention will be further illustrated by the following examples.
Example I A 5% solution of meta(lhydroxynaphthalene-2-sulfoamido)benzaldehyde polyvinyl acetal (prepared as described in application Serial Number 667,111, filed May 3, 1946, now U. S. Patent No. 2,433,572) was prepared in a waterethanol solution containing 75 parts of the former and parts of the latter by weight. resulting solution was deposited on a baryta coated paper support at a coating weight of 60 milligrams per square decimeter of said acetal.
This structure is found in The resulting layer was dried at a temperature of about l050 C. in a current of air. solution of the zinc double salt of diazotized p-amino-diethylaniline in water was supplied to the layer. The entire operation was carried out in the absence of actinic light. The resulting element, after drying, was exposed to a positive transparent image by means of a 500 watt 3200 K. lamp at a distance of three feet for ten minutes. The exposed element was subsequently developed by fuming it with ammonia vapor for a period of ten minutes. A strong, positive image, which was brown in color, was formed.
Example II A 5% solution of meta(p-[5-ethylcarbonato-3- methyl l pyrazoyl)benzamidolbenzaldehyde acetal of polyvinyl alcohol (prepared as described in application Serial Number 667,126, filed May 8,1946, now U. S. Patent No. 2,476,988) was substituted for the acetal of Example I. The resulting element was exposed and developed as described in that example whereby a magenta image was formed.
Example III A 5% solution of meta(benzoylacetamido)benzaldehyde polyvinyl acetal (prepared as described in application Serial Number 667,126, filed May 3, 1946, now U. S. Patent No. 2,464,597) was sub stituted for the acetal of Example I. The resulting element was exposed and processed as described in that example and a strong, orange image was obtained.
In place of the specific color formers of the above examples, there may be substituted other hydrophilic polymeric color formers and especially those of the aforementioned patents with similar results.
Any organic solvent or mixture of solvents may be employed in preparing the solutions as long as they are not reactive with the daizo compounds. Thus ketones, such as acetone, methyl ethyl ketone, cyclohexanone, etc., cannot be used, while alcohols, e. g., methanol, ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, etc; glycols, c. g., ethylene glycol, diethylene glycol, propylene glycol; ethlyene glycol monomethyl and monoethyl ethers; ethylene glycol dimethyl ether; tetrahydroiuran; esters, e. g., methyl acetate, ethyl acetate, ethyl propionate, ethyl butyrate, ethyl glycolate, ethyl methoxyacetate; hydrocarbons, e. g., hexane, benzene; chlorinated hydrocarbons, e. g., chloroform, carbon tetrachloride, ethylene dichloride, etc., can be used providing that they are solvents for all the constituents of the coating composition.
The preferred solvents or solvent solutions are those which are water-miscible to the extent that 10% or more water can be dissolved therein. A small amount of water in the coating composition is desirable and aids in dissolving the diazonium compound and in securing an even lightsensitive coating. Further, it is usually desirable to use those with an appreciable vapor pressure at normal temperatures so that drying times will be as short as possible. However, in addition, portions (e. g., 5 to 25%) of solvent with a higher vapor pressure, e.g., boiling between and 260 C, are advantageous as an aid in securing even flow outs and smooth coatings.
In preparing solutions for application by spraying, it is often desirable to add an anti-foaming agent, e. g., long chain aliphatic alcohol, e. g.,
decylfdodecyl, tetradecyl, etc., so that an even coating free from bubbles may be obtained.
Y Y 1 1 I R ONH- NH2 /N -NH e I I Z X Z X and R NH:
naphthalene; l-aminodieth'ylaniline, 4-aminodiaminonapthalene, 4-amino-diphenyl, 4-aminocarboethoxyaniline; methyl, 4 amino-2,5-dimethoxyphenyl urea; phenyl, 4-amino-'2,5-dichlorophenyl urea. f
Any of the various known sensitizers, such as urea, thiourea, allyl thiourea, thiosulfate, etc., and/or compounds which form double salts with diazonium compounds, such as tin," zinc, or cadmium salts, of weak acids, e. g., tartaric, citric, succinic, boric, etc., may be employed in these compositions. The latter compounds prevent coupling prior to exposure.
It is also desirable in some cases to add pigments to the compositions. For instance, if the light-sensitive composition is to be applied to a surface which is dark in color or unpainted and it is desired to have the maximum contrast, a pigment is added which is complementary in color to that of the final azo dye produced in the drawing. Thus, if the dye formed is black, a white pigment may be added, such as titanium dioxide or barium sulfate pigment. If the final colors are to be red, a green pigment may be used, or if they are to be blue, a yellow pigment may be used or any other such combination.
Suitable diazo stabilizers which prevent decomposition of the light-sensitive diazonium compounds when coated on metal plates, e. g., ferrous metal plates, are metal deactivators and corrosion inhibitors which are unreactive toward diazonium salts. Compounds useful for this purpose include water-soluble metal nitrites, e. g., alkali metal nitrites, alkyl nitrites, e. g., amyl nitrite; alkyl phosphates, e. g., monododecyl phosphate, didodecyl phosphate; and aromatic phosphates, e. g., tricresyl phosphate. These compounds may be used in small amounts, e. g., 0.01 to 0.2% based on the total weight of the hydrophilic, polymeric color former used.
Self-supporting foils may be made by coating the hydrophilic, polymeric color former solu- 6 tions onto-a smooth surface, drying the resulting film element, and Stripping it from thecasting surface.
The light-sensitive, hydrophilic, polymeric color former coating compositions hereof have the advantage that they form watei' permeable layers which are free from tackiness so that the surface will not stick to other materials, even when stored. in a humid place. The resulting layers have a tough, smooth surface and are not softened by'water sufficiently to cause scratching or marring when handled Wet.
The coating compositions of this invention have a wide utility and are generally useful where it is desired to copy a design, drawing,
lettering, plan, etc., onto any water-resistant surface.- Thus, in the manufacture of templates for-use in preparing parts of machinery, airplanes, boats, automobiles, electrical equipment, etc.,- the materials to be used, such as metal, composition boards, etc., are coated with the light-sensitive compositions ofthis invention, dried, exposedthrough the master drawing, and developed. The finished print, which adheres firmly and is an exact duplicate of the original, is used to cutout the template. Stencils or lettered transparencies may also be used to reproduce directions, identification numbers,, etc., on parts or finished articles of manufacture. Elements may also be prepared by coating the light-sensitive solutions on flexible bases, such as film base, water-proofed paper, plastic sheeting, and the like. Such elements may be used to prepare permanent records or may be fastened adhesively to"permanent.supports, e.; g., metal, boards, etc. i
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 excep as defined by the claims.
What is claimed is':- t.
l. Photographic element comprising a support bearing at least one layer composed of a hydrophilic polymeric color former having light-sensitive diazonium compounds uniformly dispersed therethrough, said color former containing a multiplicity of recurring active groups which have a structure represented by the formula where n is a number taken from the group consisting of 0 and l.
2. Photographic element comprising a support bearing at least one layer composed of a hydrophilic polymeric color former having light-sentitive diazonium salts uniformly dispersed therethrough, said color former containing a multiplicity of recurring active groups which have a structure represented by the formula where n is a number taken from the group consisting of 0 and l. p
3. Photographic element comprising a support bearing at least one layer composed of a hydrophilic hydroxyl polymer color former having light-sensitive diazonium salts uniformly dispersed th rethrough, said color former containing a multiplicity of recurring CH2--CHOH-- groups and a multiplicity of recurring active groups which have a structure represented by the formula where n is a number taken from the group consisting of 0 and 1.
4. Photographic element comprising a support bearing at least one layer composed of a hydrophilic polyvinyl acetal color former which contains a multiplicity of recurring CHzCHOH- groups and a multiplicity of recurring active groups which have a structure represented by the formula .where n. is a. number taken from the group con- :former having light-sensitive diazonium compound uniformly dispersed therethrough, said polyvinyl acetal color former containing a multiplicity of recurring extralinear active groups which have a structure represented by the formula where n is a number taken from the group consisting of 0 and. 1.
6. A photographic element comprising a waterproofed paper support bearing a layer composed of m (1-hydroxynaphthalene-2-su1fonamido)r benzaldehyde polyvinyl acetal having a zinc double salt of diazotized p-aminodiethyl aniline uniformly dispersed therethrough.
7. A photographic element comprising a water-proofed paper support bearing a layer composed of m-(p-[5-ethylcarbonato-3-methy1- 1 pyrazoybbenzamido] benzaldehyde polyvinyl acetal having a zinc double salt of diazotized p-aminodiethyl aniline uniformly dispersed therethrough.
8. A photographic element comprising a waterproofed paper support bearing a layer composed of m-(benzoylacetamido) benzaldehyde polyvinyl acetal having a zinc double salt of diazotized p-aminodiethyl aniline uiformly dispersed therethrough.
ANDREW BRADSHAW JENNINGS. OTIS WILLARD MURRAY.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 1,444,469 Kogel Feb. 6, 1923 1,756,400 Schmidt Apr. 29, 1930 2,282,001 Russell May 5, 1942 2,297,732 Woodward Oct. 6, 1942 2,310,943 Dorough Feb. 16, 1943 2,318,352 Alink May 4, 1943 2,320,422 Frohlich June 1, 1943 2,342,620 Woodward Feb. 22, 1944 2,397,864 Jennings et a1 Apr. 2, 1946 2,397,865 Jennings Apr. 2, 1946 2,397,866 McQueen Apr. 2, 1946 2,397,867 Jennings Apr. 2, 1946 2,405,523 Sease Aug. 6, 1946 2,415,381 Woodward Feb. 4, 1947 2,415,382 Woodward Feb. 4, 1947 2,423,460 McQueen July 8, 1947 FOREIGN PATENTS Number Country Date 700,252 Germany Dec. 16, 1940

Claims (1)

1. PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT BEARING AT LEAST ONE LAYER COMPOSED OF A HYDROPHILIC POLYMERIC COLOR FORMER HAVING LIGHT-SENSITIVE DIAZONIUM COMPOUNDS UNIFORMLY DISPERSED THERETHROUGH, SAID COLOR FORMER CONTAINING A MULTIPLICITY OF RECURRING ACTIVE GROUPS WHICH HAVE A STRUCTURE REPRESENTED BY THE FORMULA
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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2720467A (en) * 1951-09-11 1955-10-11 Ozalid Co Ltd Process for preparing photographic elements
US2781265A (en) * 1952-03-15 1957-02-12 Keuffel & Esser Co Photosensitive material
US2833649A (en) * 1953-08-11 1958-05-06 Keuffel & Esser Co Light-sensitive diazotype material
US2948610A (en) * 1955-07-29 1960-08-09 Eastman Kodak Co Light-sensitive compositions and their use in photomechanical processes
US3027256A (en) * 1957-11-22 1962-03-27 Dietzgen Co Eugene Production of light-sensitive diazotype materials
US3028240A (en) * 1958-01-18 1962-04-03 Keuffel & Esser Co Light sensitive diazotype materials
US3149972A (en) * 1960-08-16 1964-09-22 Gen Aniline & Film Corp Diazo and resinous coupler printing plates for photomechanical reproduction
US3164468A (en) * 1960-06-06 1965-01-05 Gen Aniline & Film Corp Photomechanical reversal process and foil and dyes for use therein
US3169869A (en) * 1958-06-04 1965-02-16 Grinten Chem L V D Diazotype material
US3275442A (en) * 1961-11-14 1966-09-27 Polacoat Inc Method of irreversibly darkening a bis (p-aminophenyl) vinyl carbonium polymethine leuco dye
US3407066A (en) * 1963-06-18 1968-10-22 Gaf Great Britain Ltd Light sensitive diazonium compounds and diazotype materials
DE1297468B (en) * 1963-06-14 1969-06-12 Gen Aniline & Film Corp Two component diazotype material
US3628954A (en) * 1970-03-24 1971-12-21 Keuffel And Esser Co Diazo material and visible light development process therefore
US3929488A (en) * 1971-06-17 1975-12-30 Howson Algraphy Ltd Light sensitive diazo composition with azo dye formed from a diazonium salt and a novolak resin
DE3118039A1 (en) * 1980-05-16 1982-03-04 Kimoto & Co. Ltd., Tokyo Photosensitive material and process for producing it
US4642283A (en) * 1984-03-14 1987-02-10 Fuji Photo Film Co., Ltd. Plate making processing for using negative working light-sensitive lithographic plate requiring no dampening solution
US4659644A (en) * 1983-12-22 1987-04-21 Ricoh Company, Ltd. Diazo-type thermosensitive recording material with hydrazone coupler and chelating metal compound
US4743524A (en) * 1986-10-17 1988-05-10 Andrews Paper & Chemical Co., Inc. Diazotype composition with a non-migrating yellow coupler of controlled coupling energy
US5424164A (en) * 1989-12-06 1995-06-13 Fuji Photo Film Co., Ltd Image forming method

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US1444469A (en) * 1917-05-31 1923-02-06 Firm Of Kalle & Co Ag Manufacture of light copy paper
US1756400A (en) * 1926-02-22 1930-04-29 Kalle & Co Ag Light-sensitive materials and process of making them
DE700252C (en) * 1938-12-16 1940-12-16 Kalle & Co Akt Ges Diazo blueprint material
US2282001A (en) * 1939-09-13 1942-05-05 Eastman Kodak Co Color-forming gelatin compound
US2297732A (en) * 1940-05-15 1942-10-06 Du Pont Photographic color process involving the formation of azo dye images
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US2318352A (en) * 1939-04-11 1943-05-04 Hartford Nat Bank & Trust Co Light-sensitive diazotype layers and method of making same
US2320422A (en) * 1939-05-09 1943-06-01 Gen Aniline & Film Corp Process for the production of photographic color images
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US2397867A (en) * 1944-05-06 1946-04-02 Du Pont Photographic elements containing protein color formers
US2397865A (en) * 1944-03-31 1946-04-02 Du Pont Processes of color photography and elements therefor
US2405523A (en) * 1944-08-09 1946-08-06 Du Pont Light-sensitive photographic compositions and elements
US2415381A (en) * 1944-03-31 1947-02-04 Du Pont Hydrophilic colloid color formers and photographic elements containing the same
US2415382A (en) * 1944-03-31 1947-02-04 Du Pont Photographic elements including hydrophilic color formers
US2423460A (en) * 1944-03-31 1947-07-08 Du Pont Photographic elements containing polyamide dye intermediate layers

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1444469A (en) * 1917-05-31 1923-02-06 Firm Of Kalle & Co Ag Manufacture of light copy paper
US1756400A (en) * 1926-02-22 1930-04-29 Kalle & Co Ag Light-sensitive materials and process of making them
US2310943A (en) * 1938-10-05 1943-02-16 Du Pont Polyvinyl acetals
DE700252C (en) * 1938-12-16 1940-12-16 Kalle & Co Akt Ges Diazo blueprint material
US2318352A (en) * 1939-04-11 1943-05-04 Hartford Nat Bank & Trust Co Light-sensitive diazotype layers and method of making same
US2320422A (en) * 1939-05-09 1943-06-01 Gen Aniline & Film Corp Process for the production of photographic color images
US2282001A (en) * 1939-09-13 1942-05-05 Eastman Kodak Co Color-forming gelatin compound
US2297732A (en) * 1940-05-15 1942-10-06 Du Pont Photographic color process involving the formation of azo dye images
US2342620A (en) * 1942-07-10 1944-02-22 Du Pont Azo-reversal process of color photography
US2397866A (en) * 1944-03-31 1946-04-02 Du Pont Photographic elements
US2397864A (en) * 1944-03-31 1946-04-02 Du Pont Color yielding photographic elements
US2397865A (en) * 1944-03-31 1946-04-02 Du Pont Processes of color photography and elements therefor
US2415381A (en) * 1944-03-31 1947-02-04 Du Pont Hydrophilic colloid color formers and photographic elements containing the same
US2415382A (en) * 1944-03-31 1947-02-04 Du Pont Photographic elements including hydrophilic color formers
US2423460A (en) * 1944-03-31 1947-07-08 Du Pont Photographic elements containing polyamide dye intermediate layers
US2397867A (en) * 1944-05-06 1946-04-02 Du Pont Photographic elements containing protein color formers
US2405523A (en) * 1944-08-09 1946-08-06 Du Pont Light-sensitive photographic compositions and elements

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2720467A (en) * 1951-09-11 1955-10-11 Ozalid Co Ltd Process for preparing photographic elements
US2781265A (en) * 1952-03-15 1957-02-12 Keuffel & Esser Co Photosensitive material
US2833649A (en) * 1953-08-11 1958-05-06 Keuffel & Esser Co Light-sensitive diazotype material
US2948610A (en) * 1955-07-29 1960-08-09 Eastman Kodak Co Light-sensitive compositions and their use in photomechanical processes
US3027256A (en) * 1957-11-22 1962-03-27 Dietzgen Co Eugene Production of light-sensitive diazotype materials
US3028240A (en) * 1958-01-18 1962-04-03 Keuffel & Esser Co Light sensitive diazotype materials
US3169869A (en) * 1958-06-04 1965-02-16 Grinten Chem L V D Diazotype material
US3164468A (en) * 1960-06-06 1965-01-05 Gen Aniline & Film Corp Photomechanical reversal process and foil and dyes for use therein
US3149972A (en) * 1960-08-16 1964-09-22 Gen Aniline & Film Corp Diazo and resinous coupler printing plates for photomechanical reproduction
US3275442A (en) * 1961-11-14 1966-09-27 Polacoat Inc Method of irreversibly darkening a bis (p-aminophenyl) vinyl carbonium polymethine leuco dye
DE1297468B (en) * 1963-06-14 1969-06-12 Gen Aniline & Film Corp Two component diazotype material
US3407066A (en) * 1963-06-18 1968-10-22 Gaf Great Britain Ltd Light sensitive diazonium compounds and diazotype materials
US3628954A (en) * 1970-03-24 1971-12-21 Keuffel And Esser Co Diazo material and visible light development process therefore
US3929488A (en) * 1971-06-17 1975-12-30 Howson Algraphy Ltd Light sensitive diazo composition with azo dye formed from a diazonium salt and a novolak resin
DE3118039A1 (en) * 1980-05-16 1982-03-04 Kimoto & Co. Ltd., Tokyo Photosensitive material and process for producing it
US4374193A (en) * 1980-05-16 1983-02-15 Kimoto & Co., Ltd. Photosensitive material and process for developing the same
US4659644A (en) * 1983-12-22 1987-04-21 Ricoh Company, Ltd. Diazo-type thermosensitive recording material with hydrazone coupler and chelating metal compound
US4642283A (en) * 1984-03-14 1987-02-10 Fuji Photo Film Co., Ltd. Plate making processing for using negative working light-sensitive lithographic plate requiring no dampening solution
US4743524A (en) * 1986-10-17 1988-05-10 Andrews Paper & Chemical Co., Inc. Diazotype composition with a non-migrating yellow coupler of controlled coupling energy
US5424164A (en) * 1989-12-06 1995-06-13 Fuji Photo Film Co., Ltd Image forming method

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