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US3469981A - Diazotype reproduction materials - Google Patents

Diazotype reproduction materials Download PDF

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US3469981A
US3469981A US482655A US3469981DA US3469981A US 3469981 A US3469981 A US 3469981A US 482655 A US482655 A US 482655A US 3469981D A US3469981D A US 3469981DA US 3469981 A US3469981 A US 3469981A
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support
diazotype
sheet
amide
developing
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US482655A
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Jaromir Kosar
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Keuffel and Esser Co
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Keuffel and Esser Co
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Assigned to BANK OF CALIFORNIA N.A. THE; A NATIONAL BANKING ASSOCIATION, CONTINENTAL ILLINOIS NATIONAL BANK & TRUST CO., OF CHICAGO, A NATIONAL BANKING ASSOCIATION, SECURITY NATIONAL BANK, A NATIONAL BANKING ASSOCIATION FOR ITSELF AND AS AGENT FOR CITIBANK, N.A. A NATIONAL BANKING ASSOCIATION, CHASE MANHATTAN BANK, N.A. THE; A NATIONAL BANKING ASSOCIATION, CHEMICAL BANK, A BANKING INSTITUTION OF reassignment BANK OF CALIFORNIA N.A. THE; A NATIONAL BANKING ASSOCIATION SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KEUFFEL & ESSER COMPANY A.N.J. CORP
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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
    • G03C1/60—Compositions containing diazo compounds as photosensitive substances with macromolecular additives

Definitions

  • the present invention relates to diazotype reproduction materials and to methods and means for their development, and refers more particularly to heat-developable diazotype reproduction materials and to methods and means for their development.
  • Diazotype reproduction materials are well known and have many advantages over other means of reproduction when considering the combined bases of quality and cost. However, they do possess some disadvantages which are inherent in the method of development.
  • the semi-moist method the exposed diazotype material is passed through a bath of coupler and squeezed dry.
  • the dry method the exposed diazotype material is passed through a chamber of gaseous ammonia to effect development.
  • the semi-moist method of development sutfers from the disadvantageous requirements of periodic replenishment of the developer supply, removal of exhausted developer, periodic cleaning of developer container, and deleterious effects of the liquid developer on the diazotype base which is usually paper.
  • the dry method has the disadvantages of requiring equipment to supply, confine, and exhaust the noxious ammonia.
  • Heat for example has been used to develop images on reproduction materials but they remained heat-sensitive and ultimately were unsatisfactory as copies.
  • Kendal et al. in British Patent 815,005 relates to multilayer diazotype reproduction material which comprised a support bearing a coupler layer, a fusible barrier layer, and a diazo layer.
  • Botkin in US. Patent 2,727,820 relates to an improvement in the production of photographic prints by the diazotype process wherein carboxamides were included in the photosensitive diazo layer to act as developing aids when the diazotype reproduction material was developed in a conventional ammonia-developing machine.
  • the system of using developing sheets containing a source of heat-liberated alkali avoided the disadvantages of liquid developers and of gaseous ammonia, but it introduced the inconvenience of a two-sheet system.
  • the developing sheet had to be placed in uniform contact with the exposed sensitized surface of the diazotype reproduction material to form a two-ply assembly which was then heated to effect development. The developing sheet was then separated from the reproduction material and set aside.
  • the major advantage of a developing sheet was the isolation of a critical ingredient until needed.
  • Isolation of the critical ingredient of the system could also be accomplished by precoatings or multilayer coatings. This would overcome the objection to the two-sheet system, but at the expense of increased cost and increased technical difiiculty.
  • the simplest system was to coat all ingredients onto one support from one solution in one layer in one operation.
  • One requirement was that both the solution and the coated layer be stabilized to prevent premature coupling of the diazo compound and the coupler.
  • the present invention provides heat-developable twocomponent light-sensitive diazotype reproduction materials, systems, and methods, which avoid the use of liquid developers and gaseous ammonia and which are stable against further development.
  • the invention is adaptable to the developing sheet system, the precoat or multilayer system, and to the single layer coating system.
  • One object of the present invention is to provide a heat-developable diazotype reproduction material, system, and method which does not have the disadvantages of prior art.
  • Another object is to provide a heat-developable diazotype reproduction material, system, and method which does not require the use of liquid developers or gaseous ammonia for development.
  • Another object is to provide a heat-developable diazotype reproduction material Which is stable against further color development.
  • Another object is to provide a heat-developable diazotype reproduction material which is inexpensive and which gives good quality diazo reproductions.
  • Another object is to provide a heat-sensitive developing sheet for the thermal development of diazotype reproduction materials.
  • Another object is to provide a system which is adaptable to the two-sheet, the precoat, and the single layer systems of thermal development of diazotype reproduction materials.
  • thermally decomposable sources of alkali are used as developing agents for the diazotype reproduction material.
  • These sources of alkali are organic nitrogen compounds which may be classified as amides. Depending upon their chemical nature, they may be used in the sensitized layer, in a precoated layer, or in a separate developing sheet. Thus these amides can be used in at least three diazotype reproduction systems.
  • the amides of the present invention are decomposed at elevated temperatures when it is desired to release ammonia. This raises the alkalinity of the sensitized layer and allows coupling to occur and thus renders the latent image visible.
  • amides found to be suitable for the present invention are those derived from monobasic saturated acids, mono-basic unsaturated acids, aromatic carboxylic acids, aromatic hydroxy acids, saturated dibasic acids, and aromatic dibasic acids. These amides have the general formula:
  • R is hydrogen, alkyl, substituted alkyl, alkylene, substituted alkylene, amidated alkyl, aryl, substituted aryl, amidated aryl, a heterocyclic ring, or a polymeric chain, and
  • n is preferably approximately 560.
  • Amides are derived from carboxylic acids by replacing the OH group with an NH group or NR R group where R and R may be hydrogen, alkyl, or aryl.
  • the amides are generally solids at room temperatures; the lower molecular weight amides being readily soluble in water, while the higher molecular weight amides are almost insoluble in water.
  • diazonium compounds and couplers that are suitable for the conventional dry developing diazotype reproduction materials can be employed in the present invention.
  • diazonium compounds are the zinc chloride and the boron trifluoride stabilized salts of p-dialkylamino benzene diazonium chlorides. These compounds are used in concentrations ranging from 1.5 to of the sensitizing solution, and they can be used singly or in combinations.
  • Couplers are phenols and naphthols, such as phloroglucinol, resorcinol, alpha-naphthol, betanaphthol, and 2,3-dihydroxynaphthalene-6 sulfonic acid (sodium salt). These couplers may be used singly or in combination to vary the color.
  • the coating solution and the sensitized layer can also contain various other chemicals commonly used in the preparation of light-sensitive diazotype reproduction materials. These include stabilizing acids, anti-oxidants, hygroscopic agents, wetting agents, and image intensifiers.
  • Acids that can be used are tartaric acid, citric acid, acetic acid, trichloroacetic acid, and 1,3,6-naphthlenetrisulfonic acid or its sodium salt.
  • Thiourea and allyl isothiocyanate are commonly used anti-oxidants.
  • the sensitizing solution and sensitized layer may further contain hygroscopic agents such as glycerine, ethylene glycol, or the like; wetting agents such as saponin and lauryl sulfonates; and image intensifiers such as Zinc chloride and nickel sulfate.
  • hygroscopic agents such as glycerine, ethylene glycol, or the like
  • wetting agents such as saponin and lauryl sulfonates
  • image intensifiers such as Zinc chloride and nickel sulfate.
  • Suitable supports include not only those types of papers such as ordinary pulp paper, rag paper, and document paper, but also starch filled cloth, felt, saponified cellulose acetate film, transparent cellulosic material such as cellophane, and the like.
  • Suitable supports include not only those types of papers such as ordinary pulp paper, rag paper, and document paper, but also starch filled cloth, felt, saponified cellulose acetate film, transparent cellulosic material such as cellophane, and the like.
  • FIGURE 1 is a sectional view of a heat-developable two-component photosensitive diazotype reproduction material 10 of the present invention comprising a support 11 and a heat-developable two-component photosensitive diazotype layer 12 coated on said support;
  • FIGURE 2 is a sectional view of a heat-developable two-component photosensitive diazotype reproduction material 20 of the present invention comprising a support 21, a precoat layer 22 coated on said support, and a two-component photosensitive diazotype layer 23 coated over said precoat layer on said support; and
  • FIGURE 3 is a sectional view of a developing sheet 30 comprising a support 31 and a heat-decomposable amide 32 impregnated in support 31, in juxtaposition with a two-component photosensitive diazotype reproduction material 33 comprising a support 34 and a two-component photosensitive diazotype layer 35 coated on support 34.
  • One method of the present invention for the preparation of a heat-developable reproduction material is to first treat a support material with a solution of an amide. After drying, the same support is treated on the same side or on the opposite side with a sensitizing solution containing as major ingredients: a diazonium compound, a coupler, and where desired, a stabilizing acid. After drying, the sensitized support is ready for use. The sensit zed support is exposed through a master to actinic radiatrons and is then developed by heat in the range between the decomposition temperature of the amide and the scorching temperature of the support material. The heat-activated liberation of alkaline vapors then causes the image to develop.
  • Example 1 The preparation and use of a heat-developable twocomponent photosensitive diazotype reproduction material precoated with an amide of the present invention is illustrated in Example 1.
  • the amide is incorporated with the photosensitive diazonium compound, a coupler, and where desired, a stabilizing acid in a sensitizing solution which is applied to a support and then dried.
  • the sensitized support can then be exposed through a master to actinic radiations. After exposure, heat is applied to the support.
  • the temperature is preferably in the range between the decomposition temperature of the amide and the scorching temperature of the support material.
  • a developing sheet was prepared by impregnating a support with a solution of an amide in an appropriate solvent. The solvent was then removed by drying. The developing sheet was then used to develop an exposed two-component photosensitive diazotype reproduction material by making face-to-face contact with the exposed sensitized surface of the diazotype material and subjecting the assembly to heat in the range between the decomposition temperature of the amide and the scorching temperature of the diazotype support. Alkaline vapors were liberated to elfect development of the latent image.
  • the preparation and use of a developing sheet utilizing an amide of the present invention is illustrated in Example 3.
  • the alkali-liberating agent may be incorporated into the pulp or raw material used to manufacture the support in suitable proportions to obtain the desired results.
  • the developing temperature range was determined by two factors: the first was the decomposition temperature of the thermally decomposable amide, and the second was the scorching temperature of the support.
  • the decompo sition temperature of the thermally decomposable amide is affected by the presence of other chemicals in the system. The presence of a good source of hydrogen ions favors decomposition by hydrolysis.
  • Example 1 30 grams of acrylamide were dissolved in 150 milliliters of water and were coated onto a paper support. After drying, the precoated support was sensitized with the following solution:
  • the coating was dried to produce a precoated and sensitized diazotype reproduction material. This was exposed through a master to actinic radiations and developed by subjecting the reproduction material to 150 C. for a few seconds. The heat liberated alkaline vapors from the amide and allowed the diazonium compound and the coupler to form a blue dye image corresponding to the master image.
  • Example 2 A sensitizing solution according to the following formula was prepared and coated on a conventional silicasized diazotype paper support:
  • the coating was dried to produce a heat-developable diazotype reproduction material. This was exposed through a master to actinic radiations and then subjected to heat in the range of C. to the scorching point of the paper support for a few second to liberate alkaline vapors and thus develop the blue dye image corresponding to the master image.
  • Diazonium compounds other than p-dimethylamino benzene diazonium chloride can be used, c.g., p-diethylamino benzene diazonium chloride, and N-ethyl-N-(2hydroxyethyl)-p-amino benzene diazonium chloride were also used.
  • Another coupler such as phloroglucinol was also used.
  • Example 3 20 grams of acrylamide were dissolved in 100 ml. of ethyl alcohol. This solution was used to impregnate a porous paper support. After drying, a developing sheet for the heat-development of exposed two-component diazotype reproduction materials was produced. On a separate paper support the sensitizing solution of Example 1 was applied and dried. This was exposed through a master to actinic radiations and developed by making face-to-face contact with the developing sheet and subjecting the whole assembly to C. for 5 seconds. A blue dye image corresponding to the master image was produced without benefit of liquid developer or gaseous ammonia. The print was stable against any further dye formation due to the application of heat.
  • This system was ideal for amides which were not compatible with the chemicals of the sensitizing solution since isolation was complete. In principle, this isolation can also be achieved by the multilayer system described in British Patent 815,005 and by microencapsulation of the developing agent or the coupler.
  • Example 4 The following sensitizing solution was prepared and coated on a support. After the coating was dried, the sensitized support was exposed to actinic radiation through a master and developed by subjecting it to heat. The color of the image was blue.
  • Example 5 A coating of the following diazo sensitizing solution was applied to a paper support:
  • the developing sheet was brought into uniform contact with the sensitized paper which had been exposed through a master to actinic radiations.
  • the assembly of developing sheet and the diazo sensitized paper was then heated at 150 deg. C. for seconds to produce a blue image on the diazo sensitized paper corresponding to the master image.
  • Example 6 The following sensitizing solution was coated on a support suitable for diazotype reproduction materials:
  • the sensitized support was then dried and exposed through a master to actinic radiation. Heat was used to develop the latent image as a blue dye image.
  • Example 7 To improve storage life, trichloroacetic acid was added according to the following formula:
  • the pH of the solution was 1.3. Storage life was improved by the addition of trichloroacetic acid. Material stored at 115 deg. F. and 47% relative humidity for three days still produced acceptable and satisfactory prints. Lesser amounts of trichloroacetic acid reduced the storage life of the sensitized reproduction material.
  • Example 8 The following sensitizing solution was prepared and coated on a support suitable for diazotype reproduction materials on a production run basis:
  • the coating speed was 16 yards per minute with an airbar pressure of 3 /2 oz. of water.
  • the drying temperature was 180 F.
  • the sensitized and dried material was then exposed through a master to actinic radiation and developed by the application of heat.
  • the developed image was blue in color and satisfactory in density.
  • Example 9 A support sheet was pre-coated with the following solution:
  • the precoated support was sensitized with the following sensitizing solution:
  • the pH of the sensitizing solution was 1.0. After drying, the sensitized sheet was exposed through a master to actinic radiations and developed by heating at 150 C. for 4 seconds. A blue image corresponding to the master image was obtained.
  • Example 10 An absorbent base sheet was soaked in a solution containing 10 grams of acetamide in 150 ml. of ethyl alcohol and then dried to remove the alcohol to produce a developing sheet.
  • a paper support was sensitized with the following solution:
  • the developing sheet and the exposed sensitized support were placed in contact and heated at 150 C. for a few seconds to produce a blue image corresponding to the master image.
  • Example 11 The following solution was prepared and coated on an absorbent support to form a developing sheet:
  • Example 12 A developing sheet prepared by coating the following solution on an absorbent support when heated in contact with printed diazotype paper as described in Example 10 caused a blue image to be produced on the diazotype paper:
  • Example 13 The following solution was prepared and coated in an absorbent support:
  • the blue image was developed by heating for 5 second at 150 C.
  • Example 14 Propionamide was used in the following solution to prepare a developing sheet:
  • Example 15 The following chemicals were substituted individually for the propionamide in Example 13 with the result that the developed images were substantially the same as for propionamide:
  • Example 17 The sensitizing solution was prepared with acrylamide according to the following formula:
  • This solution was coated on an absorbent support and dried. When heat-developed at 150 C. for 5 seconds a blue color was developed.
  • Example 18 Polyacrylamide of low molecular weight such as PAM was used in the following sensitizing solution:
  • This solution was coated on an absorbent support and was dried. After printing with ultraviolet light through a master, the image was developed by heating the coated support at 150 C. for 5 seconds.
  • Example 19 Polyacrylamide such as PAM 10 was used in the following solution to prepare a precoat solution:
  • This solution was coated on a support and dried.
  • the precoated paper was then sensitized with a solution such as described in Example 1. Heat treatment after exposing the sensitized support through a master produced a blue dye image.
  • Example 20 The same polyacrylamide solution as in Example 19 was used to coat an absorbent support to make a developing sheet. When used as in Example 3 to develop a diazotype paper by placing it in contact with the exposed diazotype paper and heating the assembly for a few seconds at C. a blue image on the diazotype paper was developed.
  • This solution was used to impregnate an absorbent sup port. After drying, this developing sheet was placed in contact with sensitized and exposed diazotype paper and heated at 150 C. for 8 seconds. A blue image was formed.
  • Example 22 Methacrylamide was used in place of the acrylamide of Examples 2 and 17, with the same results.
  • Example 23 Malonamide was used in the following sensitizing solu- 2,3 dihydroxynaphthalene-d-sulfonic acid, sodium salt, g. 5 Thiourea, g. 7 Zinc chloride, g 4 Development of a blue dye image after exposure was ac complished by heating at C. for 4 seconds.
  • Example 24 Benzamide was used in the following solution to prepare a developing sheet:
  • Example 25 The solution of Example 24 was used also as a precoat solution. It was coated on a support, dried, and then sensitized with the following solution on the same side:
  • a blue dye image was developed by heating the exposed sheet for 5 seconds at 150 C.
  • Example 26 p-Toluamide was used in the following solution to prepare a developing sheet:
  • the developing sheet was used to develop diazotype paper prepared as in Example 5. A blue color was developed by heating the developing sheet in contact with the diazotype paper for a few seconds at 165 C.
  • Example 27 p-Nitrobenzamide was used in the following solution to prepare a developing sheet:
  • This developing sheet was used to develop a red-brown dye color in the same manner as in Example 26.
  • Example 28 Anthranilamide was used in the following solution to prepare a developing sheet:
  • This solution was coated on a support to make a developing sheet which then was used to develop a diazotype paper as described in Example 5 to produce a blue dye image.
  • Example 29 Anthranilamide was also used in the following sensitiz- This was coated on a support and dried. Heating the exposed sensitized sheet at 160 C. for 6 seconds produced a blue dye image.
  • Example 30 Phthalamide :was used to make a developing sheet by coating a support with the following solution:
  • Example 31 Salicylamide was used in a developing sheet prepared by coating a support with the following solution:
  • the developing sheet was used to develop a blue dye image as in Examples 5 and 30.
  • Example 32 Salicylamide was also used in a precoat layer by coating a support with the following solution:
  • the precoated support was then sensitized as in Example 9. After exposure through a master to actinic radiations, a blue color was developed by heating the sensitized precoated support for 5 seconds at 150 C.
  • Example 33 Z-furamide was used in the following solution to coat a support to a make a developing sheet:
  • This developing sheet was used at 175 C. for 4 seconds to develop printed diazotype paper as described in Example 5.
  • Example 34 N-methylacetamide was used to prepare a developing sheet by impregnating an absorbent support with the following solution:
  • this developing sheet was used to develop exposed diazotype paper prepared as in Example 5 by placing the two sheets in contact and heating them at C. for 7 seconds to obtain a blue color.
  • Example 35 Example 34 was repeated with 2-phenylacetamide in place of N-methylacetamide. After following the same procedure, a blue green image was obtained.
  • Nicotinamide was used in the following solution to impregnate an absorbent support to make a developing sheet:
  • This sheet was then dried and used to develop an exposed diazotype paper by placing it in contact with the exposed diazotype paper and heating the assembly at 150 C. for 6 seconds to obtain a colored image.
  • Example 37 A support was precoated with the following solution:
  • the sensitized support was exposed through a master to actinic radiations and then developed by heating at 160 C. for seconds. A blue-black image was obtained.
  • a process for forming an azo dye comprising:
  • a two-component diazotype sheet material comprising a diazonium compound and an azo dye coupler capable of forming an azo dye with said diazonium compound in an alkaline environment;
  • a process for forming a diazotype image comprising:
  • said developer sheet further comprises an organic acid in an amount between about 20% and 50% of the amount of amide.
  • a process according to claim 1 wherein said amide is N,N-diphenylacetamide.
  • a process for the thermal development of twocomponent light-sensitive diazotype reproduction materials by means of a developing sheet, said reproduction material comprising a support and a light-sensitive layer coated on said support, said developing sheet comprising a separate support and a thermally decomposable alkaliliberating developing agent impregnated in said separate support, said developing agent being N,N-diphenyl formamide, said process comprising the steps of: (1) exposing said reproduction material to actinic radiations through a master, (2) separating the reproduction material from the master, (3) making an assembly with the developing sheet in uniform contact with the sensitized surface of said reproduction material, and (4) heating the assembly in the temperature range between the decomposition temperature of the developing agent and the scorching temperature of said reproduction material support, thus liberating alkali in the immediate vicinity of the sensitized surface of said reproduction material, thereby causing coupling to occur in the image areas.
  • a process for the thermal development of two-component light-sensitive diazotype reproduction materials by means of a developing sheet said reproduction material comprising a support and a light-sensitive layer coated on said support, said developing sheet comprising a separate support and a thermally decomposable alkali-liberating developing agent impregnated in said separate support, said developing agent being phenoxyacetamide
  • said process comprising the steps of: 1) exposing said reproduction material to actinic radiations through a master, (2) separting the reproduction material from the master, (3) making an assembly with the developing sheet in uniform contact with the sensitized surface of said reproduction material, and (4) heating the assembly in the temperature range between the decomposition temper- 1 ature of the developing agent and the scorching temperature of said reproduction material support, thus liberating alkali in the immediate vicinity of the sensitized surface of said reproduction material, thereby causing coupling to occur in the image areas.
  • a process for the thermal development of two-component light-sensitive diazotype reproduction materials by means of a developing sheet said reproduction material comprising a support and a light-sensitive layer coated on said support, said developing sheet comprising a separate support and a thermally decomposable alkali-liberating developing agent impregnated in said separate support, said developing agent being N,N-diphenylacetamide
  • said process comprising the steps of: (1) exposing said reproduction material to actinic radiations through a master, (2) separating the reproduction material from the master, (3) making an assembly with the developing sheet in uniform contact with the sensitized surface of said reproduction material, and (4) heating the assembly in the temperature range between the decomposition temperature of the developing agent and the scorching temperature of said reproduction material support, thus liberating alkali in the immediate vicinity of the sensitized surface of said reproduction material, thereby causing coupling to occur in the image areas.
  • a diazotype developer sheet comprising:

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Description

Sept. 30, 1969 J. KOSAR 3,469,981
DIAZO'IYPE REPRODUCTION MATERIALS Original Filed March 19, 1963 FIG.|
--- HEAT-DEVELOPABLE v TWO-COMPONENT PHOTOSENSITIVE ER l2 HEAT-DEV PABLE TWO-COMPONENT PHOTO- SENSITWE ZOTYPE REPRODUCTION MATERIAL IO FIG.2
TWO- PONENT PHOTOS TIV DIAZOTYPE LAY 3 PRECOAT LAYER SUPPORT 2| E T-DEVELOPABLE TWO-COMPON T PHOTOSENSITIVE ZOTYPE REPRODUCTION MATE L 20 FIG. 3 DEVELOPING SHEET so WHEAT'DECOMPOSABLE T AMIDE 32 suPPoRT 3| HEAT-DECOMPOSABLE AMIDE 32 -c0 s TWO-COMPONENT PHOTOSENSITIVE DIAZOTYPE REPRODUCTION MATERIAL 33 [NV OR. JAROMIR AR ATTORNEY United States Patent 3,469,981 DIAZOTYPE REPRODUCTION MATERIALS Jaromir Kosar, Bceehhurst, N.Y., assignor to Keuffel & Esser Company, Hoboken, N.J., a corporation of New Jersey Original application Mar. 19, 1963, Ser. No. 266,230, new Patent No. 3,255,007, dated June 7, 1966. Divided and this application July 12, 1965, Ser. No. 482,655
Int. Cl. G03c 1/58, 5/34 US. Cl. 96-49 24 Claims This is a division of application Ser. No. 266,230, filed Mar. 19, 1963, now Patent No. 3,255,007.
The present invention relates to diazotype reproduction materials and to methods and means for their development, and refers more particularly to heat-developable diazotype reproduction materials and to methods and means for their development.
Diazotype reproduction materials are well known and have many advantages over other means of reproduction when considering the combined bases of quality and cost. However, they do possess some disadvantages which are inherent in the method of development.
Two methods of development are generally used: the semi-moist method and the dry method, In the semimoist method the exposed diazotype material is passed through a bath of coupler and squeezed dry. In the dry method, the exposed diazotype material is passed through a chamber of gaseous ammonia to effect development.
The semi-moist method of development sutfers from the disadvantageous requirements of periodic replenishment of the developer supply, removal of exhausted developer, periodic cleaning of developer container, and deleterious effects of the liquid developer on the diazotype base which is usually paper. The dry method has the disadvantages of requiring equipment to supply, confine, and exhaust the noxious ammonia.
Other means for developing diazotype materials have been tried but were less practical than either the semimoist or dry methods.
Heat for example has been used to develop images on reproduction materials but they remained heat-sensitive and ultimately were unsatisfactory as copies.
In an attempt to eliminate the disadvantages of both the semi-moist and the dry developing systems, heat-development of diazotype reproduction materials was tried. This was feasible because exposure of a diazotype reproduction material through a master to a source of actinic radiations decomposes the diazonium compound in the non-image areas. Consequently, these areas cannot develop and the diazotype reproduction material in effect is fixed or stabilized during exposure. The latent image could then be developed by some developing agent in the sensitized layer, in a separate layer, or in a separate support.
For example, Dieterle in US. Patent 2,228,562 relates to a developing sheet treated with a heat-decomposable ammonia compound. Placed in contact with an exposed diazotype reproduction material and heated, the developing sheet liberated ammonia vapors which developed the latent image. The ammonia compounds, however, had very poor shelf-life and consequently, their practical use was limited.
Barde in U.S. Patent 2,313,288 incorporated urea into a layer with a diazoic that formed its own coupler as a photolytic decomposition product. Heat decomposed the urea to liberate ammonia vapors which then neutralized the acid formed during coupling. Morrison in US. Patent 2,732, 299, on the other hand, incorporated urea into a separate stratum on the diazotype reproduction material to serve as the source of heat-liberated ammonia.
Greig in US. Patent 2,691,587; Marron in US. Patent 2,774,669; and Benbrook in US. Patent 2,789,904
ice
all relate to developing sheets containing either the coupler or the source of heat-liberated alkali.
Kendal et al. in British Patent 815,005 relates to multilayer diazotype reproduction material which comprised a support bearing a coupler layer, a fusible barrier layer, and a diazo layer.
Botkin in US. Patent 2,727,820 relates to an improvement in the production of photographic prints by the diazotype process wherein carboxamides were included in the photosensitive diazo layer to act as developing aids when the diazotype reproduction material was developed in a conventional ammonia-developing machine.
The system of using developing sheets containing a source of heat-liberated alkali avoided the disadvantages of liquid developers and of gaseous ammonia, but it introduced the inconvenience of a two-sheet system. The developing sheet had to be placed in uniform contact with the exposed sensitized surface of the diazotype reproduction material to form a two-ply assembly which was then heated to effect development. The developing sheet was then separated from the reproduction material and set aside.
The major advantage of a developing sheet was the isolation of a critical ingredient until needed.
Isolation of the critical ingredient of the system could also be accomplished by precoatings or multilayer coatings. This would overcome the objection to the two-sheet system, but at the expense of increased cost and increased technical difiiculty.
The simplest system was to coat all ingredients onto one support from one solution in one layer in one operation. One requirement was that both the solution and the coated layer be stabilized to prevent premature coupling of the diazo compound and the coupler.
The present invention provides heat-developable twocomponent light-sensitive diazotype reproduction materials, systems, and methods, which avoid the use of liquid developers and gaseous ammonia and which are stable against further development. The invention is adaptable to the developing sheet system, the precoat or multilayer system, and to the single layer coating system.
One object of the present invention is to provide a heat-developable diazotype reproduction material, system, and method which does not have the disadvantages of prior art.
Another object is to provide a heat-developable diazotype reproduction material, system, and method which does not require the use of liquid developers or gaseous ammonia for development.
Another object is to provide a heat-developable diazotype reproduction material Which is stable against further color development.
Another object is to provide a heat-developable diazotype reproduction material which is inexpensive and which gives good quality diazo reproductions.
Another object is to provide a heat-sensitive developing sheet for the thermal development of diazotype reproduction materials.
Another object is to provide a system which is adaptable to the two-sheet, the precoat, and the single layer systems of thermal development of diazotype reproduction materials.
Other objects of the present invention will become apparent in the course of the following specification.
In the present invention, thermally decomposable sources of alkali are used as developing agents for the diazotype reproduction material. These sources of alkali are organic nitrogen compounds which may be classified as amides. Depending upon their chemical nature, they may be used in the sensitized layer, in a precoated layer, or in a separate developing sheet. Thus these amides can be used in at least three diazotype reproduction systems.
The amides of the present invention are decomposed at elevated temperatures when it is desired to release ammonia. This raises the alkalinity of the sensitized layer and allows coupling to occur and thus renders the latent image visible.
Some of the amides found to be suitable for the present invention are those derived from monobasic saturated acids, mono-basic unsaturated acids, aromatic carboxylic acids, aromatic hydroxy acids, saturated dibasic acids, and aromatic dibasic acids. These amides have the general formula:
where R is hydrogen, alkyl, substituted alkyl, alkylene, substituted alkylene, amidated alkyl, aryl, substituted aryl, amidated aryl, a heterocyclic ring, or a polymeric chain, and
NH2 n where there is at least one amido group per monomer unit for this amidated polymer thain; n is preferably approximately 560.
Amides are derived from carboxylic acids by replacing the OH group with an NH group or NR R group where R and R may be hydrogen, alkyl, or aryl. The amides are generally solids at room temperatures; the lower molecular weight amides being readily soluble in water, while the higher molecular weight amides are almost insoluble in water.
By heating in the presence of acids, the amides are bydrolyzed to carboxylic acids with consequent liberation of alkaline vapors. These alkaline vapors are utilized to develop the exposed diazotype reproduction material. The presence of acid is not required for operation of the invention. This is demonstrated by Example 17 and others.
Combinations of diazonium compounds and couplers that are suitable for the conventional dry developing diazotype reproduction materials can be employed in the present invention. Examples of the diazonium compounds are the zinc chloride and the boron trifluoride stabilized salts of p-dialkylamino benzene diazonium chlorides. These compounds are used in concentrations ranging from 1.5 to of the sensitizing solution, and they can be used singly or in combinations.
Some suitable couplers are phenols and naphthols, such as phloroglucinol, resorcinol, alpha-naphthol, betanaphthol, and 2,3-dihydroxynaphthalene-6 sulfonic acid (sodium salt). These couplers may be used singly or in combination to vary the color.
The coating solution and the sensitized layer can also contain various other chemicals commonly used in the preparation of light-sensitive diazotype reproduction materials. These include stabilizing acids, anti-oxidants, hygroscopic agents, wetting agents, and image intensifiers.
Acids that can be used are tartaric acid, citric acid, acetic acid, trichloroacetic acid, and 1,3,6-naphthlenetrisulfonic acid or its sodium salt.
Thiourea and allyl isothiocyanate are commonly used anti-oxidants.
The sensitizing solution and sensitized layer may further contain hygroscopic agents such as glycerine, ethylene glycol, or the like; wetting agents such as saponin and lauryl sulfonates; and image intensifiers such as Zinc chloride and nickel sulfate.
The coating solution is applied in a conventional manner to a suitable support, the excess removed, and the coating dried. Suitable supports include not only those types of papers such as ordinary pulp paper, rag paper, and document paper, but also starch filled cloth, felt, saponified cellulose acetate film, transparent cellulosic material such as cellophane, and the like. In the drawmgs:
FIGURE 1 is a sectional view of a heat-developable two-component photosensitive diazotype reproduction material 10 of the present invention comprising a support 11 and a heat-developable two-component photosensitive diazotype layer 12 coated on said support;
FIGURE 2 is a sectional view of a heat-developable two-component photosensitive diazotype reproduction material 20 of the present invention comprising a support 21, a precoat layer 22 coated on said support, and a two-component photosensitive diazotype layer 23 coated over said precoat layer on said support; and
FIGURE 3 is a sectional view of a developing sheet 30 comprising a support 31 and a heat-decomposable amide 32 impregnated in support 31, in juxtaposition with a two-component photosensitive diazotype reproduction material 33 comprising a support 34 and a two-component photosensitive diazotype layer 35 coated on support 34.
One method of the present invention for the preparation of a heat-developable reproduction material is to first treat a support material with a solution of an amide. After drying, the same support is treated on the same side or on the opposite side with a sensitizing solution containing as major ingredients: a diazonium compound, a coupler, and where desired, a stabilizing acid. After drying, the sensitized support is ready for use. The sensit zed support is exposed through a master to actinic radiatrons and is then developed by heat in the range between the decomposition temperature of the amide and the scorching temperature of the support material. The heat-activated liberation of alkaline vapors then causes the image to develop.
The preparation and use of a heat-developable twocomponent photosensitive diazotype reproduction material precoated with an amide of the present invention is illustrated in Example 1.
In another method of preparation of the present invention, the amide is incorporated with the photosensitive diazonium compound, a coupler, and where desired, a stabilizing acid in a sensitizing solution which is applied to a support and then dried. The sensitized support can then be exposed through a master to actinic radiations. After exposure, heat is applied to the support. The temperature is preferably in the range between the decomposition temperature of the amide and the scorching temperature of the support material. This method of preparation is illustrated in Example 2.
A developing sheet was prepared by impregnating a support with a solution of an amide in an appropriate solvent. The solvent was then removed by drying. The developing sheet was then used to develop an exposed two-component photosensitive diazotype reproduction material by making face-to-face contact with the exposed sensitized surface of the diazotype material and subjecting the assembly to heat in the range between the decomposition temperature of the amide and the scorching temperature of the diazotype support. Alkaline vapors were liberated to elfect development of the latent image. The preparation and use of a developing sheet utilizing an amide of the present invention is illustrated in Example 3.
As an alternative procedure, the alkali-liberating agent may be incorporated into the pulp or raw material used to manufacture the support in suitable proportions to obtain the desired results.
The developing temperature range was determined by two factors: the first was the decomposition temperature of the thermally decomposable amide, and the second was the scorching temperature of the support. The decompo sition temperature of the thermally decomposable amide is affected by the presence of other chemicals in the system. The presence of a good source of hydrogen ions favors decomposition by hydrolysis.
The following examples further illustrate the present invention and are not intended to restrict or limit the scope of the invention.
Example 1 30 grams of acrylamide were dissolved in 150 milliliters of water and were coated onto a paper support. After drying, the precoated support was sensitized with the following solution:
The coating was dried to produce a precoated and sensitized diazotype reproduction material. This was exposed through a master to actinic radiations and developed by subjecting the reproduction material to 150 C. for a few seconds. The heat liberated alkaline vapors from the amide and allowed the diazonium compound and the coupler to form a blue dye image corresponding to the master image.
No liquid developer or gaseous ammonia was required for development. In addition the developed reproduction material was stable against further dye formation under the influence of heat. This precoating system was particularly suitable for amides which were not water-soluble or which were not compatible with the chemicals in the sensitizing solution.
Example 2 A sensitizing solution according to the following formula was prepared and coated on a conventional silicasized diazotype paper support:
Water, ml. 4,500
The coating was dried to produce a heat-developable diazotype reproduction material. This was exposed through a master to actinic radiations and then subjected to heat in the range of C. to the scorching point of the paper support for a few second to liberate alkaline vapors and thus develop the blue dye image corresponding to the master image.
This system and method was preferred whenever the water solubility and the chemical compatibility of the amide with the other chemicals permitted incorporation into a single solution. Diazonium compounds other than p-dimethylamino benzene diazonium chloride can be used, c.g., p-diethylamino benzene diazonium chloride, and N-ethyl-N-(2hydroxyethyl)-p-amino benzene diazonium chloride were also used. Another coupler such as phloroglucinol was also used.
Example 3 20 grams of acrylamide were dissolved in 100 ml. of ethyl alcohol. This solution was used to impregnate a porous paper support. After drying, a developing sheet for the heat-development of exposed two-component diazotype reproduction materials was produced. On a separate paper support the sensitizing solution of Example 1 was applied and dried. This was exposed through a master to actinic radiations and developed by making face-to-face contact with the developing sheet and subjecting the whole assembly to C. for 5 seconds. A blue dye image corresponding to the master image was produced without benefit of liquid developer or gaseous ammonia. The print was stable against any further dye formation due to the application of heat.
This system was ideal for amides which were not compatible with the chemicals of the sensitizing solution since isolation was complete. In principle, this isolation can also be achieved by the multilayer system described in British Patent 815,005 and by microencapsulation of the developing agent or the coupler.
These first three examples demonstrate the fact that an amide can be used in three dilferent systems as the source of alkali for the heat-development of diazotype reproduction materials.
Example 4 The following sensitizing solution was prepared and coated on a support. After the coating was dried, the sensitized support was exposed to actinic radiation through a master and developed by subjecting it to heat. The color of the image was blue.
Formamide, g. 10
Example 5 A coating of the following diazo sensitizing solution was applied to a paper support:
Water, ml. 150 p-Dimethylamino benzene diazonium chloride, zinc chloride salt, g 4 2,3-dihydroxynaphthalene 6 sulfonic acid, sodium salt, g. 5 Thiourea, g. 7 Zinc chloride, g. 4
An absorbent sheet was soaked with the following solution:
Etthyl alcohol, ml. 100 N,N-diphenylfor mamide, g. 10 Trichloroacetic acid, g. 5
After drying, the developing sheet was brought into uniform contact with the sensitized paper which had been exposed through a master to actinic radiations. The assembly of developing sheet and the diazo sensitized paper was then heated at 150 deg. C. for seconds to produce a blue image on the diazo sensitized paper corresponding to the master image.
Example 6 The following sensitizing solution was coated on a support suitable for diazotype reproduction materials:
Water, ml. 150 Trisodium salt of 1,3,6-na1phthalene trisulfonic acid, g. 6 p-Dimethylamino benzene diazonium chloride, zinc chloride salt, g. 4 Sodium salt of 2,3-dihydroxynaphthalene-6-sulfonic acid, g. 5 Thiourea, g. Zinc chloride, g. 4 Acetamide, g. 30
pH adjusted to 3.4 with trichloroacetic acid.
The sensitized support was then dried and exposed through a master to actinic radiation. Heat was used to develop the latent image as a blue dye image.
Example 7 To improve storage life, trichloroacetic acid was added according to the following formula:
Water, ml. 150 Tartaric acid, g /2 Trisodium salt of 1,3,6-naphthalene trisulfonic acid, g. 6 p-Dimethylamino benzene diazonium chloride, zinc chloride salt, g. 4 Acetamide, g. 30 Sodium salt of 2,3-dihydroxynaphthalene-6-sulfonic acid, g. 5 Thiourea, g. 10 Zinc chloride, g. 4 Trichloroacetic acid, g. 5
The pH of the solution was 1.3. Storage life was improved by the addition of trichloroacetic acid. Material stored at 115 deg. F. and 47% relative humidity for three days still produced acceptable and satisfactory prints. Lesser amounts of trichloroacetic acid reduced the storage life of the sensitized reproduction material.
Example 8 The following sensitizing solution was prepared and coated on a support suitable for diazotype reproduction materials on a production run basis:
The coating speed was 16 yards per minute with an airbar pressure of 3 /2 oz. of water. The drying temperature was 180 F.
The sensitized and dried material was then exposed through a master to actinic radiation and developed by the application of heat. The developed image was blue in color and satisfactory in density.
Example 9 A support sheet was pre-coated with the following solution:
Water, ml. Acetamide, g. 30
After drying, the precoated support was sensitized with the following sensitizing solution:
Water, ml. 150 Trisodium salt of 1,3,6-naphthalene trisulfonic acid, g. 6 Trichloroacetic acid, g. 5 p-Dimethylamino benzene diazonium chloride, zinc chloride salt, g. 4 Sodium salt of 2,3-dihydroxynaphthalene-6-sulfonic acid, g. 5 Thiourea, g. 7 Zinc chloride, g 4
The pH of the sensitizing solution was 1.0. After drying, the sensitized sheet was exposed through a master to actinic radiations and developed by heating at 150 C. for 4 seconds. A blue image corresponding to the master image was obtained.
Example 10 An absorbent base sheet was soaked in a solution containing 10 grams of acetamide in 150 ml. of ethyl alcohol and then dried to remove the alcohol to produce a developing sheet.
A paper support was sensitized with the following solution:
Water, ml. 150 Trisodium salt of 1,3,6-naphthalene trisulfonic acid, g. 6 Trichloroacetic acid, g. 5 p-Dimethylamino benzene diazonium chloride, zinc chloride salt, g. 4 Sodium salt of 2,3-dihydroxynaphthalene-6-sulfonic acid, g. 5 Thiourea, g. 7 Zinc chloride, g 4
After drying, the developing sheet and the exposed sensitized support were placed in contact and heated at 150 C. for a few seconds to produce a blue image corresponding to the master image.
Example 11 The following solution was prepared and coated on an absorbent support to form a developing sheet:
Ethyl alcohol, ml. 25 Trichloroacetic acid, g. 1 Phenoxyacetamide, g. 2.5
Heating this sheet in contact at 175 C. for 5 seconds with a printed but undeveloped diazotype paper such as that described in Example 10 produced a brown image.
Example 12 A developing sheet prepared by coating the following solution on an absorbent support when heated in contact with printed diazotype paper as described in Example 10 caused a blue image to be produced on the diazotype paper:
Ethyl alcohol, cc. 100 Trichloroacetic acid, g 3 N,N-diphenylacetamide, g. 10
Contact time was 6 seconds at C.
9 Example 13 The following solution was prepared and coated in an absorbent support:
Water, cc. 150 Propionamide, g. 30 1,3,6-naphthalene trisulfonic acid, trisodium salt, g. 6 Trichloroacetic acid, g.
p-Dimethylamino benzene diazonium chloride, zinc chloride salt, g. .2 4 2,3 dihydroxynaphthalene-6-sulfonic acid, soduim salt, g. 5 Thiourea, g. 7 Zinc chloride, g. 4
After printing through a master, the blue image was developed by heating for 5 second at 150 C.
Example 14 Propionamide was used in the following solution to prepare a developing sheet:
Water, cc. 100 Trichloroacetic acid, g. 2 Propionamide, g. 5
When used to develop a printed diazotype paper such as that described in Example 10, a blue image was obtained. Contact time was 5 seconds at 150 C.
Example 15 The following chemicals were substituted individually for the propionamide in Example 13 with the result that the developed images were substantially the same as for propionamide:
n-Butyramide iso-Butyramide n-Valeramide iso-Valeramide Example 16 Hexanamide, nonanamide, and stearamide were used separately in the following solution formula to prepare developing sheets:
Ethyl alcohol, cc. 50 Trichloroacetic acid, g. 1.5 Amide, g. 5
When these developing sheets were used to develop printed diazotype sheets prepared as described in Example 10, blue images were obtained. Contact time was 5 seconds at 160 C.
Example 17 The sensitizing solution was prepared with acrylamide according to the following formula:
Water, cc. 100 p-Diethylamino benzene diazonium chloride, zinc chloride salt, g. 4
2,3 dihydroxynaphthalene-6-sulfonic acid, sodium salt, g. 5 Acrylamide, g. 50
This solution was coated on an absorbent support and dried. When heat-developed at 150 C. for 5 seconds a blue color was developed.
Example 18 Polyacrylamide of low molecular weight such as PAM was used in the following sensitizing solution:
Water, cc. 100 Polyacrylamide PAM 10, g. 50 Trichloroacetic acid, g. 8 1,3,6-naphthalene trisulfonic acid, trisodium salt, g. 6 p-Dimethylamino benzene diazonium chloride, zinc chloride salt, g. 4
10 2,3 dihydroxynaphthalene-6-sulfonic acid, sodium salt, g. 5 Thiourea, g. 7 Zinc chloride, g 4
This solution was coated on an absorbent support and was dried. After printing with ultraviolet light through a master, the image was developed by heating the coated support at 150 C. for 5 seconds.
Example 19 Polyacrylamide such as PAM 10 was used in the following solution to prepare a precoat solution:
Water, cc. Polyacrylamide PAM 10, g. 50 Trichloroacetic acid, g. 10
This solution was coated on a support and dried. The precoated paper was then sensitized with a solution such as described in Example 1. Heat treatment after exposing the sensitized support through a master produced a blue dye image.
Example 20 The same polyacrylamide solution as in Example 19 was used to coat an absorbent support to make a developing sheet. When used as in Example 3 to develop a diazotype paper by placing it in contact with the exposed diazotype paper and heating the assembly for a few seconds at C. a blue image on the diazotype paper was developed.
Example 21 Hexamethylene-bis-acrylamide was used to prepare a solution according to the following formula:
Ethyl alcohol, cc 100 Hexamethylene-bis-acrylamide, g. 10 Trichloroacetic acid, g. 5
This solution was used to impregnate an absorbent sup port. After drying, this developing sheet was placed in contact with sensitized and exposed diazotype paper and heated at 150 C. for 8 seconds. A blue image was formed.
Example 22 Methacrylamide was used in place of the acrylamide of Examples 2 and 17, with the same results.
Example 23 Malonamide was used in the following sensitizing solu- 2,3 dihydroxynaphthalene-d-sulfonic acid, sodium salt, g. 5 Thiourea, g. 7 Zinc chloride, g 4 Development of a blue dye image after exposure was ac complished by heating at C. for 4 seconds.
Example 24 Benzamide was used in the following solution to prepare a developing sheet:
Ethyl alcohol, cc 100 Benzamide, g. 5
This solution was then used to impregnate an absorbent support. Heating the developing sheet while it was in contact with a diazotype paper prepared as in Example 5 resulted in development of a blue color on the diazotype sheet.
Example 25 The solution of Example 24 was used also as a precoat solution. It was coated on a support, dried, and then sensitized with the following solution on the same side:
Water, cc. 150 1,3,6-naphthalene trisulfonic acid, trisodium salt, g. 6 Tartaric acid, g. /2 p-Dimethylamino benzene diazonium chloride, zinc chloride salt, g. 4 2,3-dihydroxynaphthalene-6-sulfonic acid, sodium salt, g Thiourea, g. 7 Zinc chloride, g. 4
After exposure through a master, a blue dye image was developed by heating the exposed sheet for 5 seconds at 150 C.
Example 26 p-Toluamide was used in the following solution to prepare a developing sheet:
Ethyl alcohol, cc. 50 p-Toluamide, g. 5 Trichloroacetic acid, g. 1.5
The developing sheet was used to develop diazotype paper prepared as in Example 5. A blue color was developed by heating the developing sheet in contact with the diazotype paper for a few seconds at 165 C.
Example 27 p-Nitrobenzamide was used in the following solution to prepare a developing sheet:
Ethyl alcohol, cc. 25 p-Nitrobenzamide, g. 2.5 Trichloroacetic acid, g. 1.0
This developing sheet was used to develop a red-brown dye color in the same manner as in Example 26.
Example 28 Anthranilamide was used in the following solution to prepare a developing sheet:
Ethyl alcohol, cc 100 Anthranilamide, g Trichloroacetic acid, g. 5
This solution was coated on a support to make a developing sheet which then was used to develop a diazotype paper as described in Example 5 to produce a blue dye image.
Example 29 Anthranilamide was also used in the following sensitiz- This was coated on a support and dried. Heating the exposed sensitized sheet at 160 C. for 6 seconds produced a blue dye image.
Example 30 Phthalamide :was used to make a developing sheet by coating a support with the following solution:
Ethyl alcohol, cc 100 Phthalamide, g. 5 Trichloroacetic acid, g, 2.5
Placing this developing sheet in contact with a printed diazotype paper and subjecting the assembly to heat at 175 C. for several seconds produced a blue image.
Example 31 Salicylamide was used in a developing sheet prepared by coating a support with the following solution:
Ethyl aclohol, cc. Salicylamide, g. 5
The developing sheet was used to develop a blue dye image as in Examples 5 and 30.
Example 32 Salicylamide was also used in a precoat layer by coating a support with the following solution:
Ethyl alcohol, cc Salicylamide, g. 10
The precoated support was then sensitized as in Example 9. After exposure through a master to actinic radiations, a blue color was developed by heating the sensitized precoated support for 5 seconds at 150 C.
Example 33 Z-furamide was used in the following solution to coat a support to a make a developing sheet:
Ethyl alcohol, cc. 50 2-furamide, g. 5 Trichloroacetic acid, g 1.5
This developing sheet was used at 175 C. for 4 seconds to develop printed diazotype paper as described in Example 5.
Example 34 N-methylacetamide was used to prepare a developing sheet by impregnating an absorbent support with the following solution:
Ethyl alcohol, cc. 25.0 N-methylacetamide, g. 2.5 Trichloroacetic acid, g 1.0
After drying, this developing sheet was used to develop exposed diazotype paper prepared as in Example 5 by placing the two sheets in contact and heating them at C. for 7 seconds to obtain a blue color.
Example 35 Example 34 was repeated with 2-phenylacetamide in place of N-methylacetamide. After following the same procedure, a blue green image was obtained.
Example 36 Nicotinamide was used in the following solution to impregnate an absorbent support to make a developing sheet:
Water, cc. 50 Nicotinamide, g. 5
This sheet was then dried and used to develop an exposed diazotype paper by placing it in contact with the exposed diazotype paper and heating the assembly at 150 C. for 6 seconds to obtain a colored image.
Example 37 A support was precoated with the following solution:
Water, cc. 50 Nicotinamide, g. 5 Trichloroacetic acid, g. 2
13 After drying, the precoated support was sensitized with the following solution:
After drying, the sensitized support was exposed through a master to actinic radiations and then developed by heating at 160 C. for seconds. A blue-black image was obtained.
It is apparent that the described examples are capable of many modifications and variations with the scope of the present invention. All such modifications and variations are to be included :within the scope of the present invention.
What is claimed is:
1. A process for forming an azo dye comprising:
(a) placing in face-to-face combination:
(1) a two-component diazotype sheet material comprising a diazonium compound and an azo dye coupler capable of forming an azo dye with said diazonium compound in an alkaline environment; and
(2) a developer sheet comprising a support, and
an alkali-liberating amide thermally-decomposable at a temperature below the scorching temperature of said support and having the general formula wherein R is hydrogen, alkyl, alkylene, aryl or an amidated polymeric radical having a molecular weight of about 40,000, and R and R are, individually, hydrogen, alkyl or aryl; and
(b) heating said combination to atemperature between the decomposition temperature of said amide and the scorching temperature of said support.
2. A process for forming a diazotype image comprising:
(a) imagewise exposing to actinic radiation diazotype sheet material comprising a light-sensitive diazonium compound and an azo dye coupler capable of forming an azo dye with said diazonium compound in an alkaline environment;
(b) placing said diazotype material in face-to-face contact with a developer sheet comprising a support, and an alkali-liberating amide thermally-decomposable at a temperature below the scorching temperature of said support and having the general formula wherein R is hydrogen, alkyl, alkylene, aryl or an amidated polymeric radical having a molecular weight of about 40,000, and R and R are, individually, hydrogen, alkyl or aryl; and
(c) heating said combination to a temperature between the decomposition temperature of said amide and the scorching temperature of said support.
3. A process according to claim 1 wherein said developer sheet further comprises an organic acid in an amount between about 20% and 50% of the amount of amide.
4. A process according to claim 3 wherein said acid is trichloracetic acid.
5. A process according to claim 2 wherein said developer sheet further comprises an organic acid in an amount between about 20% and 50% of the amount of amide.
6. A process according to claim 5 wherein said acid is trichloroacetic acid.
7. A process according to claim 1 wherein said amide is acrylamide.
8. A process according to claim 1 wherein said amide is N,N-diphenyl formamide.
9. A process according to claim 1 wherein said amide is acetamide.
10. A process according to claim 1 wherein said amide is phenoxyacetamide.
11. A process according to claim 1 wherein said amide is N,N-diphenylacetamide.
12. A process according to claim 1 wherein said amide is stearamide.
13. A process according to claim 1 wherein said amide is polyacrylamide.
14. A process according to claim 1 wherein said amide is hexamethylene-bis-acrylamide.
15. A process according to claim 1 wherein said amide is benzamide.
16. A process for the thermal development of twocomponent light-sensitive diazotype reproduction materials, by means of a developing sheet, said reproduction material comprising a support and a light-sensitive layer coated on said support, said developing sheet comprising a separate support and a thermally decomposable alkaliliberating developing agent impregnated in said separate support, said developing agent being N,N-diphenyl formamide, said process comprising the steps of: (1) exposing said reproduction material to actinic radiations through a master, (2) separating the reproduction material from the master, (3) making an assembly with the developing sheet in uniform contact with the sensitized surface of said reproduction material, and (4) heating the assembly in the temperature range between the decomposition temperature of the developing agent and the scorching temperature of said reproduction material support, thus liberating alkali in the immediate vicinity of the sensitized surface of said reproduction material, thereby causing coupling to occur in the image areas.
17. A process for the thermal deveopment of two-component light-sensitive diazotype reproduction materials by means of a developing sheet, said reproduction material comprising a support and a light-sensitive layer coated on said support, said developing sheet comprising a separate support and a thermally decomposable alkali-liberating developing agent impregnated in said separate support, said developing agent being acetamide, said process comprising the steps of: (1) exposing said reproduction material to actinic radiations through a master, (2) separating the reproduction material from the master, (3) making an assembly with the developing sheet in uniform contact with the sensitized surface of said reproduction material, and (4) heating the assembly in the temperature range between the decomposition temperature of the developing agent and the scorching temperature of said reproduction material support, thus liberating alkali in the immediate vicinity of the sensitized surface of said reproduction material, thereby causing coupling to occur in the image areas.
18. A process for the thermal development of two-component light-sensitive diazotype reproduction materials by means of a developing sheet, said reproduction material comprising a support and a light-sensitive layer coated on said support, said developing sheet comprising a separate support and a thermally decomposable alkali-liberating developing agent impregnated in said separate support, said developing agent being phenoxyacetamide, said process comprising the steps of: 1) exposing said reproduction material to actinic radiations through a master, (2) separting the reproduction material from the master, (3) making an assembly with the developing sheet in uniform contact with the sensitized surface of said reproduction material, and (4) heating the assembly in the temperature range between the decomposition temper- 1 ature of the developing agent and the scorching temperature of said reproduction material support, thus liberating alkali in the immediate vicinity of the sensitized surface of said reproduction material, thereby causing coupling to occur in the image areas.
19. A process for the thermal development of two-component light-sensitive diazotype reproduction materials by means of a developing sheet, said reproduction material comprising a support and a light-sensitive layer coated on said support, said developing sheet comprising a separate support and a thermally decomposable alkali-liberating developing agent impregnated in said separate support, said developing agent being N,N-diphenylacetamide, said process comprising the steps of: (1) exposing said reproduction material to actinic radiations through a master, (2) separating the reproduction material from the master, (3) making an assembly with the developing sheet in uniform contact with the sensitized surface of said reproduction material, and (4) heating the assembly in the temperature range between the decomposition temperature of the developing agent and the scorching temperature of said reproduction material support, thus liberating alkali in the immediate vicinity of the sensitized surface of said reproduction material, thereby causing coupling to occur in the image areas.
20. A diazotype developer sheet comprising:
(a) a support;
(b) an alkali-liberating amide thermally-decomposable at a temperature below the scorching temperature of said support and having the general formula wherein R is hydrogen, alkyl, alkylene, aryl or an amidated polymeric radical having a molecular 16 Weight of about 40,000, and R and R are, individually, hydrogen, alkyl or aryl; and (c) an organic acid in an amount between about 20% and of the amount of amide. 21. A developer sheet according to claim 20 wherein said acid is trichloroacetic acid.
22. A developer sheet according to claim 20 wherein said amide is acetamide.
23. A developer sheet according to claim 20 wherein said amide is stearamide.
24. A developer sheet according to claim 20 wherein said amide is acrylamide.
References Cited UNITED STATES PATENTS 2,358,871 9/1944 Maxwell 117-154 2,687,958 8/1954 Neugebauer 96-93 X 2,727,820 11/1955 Botkin 96-49 2,774,669 12/1956 Marron et al. 9649 3,206,311 9/1965 Campbell et al. 117-154 X 3,224,902 12/1965 Sodler et al. 117-154 X 3,244,734 4/1966 Sommtag 117-154 X 2,653,091 9/1953 Greig 96-49 3,203,797 8/1965 Muller 96-49 FOREIGN PATENTS 816,601 7/1959 Great Britain. 459,141 8/ 1949 Canada.
I. TRAVIS BROWN, Primary Examiner O. BOWERS, Assistant Examiner U.S. Cl. X.R.

Claims (3)

1. A PROCESS FOR FORMING AN AZO DYE COMPRISING: (A) PLACING IN FACE-TO-FACE COMBINATION: (1) A TWO-COMPONENT DIAZOTYPE SHEET MATERIAL COMPRISING A DIAZONIUM COMPOUND AND AN AZO DYE COUPLER CAPABLE OF FORMING AN AZO DYE WITH SAID DIAZONIUM COMPOUND IN AN ALKALINE ENVIRONMENT; AND (2) A DEVELOPER SHEET COMPRISING A SUPPORT, AND AN ALKALI-LIBERATING AMIDE THERMALLY-DECOMPOSABLE AT A TEMPERATURE BELOW THE SCORCHING TEMPERATURE OF SAID SUPPORT AND HAVING THE GENERAL FORMULA
2. A PROCESS FOR FORMING A DIAZOTYPE IMAGE COMPROSING: (A) IMAGEWISE EXPOSING TO ACTINIC RADIATION DIAZOTYPE SHEET MATERIAL COMPRISING A LIGHT-SENSITIVE DIAZONIUM COMPOUND AND AN AZO DYE COUPLER CAPABLE OF FORMING AN AZO DYE WITH SAID DIAZONIUM COMPOUND IN AN ALKALINE ENVIRONMENT; (B) PLACING SAID DIAZOTYPE MATERIAL IN FACE-TO-FACE CONTACT WITH A DEVELOPER SHEET COMPRISING A SUPPORT, AND AN ALKALI-LIBERATING AMIDE THERMALLY-DECOMPOSABLE AT A TEMPERATURE BELOW THE SCORCHING TEMPERATURE OF SAID SUPPORT AND HAVING THE GENERAL FORMULA
20. A DIAZOTYPE DEVELOPER SHEET COMPRISING: (A) A SUPPORT; (B) AN ALKALI-LIBERATING AMIDE THERMALLY-DECOMPOSABLE AT A TEMPERATURE BELOW THE SCORCHING TEMPERATURE OF SAID SUPPORT AND HAVING THE GENERAL FORMULA
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US48265565A 1965-07-12 1965-07-12

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US3607275A (en) * 1967-11-29 1971-09-21 Keuffel & Esser Co Diazo-type material
US3918974A (en) * 1970-05-01 1975-11-11 Mita Industrial Co Ltd Process for the diazo-type multicolor reproduction
US4400456A (en) * 1980-08-29 1983-08-23 Ricoh Co., Ltd. Thermo-developable type diazo copying material
US4497887A (en) * 1981-06-09 1985-02-05 Ricoh Compay, Ltd. Thermal development type diazo copying material with hydrophobic resin encapsulated coupler particle

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US2358871A (en) * 1940-05-20 1944-09-26 Du Pont Textile treatment
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US2653091A (en) * 1950-01-31 1953-09-22 Rca Corp Photographic diazotype composition and heat development thereof
US2687958A (en) * 1949-05-14 1954-08-31 Azoplate Corp Light-sensitive layers for the printing industry
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US2774669A (en) * 1953-04-13 1956-12-18 Dick Co Ab Diazotype reproduction process
GB816601A (en) * 1954-07-09 1959-07-15 Arnold Tanenbaum Improvements in or relating to diazotype processes
US3203797A (en) * 1962-10-16 1965-08-31 Andrews Paper & Chem Co Inc Thermal diazotype method and developer sheet for use therein
US3206311A (en) * 1961-05-05 1965-09-14 Polaroid Corp Stacked photosensitive elements
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CA459141A (en) * 1949-08-23 Allan Schenck Willard Paper and method of making same
US2358871A (en) * 1940-05-20 1944-09-26 Du Pont Textile treatment
US2687958A (en) * 1949-05-14 1954-08-31 Azoplate Corp Light-sensitive layers for the printing industry
US2653091A (en) * 1950-01-31 1953-09-22 Rca Corp Photographic diazotype composition and heat development thereof
US2727820A (en) * 1952-04-29 1955-12-20 Gen Aniline & Film Corp Light-sensitive diazotype layers containing carboxamides
US2774669A (en) * 1953-04-13 1956-12-18 Dick Co Ab Diazotype reproduction process
GB816601A (en) * 1954-07-09 1959-07-15 Arnold Tanenbaum Improvements in or relating to diazotype processes
US3206311A (en) * 1961-05-05 1965-09-14 Polaroid Corp Stacked photosensitive elements
US3224902A (en) * 1961-09-07 1965-12-21 Mc Graw Edison Co Thermally stabilized cellulose materials
US3203797A (en) * 1962-10-16 1965-08-31 Andrews Paper & Chem Co Inc Thermal diazotype method and developer sheet for use therein
US3244734A (en) * 1963-05-31 1966-04-05 Nat Dairy Prod Corp Manufacture of fatty acid amide compounds

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607275A (en) * 1967-11-29 1971-09-21 Keuffel & Esser Co Diazo-type material
US3918974A (en) * 1970-05-01 1975-11-11 Mita Industrial Co Ltd Process for the diazo-type multicolor reproduction
US4400456A (en) * 1980-08-29 1983-08-23 Ricoh Co., Ltd. Thermo-developable type diazo copying material
US4497887A (en) * 1981-06-09 1985-02-05 Ricoh Compay, Ltd. Thermal development type diazo copying material with hydrophobic resin encapsulated coupler particle

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