Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • 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

• a heat-developable diazotype reproduction material is prepared by impregnating, during the paper-making process, a paper carrier sheet with a heat-active source of alkaline material, such as urea. Upon completion of the paper-making process, the impregnated paper sheet is coated with a composition including a light-sensitive diazonium compound and a coupler compound capable of forming an azo dye with such diazoniurn compound in an alkaline medium. Heating of the resulting sheet material creates an alkaline medium conducive to the coupling reaction between the diazonium and the azo coupler compounds and effects development of an azo dye.
• the present invention relates to reproduction materials and refers more particularly to a heat-developable twocomponent diazotype reproduction material.
• the dry process the copying material includes a diazo compound and an azo coupling component, and development is effected with ammonia gas.
• the semi-wet process the copying material includes a diazo compound and development is effected in acid or alkaline solution with an azo coupling component to form an azo dye in the unexposed areas.
• one object of the present invention is to provide a heat-developable, two-component diazotype reproduction material which overcomes these disadvantages.
• Another object is to provide a heat-developable reproduction material having excellent shelf life with excellent quality in the photocopies produced therefrom.
• the object of the present invention may be realized by providing a heat-developable, two-component diazotype copying material comprising a support and a light-sensitive coating on the support, the support containing at least one compound which under the action of heat pro- 3,434,838 Patented Mar. 25, 1969 prises a neutral or alkaline environment suitable for development in the light-sensitive coating.
• the preparation of the present copying material comprises the step of impregnating a support with at least one compound, with or without additives, which under the action of heat produces a neutral or alkaline environment in the light-sensitive coating.
• Support materials Materials commonly employed in diazotype techniques are suitable as support materials. It has proved advantageous to choose a support that is permeable to the compound which creates the environment in the light-sensitive mixture. Supports which fulfill this requirement are preferably paper with weights of 50 to grams per square meter. These are available commercially as photocopying base papers. Transparent papers may also be used.
• Suitable compounds are those which initially exhibit no neutral or alkaline reaction and which must be heated to become converted, as by decarboxylation or fission, into products which exhibit neutral or alkaline characteristics.
• the following classes of compounds are suitable: monoamides or oligo-amides of organic, aliphatic, monovalent or polyvalent carboxylic acids With straight or branched chains up to approximately fifteen carbon atoms, such as acetic acid, mono-, diand trichloroacetic acid; the diamides of carbonic acid, oxalic acid, fumaric acid or succinic acid; the amides of acids which also hear one or several hydroxyl groups in the aliphatic chain, such as the amine of malic acid, tartaric acid, citric acid, hydroxy-acetic acid, hydroxy-butyric acid, and lactic acid; and corresponding alkyl-ethers of these hydroxy carboxylic acids, such as the amide of Z-methoxy-acetic acid.
• Urea is preferred, particularly when used in combination with zinc chloride or trichloroacetic acid as stated below.
• Additives which substantially improve the desired effect are small amounts of acids, such a trichloroacetic acid, vinylphosphonic acid and organic compounds which decompose through decarboxylation when heated to form anhydrides or ketones and thus lose their acidity.
• acids such as a trichloroacetic acid, vinylphosphonic acid and organic compounds which decompose through decarboxylation when heated to form anhydrides or ketones and thus lose their acidity.
• Other additives are: beta-ketonic acids, such as pyroacemic acid; beta-hydroxy acids, such as lactic acid; and malic acid. These compounds have given good results in the case of amides whose decomposition temperatures are comparatively high. Lower temperatures are afforded.
• Incorporation of the substances creating the neutral or alkaline environment is preferably effected before all other process steps in the preparation of the heat-developable copying paper. Incorporation of these substances into the support material when it is not yet dry has proved particularly effective; for example, into a paper web during the paper-making process in the paper machine. By this step, the penetration of these substances into the support material is thorough. As a result, they are already present at the optimum position from which they can exert their action. Since they are not concentrated on the side which subsequently bears the light-sensitive mixture as in the usual processes, the shelf life of the copying material is substantially increased by avoidance of the premature reaction between diazo compound and coupling component.
• the papers generally used have a strong sizing effect which inhibits the penetration of water and aqueous solutions. Sizings of this nature are known. This inhibitory effect of the papers sizing does not occur in the papermaking process until the end of the drying of the paper.
• Sizings of this nature are known. This inhibitory effect of the papers sizing does not occur in the papermaking process until the end of the drying of the paper.
• Suitable applicator devices are located in the final wet press and in the dry end of the paper machine.
• Roller applicators such as the known sizing presses of various designs, are preferred.
• Other applicators include air brushes, trailing blades, and similar coating devices. The amount may vary within large or wide limits; for example, approximately one to five mole parts, preferably 1.5 to 3 mole parts theoretically necessary for the complete neutralization of the light-sensitive coating.
• a second coating of small amounts of the substance may be made as a separate coating on the front side, although this is not necessary.
• the amounts of the second coating should be kept Within narrow limits, such as approximately 0.1 to 0.5 mole parts for the theoretical neutralization of the other components in the light-sensitive structure.
• the light-sensitive mixture is coated.
• the mixture comprises the diazo and azo components and additives conventional in diazotype techniques.
• the support material is provided with a precoat which prevents or at least inhibits penetration of the light-sensitive mixture into the support.
• These precoat properties must apply only to the light-sensitive mixture.
• the precoat must not inhibit egress of the alkaline-reacting substances or fission products out of the support.
• Suitable precoat materials are: cellulose derivatives such as carboxymethyl cellulose, hydroxymethylethyl cellulose; alginates such as sodium or ammonium alginate; organic condensates such as urea-formaldehyde or ureaglycerol resins; and many synthetic resins for the surface treatment of paper such as water-soluble resins, polyamide derivatives, alkoxy methyl/ nylon, polyamine-epoxy resin, polymethyl siliconic acid sodium salt, finely-divided silicic acid of a particle size between 0.2 and 10 microns, and rice starch or oat starch. Combinations of these materials have also proved suitable. Many of them simultaneously improve contrast in the developed images.
• precoat materials which are applied in the form of their soluble alkali metal salts or ammonium salts
• agents which have proved especially suitable for neutralization are the aqueous solutions of trichloroacetic acid, hydrochloric acid, vinyl phosphonic acid, and the like.
• diazo and azo components may be used in a light-sensitive mixture.
• diazo components 4-dimethylamino-benzene diazonium chloride, 4 diethylamino-benzene diazonium chloride, 4-N-ethyl-N-hydroxyethylamino-benzene diazonium chloride, 4-morpholinobenzene diazonium chloride, and 4-pyrrolidino-3-br0mobenzene diazonium chloride are suitable diazo components
• Suitable coupling components are: 2,3-dihydroxynaphthalene-6-sulfonic acid; 2-hydroxy-(N-dimethyl)- naphthoic acid amide-(3); 2-hydroxy-benzotriazole (1,2); 1,3,5- resorcyclic acid diethylamide; acetoacetic anilide; and l-(N-ethylamino)-3hydroxy-4-methyl-benzene.
• Mixtures of the individual components of the respective groups may also
• the light-sensitive mixture which is on at least one side of the support may contain additives. These additives may be classified into two groups:
• Additives of this group are: thiourea, glycerol, glycol, triethanolamine hydrochloride, saponin, zinc chloride, trisodium naphthalene-1,3,6-trisulfonate, and the like.
• additives may also be included agents which influence the application properties and surface properties of the mixture with respect to its processing. These are thickening and smoothing agents, such as gelatin, carboxymethyl cellulose, and polyvinyl acetate suspensions.
• Additives which create a neutral or alkaline condition by the action of heat are the same as those described above for the substances in the mass of the support.
• a two-component diazotype material thus prepared is capable of being developed by heat and also may be used in the conventional copying processes.
• the copying material is covered with the original to be reproduced, and exposed in contact.
• the copying material is exposed to a brief heat treatment. This may be effected for example by irradiation with an infrared source under an infrared-absorbing material, such as a nylon sieve which has been dyed black or an infrared-absorbing paper or foil which is heat resistant up to 210 C. Treatment by pressing between two heated rollers or by passing a hot air stream over the material also yields welldeveloped copies. In many cases it is expedient to supply the heat by contact from the back of the copying material. A marginally sharp copy with excellent covering power of the image area is formed.
• the copies prepared with the material according to the invention are distinguished by great sharpness. Even when the finished copies are stored for an appreciable period, the support exhibits no effect, so that legibility and contrast of the copies do not change.
• EXAMPLE 1 A base paper suitable for diazotype techniques was impregnated in a paper making machine by means of a sizing press at the dry end with an aqueous solution of the following composition:
• the copying material was exposed under an original and developed by heat to yield contrasty, blue-colored copies with good keeping qualities.
• EXAMPLE 3 A suitable base paper as described in Example 1 was impregnated on the introducing or offset press of the paper machine with the following solution:
• Triohloroacetic acid 1.0 Tartaric acid 0.2 2,3 -dihydroxy-naphthalene-G-sulfonic acid (sodium salt) 4.0 'Ilhiourea 4.0 Naphthalene-1,3,6-trisulfonic acid (sodium salt) 7.0 Urea 4.0 4 N ethyl N hydroxyethylamino benzene diazonium chloride 2.4 Gelatin 0.09 Saponin 0.04 Water 90 When developing by heat was elfectted, a blue-colored copy was obtained.
• EXAMPLE 4 A base paper as described in Example 1 was impregnated on the sizing press of the paper machine with the following solution:
• Trichloroacetic acid 2.0 Tartaric acid 0.2 Naphthalene-1,3,6-trisulfonic acid (sodium salt) 7.0 Thiourea 4.0 2,3 -dihydroxy-naphthalene-6-sulfonic acid (sodium salt) 4.0 Lactic acid amide 10.0 Zinc chloride 0.5 4 N ethyl N hydroxyethylamino benzene diazonium chloride 2.4 Gelatin 0.09 Saponin 0.04 Water When developing by heat was elfected after exposure, a dark blue color was obtained. Copying material had excellent shelf life.
• EXAMPLE 5 A base paper as described in Example 1 was impregnated on the introducing or oflF-set press of the papermaking machine with the solution described as follows:
• EXAMPLE 6 A base paper as described in Example 1 was impregnated on the introducing or off-set press of the papermaking machine with the following solution:
• Trichloroacetic acid 1.0 Tartaric acid 0.2 2,3-dihydroxy-naphthalene-6-sulfonic acid (sodium salt) 4.0 Thiourea 4.0 Naphthalene-1,3,6-trisulfonic acid (sodium salt) 7.0 Urea 2.5 Zinc chloride 0.5 4-dimethylamino-benzene diazonium chloride 2.4 Gelatin 0.09 Saponin 0.04 Water 80 After exposure, there was obtained by heating, a very contrasty, blue copy of the original.
• EXAMPLE 7 A base paper as described in Example 1 was impregnated on the final wet press of the paper machine with the following solution:
• EXAMPLE 8 A base paper as described in Example 1 was impregnated in the paper machine by means of a sizing press inside the dry end with an aqueous solution of the following composition:
• EXAMPLE 9 A transparent base paper suitable for diazotype techniques was impregnated in the paper machine by means of an air brush applicator inside the dry end with the following solution:
• the pretreated paper was coated on the same side with a solution of the following composition:
• the paper thus prepared was distinguished by particularly good shelf life and high contrast. After exposure under a transparent original, it was developed by heating up to 160 to 170 C. A good blue-colored positive copy of the orginal was obtained.
• a heat-developable reproduction material which comprises:
• a light-sensitive diazo coating comprising a diazonium compound, an azo coupling component and an acid stabilizer on at least one side of the support, said I coating being developable by the action of heat on the mixture of urea and urea-glycerol resin.
• a heat-developable reproduction material which comprises:
• a light-sensitive diazo coating comprising a diazonium compound, an azo coupling component and an acid stabilizer on at least one side of the support, said coating containing urea and being developable by the action of heat on the mixture of lactic acid amide and pyroracemic acid and the urea.
• a heat-developable reproduction material which comprises:
• a light-sensitive diazo coating comprising a diazonium compound, an azo coupling component and an acid stabilizer on at least one side of the support, said coating containing tartaric acid amide and being developable by the action of heat on the urea and the tartaric acid amide.
• a heat-developable reproduction material which comprises:
• a light-sensive diazo coating comprising a diazonium compound, an azo coupling component and an acid stabilizer on the layer, said coating containing urea and being developable by the action of heat of the urea.
• a heat-developable reproduction material which comprises:
• a heat-developable reproduction material which comprises:
• a heat-developable reproduction material which comprises:
• a heat-developable reproduction material which comprises:
• a paper support impregnated in the paper-making process with urea a first layer of polyvinyl phosphonic acid coated on at least one side of the support; a second layer of polymethyl siliconic acid sodium salt coated on the first layer; and a light-sensitive diazo coating comprising a diazonium compound, an azo coupling component and an acid stabilizer on the second layer, said coating containing lactic acid amide and being developable by the action of heat on the urea and the lactic acid amide.

Landscapes

• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Paper (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=7226281

Family Applications (1)

Country Status (5)

Cited By (6)

Citations (10)

• 1964
  • 1964-02-29 DE DE1964K0052254 patent/DE1447736A1/de active Pending
• 1965
  • 1965-02-24 US US435027A patent/US3434838A/en not_active Expired - Lifetime
  • 1965-02-26 GB GB8443/65A patent/GB1092293A/en not_active Expired
  • 1965-02-26 FR FR7180A patent/FR1431182A/fr not_active Expired
  • 1965-02-26 BE BE660356A patent/BE660356A/xx unknown

Patent Citations (11)

Also Published As

Similar Documents

Legal Events