US3715213A - Diazo-type multicolor reproduction - Google Patents

Diazo-type multicolor reproduction Download PDF

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Publication number
US3715213A
US3715213A US00012049A US3715213DA US3715213A US 3715213 A US3715213 A US 3715213A US 00012049 A US00012049 A US 00012049A US 3715213D A US3715213D A US 3715213DA US 3715213 A US3715213 A US 3715213A
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Prior art keywords
coupler
original
diazo
photosensitive
heat
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T Aizawa
Y Ueda
Y Kamezawa
K Nihyakumen
T Yokoyama
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Kyocera Mita Industrial Co Ltd
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Mita Industrial Co Ltd
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Priority claimed from JP44091964A external-priority patent/JPS4918263B1/ja
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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
    • 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

Definitions

  • DIAZO-TYPE MULTICOLOR REPRODUCTION Filed Feb. 17 1970 4 Sheets-Sheet 4 ⁇ KC ⁇ 8 ⁇ / 23 "l n y le CHRNGEOVER 5W ⁇ TCH 7 HEAT ⁇ JGHT $OUQCE SOURCE VOLTAGE ADJUST ER COOUNG T MECHAWSM l A V Y SECTOR CYUNDER TEMPERATURE smss DET EcT ⁇ oN TEMPERATURE CONTROL I l DELNERY coo UNG BELT *"MEcHmTsM J United States Patent 3,715,213 DIAZO-TYPE MULTICOLOR REPRODUCTION Kouzi Nihyakumen and Taizo Yokoyama, Osaka, Yasuo Ueda, Kobe, and Yasutoki Kamezawa and Tatsuo Aizawa, Osaka, Japan, assignors to Mita Industrial Company Limited, Osaka, Japan Filed Feb. 17, 1970, Ser. No. 12,
  • This invention relates to the diazo-type multicolor reproduction. More specifically, it relates to a process for the diazo-type multicolor reproduction by which portions of a sensitive paper corresponding to predetermined portions of an original can be colored selectively to diiferent hues.
  • Dyestuff (b)-(c), dyestuff (a)-(c), dyestuif (a')(c) formed at the development have hues different from one another.
  • thermovolatile or thermosulzlimative coupler (a) any coupler that can be volatilized or sublimated by heating and be coupled with a photosensitive diazonium salt may be used as the thermovolatile or thermosulzlimative coupler (a) in this invention.
  • coupler (a) phenol derivatives, hydroxynaphthalene derivatives, aniline derivatives and active methylene group-containing compounds may be mentioned. It is generally preferred that these derivatives do not contain soluble groups such as a sulfonic acid group for the purpose of facilitating the heat transfer operation.
  • Phenol derivatives Phenol Pyrocatechol semi-exposed portions are mingled with image colors of non-exposed portions to form a compound color, and the color contrast in the image becomes faded. Further, in such known reproduction process it is impossible to reproduce an original having a similar image concentration or light transmission throughout the entire original, into different hues.
  • thermovolatile or thermosublimative coupler a layer of at least one thermovolatile or thermosublimative coupler (a) disposed in face-to-face contact with a predetermined portion of the diazo-type photosensitive material, the steps being carried out coincidentally or in an order of (A) to (B) or (B) to (A), and then developing the exposed photosensitive material in the presence of a coupler (b) having a lower coupling rate under developing conditions than the thermovolatile or thermosublimative coupler (a).
  • thermovolatile or thermosublimative coupler (a), coupler (b) and diazonium salt (0) used in this invention there should be established the following relations:
  • thermosublimative coupler (a) Resorcin Phloroglucinol o-Hydroxybenzalcohol Resorcin monoglycol ether Resorcin glycol ether Hydrotholuquinone Pyrogallol-4-carboxylic acid Vanillin Isovanillic acid Vanillic acid S-hydroxy-isophthalic acid 2-hydroxy-terephthalic acid 2-hydrxy-p-toluylic acid 3-hydroxy-p-toluylic acid S-hydroxy-o-toluylic acid 6-hydroxy-m-toluylic acid S-hydroxy-l-naphthonic acid Para-hydroxyphenylacetic acid Para-hydroxybenzaldehyde Ortho-hydroxybenzoic acid Ortho-hydroxybenzyl alcohol 4,4-dihydroxybiphenol 3,5-dichloro-salicylic acid S-chloro-Z-nitrophenol 2,S-dihydroxyacetophenone 2,5-dinitrophenol 2,4-dinitrophenol
  • the coupling rate of coupler (b) should be lower than that of any of couplers (a). Selection of couplers (a) and (b) meeting the above requirements may be easily performed by those skilled in the art based on a simple experiment.
  • coupler (b) In addition to those having relatively low coupling rates among the above exemplified couplers, the following compounds may be used as coupler (b):
  • Phenol derivatives 2,5,6-trimethylphenol Z-hydroxymethylphenol ,8-(2-hydrovypheny1)-propionic acid 2-( w-phenylaminomethyl) -pheno1 fi-(4-methyl-2-hydroxyphenyl)-glutaric acid 2,5-dimethyl-6-(N-dimethylaminornethyl)-phenol 1,3-dimethyl ether of pyrogallol N-lauryl-p-aminophenol N-acyl-m-aminophenol Meta-hydroxy-acetoanilide Ortho-N-hydroxyphenyl-monoguanidine Para-N-hydroxyphenyl-biguanidine 2,5-dimethyl-4-morpholinomethyl phenol Z-methyl-S-isopropyl-morpholinomethyl phenol 4rnorpholinomethylresorcinol monomethyl ether 3,3',5-trihydroxydiphenyl 3,3',5,5'-tetrahydroxydiphenyl 2,2',4,4-
  • thermovolatile or thermosublimative coupler (a) is heattransferred to the surface of the predetermined portion of the photosensitive material, and the light resolution of the diazonium salt (c) in the photosensitive material is caused to occur depending on the light transmission.
  • the diazonium salt (c) at the non-exposed area is selectively reacted with the coupler (a) to form a dyestuff (c)(a) and at other portion the diazonium salt (c) at the nonexposed portions is reacted with coupler (b) to form a dyestuff (c)-(b).
  • a multicolored reproductive copy in which the predetermined portion is colored in a hue different from that of the other portion is'obtained.
  • the above-mentioned original for multicolor development may be prepared, for instance, by a method comprising applying a coating composition containing the above-mentioned thermovolatile or thermosublimative coupler (a) onto the back surface of a portion predetermined to have a dififerent hue, of a transparent or semitransparent original, or by a method comprising coating or impregnating a transparent or semi-transparent sub strate with the coating composition and combining the resulting sheet for heat-transferring the coupler with the back surface of the specific portion of the original predetermined to have a difierent hue in a manner such that the layer for heat-transferring the coupler will confront the photosensitive material.
  • a coating composition for treating the back surface of an original and forming a layer for heat-transferring the coupler can be easily prepared by dispersing a coupler (a) into a liquid, semi-solid or solid dispersion medium.
  • Percent Coupler 5.0-25.0 Coloring material 0-3.0
  • Dispersion assistant 0-2.0 Dispersion medium Balance
  • water and organic solvents such as alcohol, toluene, xylene, esters and methyl ethyl ketone may be used. It is possible to incorporate a coloring material so as to confirm the formation of a film of the treating agent, or to use a binder for the purpose of obtaining a good fixation of the coupler.
  • composition of the above recipe is applied to the back surface of a portion predetermined to have a different hue by means of a brush, an installed felt pen, a ball pen, a coating roller, 2. sprayer or a printing machine.
  • the composition of the above recipe is shaped to have a crayon stick-like form or a chalk-like form, and the back surface of a portion of an original predetermined to have a different hue is painted therewith. It is also possible to form a pressure-sensitive transfer sheet by melting the above composition or dissolving it in a suitable solvent and coating the melt or solution on a substrate such as paper and plastic film. The so-formed pressure-sensitive transfer sheet is overlapped on the back surface of an original sheet, and then pressing is effected thereon by means of a typewriter or other writing means to form a heat-transferable layer on the back surface of an image predetermined to have a different hue.
  • Coupler-transferring sheet for treating the back surface of an original The ink-like composition for treating the back surface of an original, which was described in (1), or a composition obtained by incorporating a binder or an extender into such ink-like composition is coated on a transparent or semi-transparent sheet such as paper, plastic film or non-woven fabric. The so formed sheet for heat-transferring the coupler is cut into a desired size, if necessary,
  • the original for multicolor development prepared with the use of the above-mentioned agent for treating the back surface of an original to be reproduced may be generally used 5 to 100 times repeatedly for the multicolor development, though the applicable frequency of the repeated use varies depending on the amount coupler (a) coated, the coating method, the heating method and the developing method.
  • coupler (a) coated, the coating method, the heating method and the developing method varies depending on the amount coupler (a) coated, the coating method, the heating method and the developing method.
  • the above-mentioned original for multicolor devevlopment is overlapped on the photosensitive material in a manner such that the coupler-transferring layer applied on the original will confront the photosensitive surface of the photosensitive material, and the exposure and heating are effected.
  • photosensitive materials containing a diazonium salt are used in this invention according to the developing method. They are usually formed by coating a sensitizing composition containing a diazonium compound and, if necessary, a coupler (b) on a substrate such as paper, plastic film, fibrous fabric, non-woven fabric and metal foil.
  • a sensitizing composition containing a diazonium compound and, if necessary, a coupler (b) on a substrate such as paper, plastic film, fibrous fabric, non-woven fabric and metal foil.
  • Percent Azo coupling component (b) 0.2-5.0 Diazo compound 0.2-5.0 Organic acid 0.1-5.0 Coloring matter 0.001-0.025 Development promoter 1.0-10.0 Extender 0-2.5 Solvent Balance
  • the sensitizing composition of the above recipe is coated on a substrate such as paper and plastic film, and dried to form a photosensitive sheet.
  • Percent Azo coupling component (b) 0.2-5.0 Diazo compound 0.2-5.0 Organic acid O.15.0 Stabilizer 05.0 Extender 0-2.5 Coloring matter 0.001-0.025 Solvent Balance
  • the sensitizing composition of the above receipe is coated on a substrate such as paper and plastic film, and dried to form a photosensitive sheet.
  • Percent Diazo compound O.2-5.0 Organic acid 0.1-5.0 Extender 0-2.5 Coloring matter 0.00l-0.025 Solvent Balance The sensitizing composition of the above recipe is coated on a substrate such as paper, and dried to form a photosensitive paper.
  • diazonium compound (0) any diazonium compound that is capable of being coupled with the above-mentioned couplers (a) and (b) under ordinary developing conditions may be used as the diazonium compound (0) in this invention.
  • diazonium compound examples include as follows:
  • N-Q-NZ X RI! wherein X stands for an anion, R and R" each are aliphatic groups, and Z and Y denote groups which can be introduced into the benzene nucleus.
  • R is a divalent aryl group
  • R is a monovalent or divalent aryl or alkyl group
  • A is a divalent group or a direct bond
  • X stands for an anion
  • Y and Z are groups which can be introduced into the benzene nucleus
  • A is a direct bond or a divalent group such as O, S and methylene.
  • diazonium compounds may be used in the form of a relatively stable salt with sulfuric acid or hydrochloric acid. They may also be used in the form of a double salt with zinc chloride, tin chloride, aluminum sulfate or the like. Further, they may be used in the state stabilized by an aryl sulfonate (in the form of a diazonium salt of an aromatic sulfonic acid), a diazosulfonate or the like.
  • the development may be performed suificiently only by exposing the lightexposed photosensitive material to a mixture of ammonia and steam.
  • the development of a one-component-type photosensitive paper in use for the dry method may be carried out by coating a liquid developer having, for instance, the following recipe, on the photosensitive material by dipping, roller coating or spraying:
  • the development is achieved by contacting the photosensitive paper with an aqueous liquid developer containing an alkali.
  • FIG. 2 is a view illustrating an embodiment similar to the above embodiment shown in FIG. 1, except that a heat-transferable sheet containing coupler 2 and another heat-transferable sheet containing coupler 3' are applied to the back surfaces of images 2 and 3, respectively.
  • the process of this invention can be performed by the following apparatus, namely, an apparatus for the diazotype multicolor reproduction which comprises a light source for exposing a diazo-type photosensitive material to light; a heat source for transferring a thermovolatile or thermosublimative coupler from a layer of coupler to a photosensitive layer of the photosensitive material on which the coupler layer is overlapped; a developing mechanism for developing the light-exposed photosensitive material on which the coupler has been heat-transferred; and a delivery mechanism for feeding the diaZo-type photosensitive material, the thermovolatile or thermo sublimative coupler layer and the original to a device for subjecting them to actions of the light source and heat source while maintaining them in the overlapped state and contacting them with such device, and feeding only the light-exposed and heat-transferred photosensitive material to the development mechanism.
  • an apparatus for the diazotype multicolor reproduction which comprises a light source for exposing a diazo-type photosensitive material to light; a heat source for transferring a thermo
  • Any light source that can emit a light of a wavelength sufficient to resolve the diazonium salt in the photosensitive material may be used as a light source of the apparatus of this invention.
  • a fluorescent lamp, a low voltage or high voltage mercury lamp, a xenon lamp, an arc lamp or an incandescent lamp may be optionally used. It is preferable that such light sources are contained in a rotatable transparent cylinder, so that the diazo-type photosensitive material is exposed to light in close contact with the original.
  • a suitable cooling mechanism may be provided to cool the light source and transparent cylinder to suitable temperatures.
  • an infrared lamp Radiations emitted from an infrared lamp selectively heat images of the original, whereby the thermovolatile or thermosublimative coupler can be effectively heat-transferred to the diazo-type photosensitive layer from portions of the coupler layer corresponding to images.
  • the wavelength of an infrared lamp is not critical, but based on experiments it was confirmed that in order to obtain as many multicolored reproductive copies as possible from one original treated with the thermovolatile or thermosublimative coupler it is most preferred to use an infrared lamp that can radiate sub stantially near infrared rays.
  • these heat sources may be contained in a rotatable cylinder in which they are contacted with a piled assembly of the original, the coupler layer and the photosensitive layer.
  • a piled assembly of the original, the coupler layer and the photosensitive layer may be subjected to actions of the light source and heat source coincidentally. Alternatively, it may be exposed at first to light by means of the light source and then heated by means of the heat source to effect the heat transfer. It is also possible to effect the heat transfer by means of the heat source first, followed by the light exposure by the light source.
  • the delivery mechanism comprises a device for subjecting the photosensitive material, the coupler layer and the original to actions of the light source and heat source, for instance, an endless belt driven in contact with a rotatable transparent cylinder, and a moving endless belt or at least one pair of rollers provided in contact with, or in proximity of, the development mechanism.
  • thermovolatile or thermosublimative coupler layer and the diazo-type photosensitive layer overlapped in this order are allowed to pass through a passage formed between the endless belt and the light-exposure and heattransfer zone Where they are subjected to actions of the heat and light sources, whereby the photosensitive layer is exposed and the coupler is heat-transferred on the photosensitive layer, after which the photosensitive layer is forwarded from the light-exposure and heat-transfer zone, separated from the original and coupler layer manually or by suitable means, and then delivered to the development mechanism by means of an endless belt or rollers.
  • Another endless belt 16 is provided between rollers 17 and 18 in the position adajcent to the endless belt 11 and contacting a developer 19.
  • the endless belt 16 is driven by means of a roller 18 at the rate synchronized with the endless belt 11.
  • a plate 20 for evaporating aqueous ammonia and an evaporation heater 21 are provided in the developer 19 .
  • the gasified ammonia and steam are introduced onto photosensitive layer through a plurality of openings formed on a wall 22 of the endless belt 16. It is possible to provide a saucer 23 for receiving reproductive copies on the discharge side of the endless belt 16.
  • thermoelectric coupler it is also possible to effect the heat transfer of the coupler at first and then the light exposure by providing, as is shown in FIG. 4, a heat source 6 consisting of an infrared lamp in the lower portion of the cylinder 1 and a light source 5 consisting of a high voltage mercury lamp in the upper portion of the cylinder 1.
  • a heat source 6 consisting of an infrared lamp in the lower portion of the cylinder 1
  • a light source 5 consisting of a high voltage mercury lamp in the upper portion of the cylinder 1.
  • the separation of the original from the photosensitive material which has been exposed to light and on which the coupler has been heattransferred can be achieved automatically, and the photosensitive material can be automatically fed to the development mechanism. Further, the belt 11 is cooled by the suction mechanism provided adjacently thereto. Accordingly, the apparatus of this type is very advantageous.
  • a suitable temperature 13 control mechanism adoptable in this invention is illustrated in the block diagram of FIG. 10.
  • a temperaturedetecting member such as a thermocouple or a thermistor is provided adjacent to the glass cylinder containing light and heat sources or in contact therewith.
  • a cold air duct such as described hereinabove is provided in the cylinder glass and the cooling of the cylinder glass may be effected and adjusted by the changeover of a motor switch of a cold air-feeding fan or by means of a throttle valve mounted on a duct of the fan. It is also possible to provide the delivery belt with a cooling mechanism such as described above.
  • the heat-transferable coupler layer which is positioned between the cylinder glass and delivery belt is more greatly heated by means of a heat source such as an infrared lamp, among the coupler layer, the photosensitive layer and the delivery belt, a temperature gradient suitable for the effective heat transfer can be obtained.
  • a heat source such as an infrared lamp
  • the reproduction process of this invention is particularly advantageous for reproducing important or significant portions of originals such as papers, drawings and charts into hues different from those of other portions and is effective for obtaining ordinary multicolor copies or colored copies.
  • Example B An ink-like composition for treating the back surface of an original, which resembles that of Example A, is prepared by using acetoacetic-o-chloroanilide instead of acetoacetic anilide in Example A.
  • Example C An ink-like composition of the following recipe is prepared as a red color-forming agent for treating the back surface of an original:
  • Resorcin g 20 Vinyl acetate resin g 5 Methanol ml The above composition is directly used as a material to be coated on the back surface of a portion of the original to be reproduced in red to brown by means of a brush, a coating roller or a sprayer, or after it has been charged in a felt pen or a ball pen, it is used as a material for treating the back surface of a portion of the original to be reproduced in red to brown.
  • Example E An ink-like composition of the following recipe is prepared as a blue color-forming agent for treating the back surface of an original:
  • Example F A treating agent similar to that of Example E is prepared by using 2,7-naphthylene diamine instead of 2,3-dihydroxynaphthalene in Example E.
  • Acetoacetic anilide 30 Stearic acid 100 Parafiin 50 Terra alba 50 Diatomaceous earth 20 and solidifying the melt.
  • the above composition is molded into a crayon sticklike form and is used as a material to be coated on the back surface of a portion of the original desired to be reproduced into a different hue.
  • Example H To the composition of Example G are added 100 g. of mineral oil, 50 g. oleic acid and 20 g. of Aureamine, and the mixture is kneaded in a bowl mill to disperse additional components uniformly. Then, the kneaded mixture is coated on a substrate such as paper to obtain a pressuresensitive copy sheet. The so formed copy sheet is overlapped on the back surface of an original and the pressing is effected thereon by means of a typewriter or other writing means. Thus, the sheet is used as a material for forming a layer of the waxy agent on the back surface of an image of the original to be reproduced in a different hue.
  • Example I A waxy composition to be used as a red color-forming agent for treating the back surface of an original is prepared by heat melting G. Resorcin monoglycol ether 20 Paraifin 50 Terra alba 70 Haze wax 20 Stearic acid 100 Magnesium carbonate 20 and solidifying the melt.
  • the so formed composition is molded into a crayon stick-like or chalk-like form and is used as a material for coating the back surface of a portion of an original desired to be reproduced in a different hue.
  • Example I A waxy composition of the following recipe is prepared as a blue color-forming agent for treating the back surface of an original:
  • Example L To the composition of Example K are added 100 g. of mineral oil, 30 g. of oleic acid, 20 g. of Oil Blue and 50 ml. of ethanol, and the mixture is kneaded in a bowl mill, coated on a substrate such as paper and dried to obtain a pressure-sensitive copy sheet. This sheet is used as a material for forming a layer of the waxy agent on the back surface of an original in a manner as described in Example H.
  • Example N A composition to be used as a red color-forming agent for treating the back surface of an original is prepared by using resorcin instead of acetoacetic acid aniline in Example M. From this composition there is formed a sheet for heat-transferring the coupler capable of forming a red color.
  • Example 0 A composition to be used as a blue color-forming agent for treating the back surface of an original is prepared by using 1,6-dihydroxynaphthalene instead of acetoacetic acid aniline in Example M. From this composition there is formed a heat-transferable sheet capable of forming a blue color.
  • Example P A waxy composition of the following recipe is used as a black color-forming agent for treating the back surfac of an original:
  • Example H Mineral oil Diatomaceous earth 50 Stearic acid 30 Resorcin 10 Acetoacetic anilide 20 Carbon black 30 Alkali Frex Blue 5
  • the above composition is well kneaded in a bow mill, coated on a substrate such as paper and dried to form a pressure-sensitive copy sheet.
  • the sheet is used as a material for forming a layer of the waxy composition on the back surface of the original in a manner as described in Example H.
  • Multicolor-forming diazo-type photosensitive paper in use for wet development 10 g. of a double salt of 4-diazo-2,S-diethyloxybenzoylaniline chloride-V2 ZnCl 8 g. of citric acid, 0.1 g. of Patent Blue and 10 g. of dextrin are successively dissolved in water, to make 1 liter of a solution.
  • the solution is coated on a base paper and dried to obtain a diazo-type photosensitive sheet for wet development.
  • the photosensitive paper is overlapped on an original in which a portion is treated with the treating material prepared in Example A and another portion is treated with the treating material prepared in Example C.
  • the solution is coated on a base paper by a customary coating procedure such as using an air knife coater and dried to form a photosensitive sheet.
  • the sheet is overlapped on an original in which the back surface of a portion is treated with the treatingmaterial prepared in Example B, the back surface of another portion is treated with the treating material prepared in Example C and the back surface of still another portion is treated with the treating material obtained in Example E. Then, the assembly is heated and exposed to light by means of a mercury lamp to form a latent image of the diazonium salt.
  • the so treated sheet is subjected to development with gasified ammonia and steam.
  • a clear multicolor copy in which a portion corresponding to the portion treated with the material of Example B is colored in an orange color, a portion corresponding to the portion treated with the material of Example C is colored in reddish brown, a portion corresponding to the portion treated with the material of Example E is colored in bluish violet, and other portion corresponding to the untreated portion is colored in dark blue is obtained.
  • Example 4 When Example 3 is repeated by. using N,N-[1-hydroxy- 3-sulfonaphthyl(6)] thiourea instead of bis-[S-hydroxy- 7-sulfonaphthyl(2)] amine, a multicolor reproductive copy similar to that of Example 3 is obtained.
  • a photosensitive paper is prepared from the above solution.
  • the photo- 18 sensitive paper is overlapped on an original in which the sheet for heat-transferring the coupler prepared in Example N is made to confront a part of the back surface of the original.
  • the assembly is exposed to light and heated by means of a mercury lamp.
  • the so treated sheet is subjected to development with gasified ammonia and steam.
  • a clear two-color reproductive copy in which a portion corresponding to the portion of the original which has been made to confront to the heattransfer sheet is colored in reddish brown and other portion corresponding to the untreated portion of the original is colored in blue is obtained.
  • EXAMPL 6 The-photosensitive sheet of Example 6 is placed on an original, a part of the back surface of which is treated with the waxy composition obtained in Example G and another part of the back surface of which is treated with the treating material obtained in Example I.
  • a mercury lamp is placed above the assembly and it is exposed to light and heated to form a latent image of the diazonium salt.
  • the development is effected with gasified ammonia and steam, a clear multicolor reproductive copy in which a portion corresponding to the portion of the original treated with the material of Example G is colored in yellow, a portion corresponding to the portion treated with the material of Example I is colored in reddish brown and a portion corresponding to the untreated portion of the original is colored in dark blue is obtained.
  • Citric acid 30
  • Zinc chloride 30
  • the solution is coated on a polyester film by a rod coater and dried at a relatively low temperature (40-50 C.) by warm air to form a photosensitive film.
  • the film is piled on an original in which a part of the back surface of an original image is treated with the ink-like agent prepared in Example A and the back surface of another part of the original image is treated with the treating agent prepared in Example C.
  • the assembly is exposed to light by a mercury lamp and heated and printed.
  • the photosensitive film containing a latent image of the diazonium salt is developed with gasified ammonium and steam.
  • EXAMPLE 9 The photosensitive sheet obtained in Example 3 is overlapped on an original in which at one part a pattern is formed by using the waxy treating agent obtained in Example H and effecting pressing by a typewriter or other writing tool, at another part another image is formed as above with the use of the treating agent obtained in Example I, and still another pattern is formed at still another part according to an ordinary pattern-forming procedure.
  • the assembly is heated and exposed to light by means of a mercury lamp to form a latent image of the diazonium salt, followed by development with gasified ammonium and steam.
  • a clear multicolor reproductive copy in which a portion corresponding to the part where the pattern has been formed with the treating material of Example H is colored in yellowish brown, a portion corresponding to the part where the pattern has been formed with the treating material of Example I is colored in reddish brown and a portion corresponding to the part where the pattern has been formed in a customary manner is colored in dark blue is obtained.
  • a process for multi-color reproduction which comprises:
  • A exposing image-wise a diazo-type photosensitive material to actinic light by exposing through an original sheet of an assembly, said assembly consisting of (i) an original sheet having opaque image areas and transparent non-image areas on one surface and a layer containing at least one thermovolatile or sublimable azo 'coupler (a), said layer being on the opposite surface of said original'sheet, and coupler .
  • (a) being located in only preselected areas which are contiguous with opaque image areas of said original sheet, said preselected areas being present in only a portion of the areas contiguous with said opaque image areas of said original sheet, and (ii) a diazo-type photosensitive material having a photosensitive layer containing at least one photosensitive diazonium salt (c), an acidic stabilizer and an azo coupler (b) having a substantially lower rate of coupling with the diazonium salt (c) under the developing conditions than that of the azo coupler (a), said original sheet (i) being superposed on said diazo-type photosensitive
  • said coupler (a) is a compound free of sulphonic acid groups and selected from a phenol compound, a hydroxynaphthalene compound, an aniline compound and a compound containing an active methylene group.
  • A exposing image-wise a diazo-type photosensitive material to actinic light by exposing through an original sheet of an assembly, said assembly consisting of (i) an original sheet having opaque image areas and transparent non-image areas on one surface and a layer containing at least one thermovolatile or sublimable azo coupler (a), said layer being on the opposite surface of said original sheet, and coupler (a) being located in only preselected areas which are contiguous with opaque image areas of said original sheet, said preselected areas being present in only a portion of the areas contiguous with said opaque image areas of said original sheet, and (ii) a diazotype photosensitive material having a photosensitive layer containing at least one photosensitive diazonium salt (0), said original sheet (i) being superposed on said diazo-type photosensitive material (ii) so that the layer of the azo coupler (a) comes into faceto-face contact with the photosensitive layer;
  • steps (A) and (B) being performed simultaneously or (in the time sequence of (A) to (B) or (B) to (A);
  • the coupler (a) is applied in the form of a composition comprising from 5 to 25% by weight of the coupler (a), to 3% by weight of a colorant, 0 to by weight of a binder, 0 to 2% by weight of a dispersant and the balance an organic solvent.
  • said coupler (a) is a compound free of sulphonic acid groups and selected from a phenol compound, a hydroxynaphthalene compound, an aniline compound and a compound containing an active methylene group.

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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)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Photographic Developing Apparatuses (AREA)
US00012049A 1969-02-19 1970-02-17 Diazo-type multicolor reproduction Expired - Lifetime US3715213A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP1191469 1969-02-19
JP6598069 1969-08-22
JP44091964A JPS4918263B1 (de) 1969-11-18 1969-11-18

Publications (1)

Publication Number Publication Date
US3715213A true US3715213A (en) 1973-02-06

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Family Applications (1)

Application Number Title Priority Date Filing Date
US00012049A Expired - Lifetime US3715213A (en) 1969-02-19 1970-02-17 Diazo-type multicolor reproduction

Country Status (4)

Country Link
US (1) US3715213A (de)
DE (1) DE2007690C3 (de)
FR (1) FR2037103A1 (de)
GB (1) GB1292163A (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852093A (en) * 1972-12-13 1974-12-03 Minnesota Mining & Mfg Heat-sensitive copy-sheet
US3895173A (en) * 1972-02-17 1975-07-15 Matsushita Electric Ind Co Ltd Dichromatic thermo-sensitive recording paper
US3907567A (en) * 1970-05-01 1975-09-23 Mita Industrial Co Ltd Waxy crayon or ink-like diazotype developer composition comprising heat transferrable azo coupler and transfer promotor
US3918974A (en) * 1970-05-01 1975-11-11 Mita Industrial Co Ltd Process for the diazo-type multicolor reproduction
US3948661A (en) * 1969-02-19 1976-04-06 Mita Industrial Company Ltd. Process for diazo-type multicolor reproduction
US3950171A (en) * 1970-07-27 1976-04-13 Mita Industrial Co. Ltd. Diazotype multicolor reproduction process
US3981730A (en) * 1973-04-18 1976-09-21 Mita Industrial Company, Ltd. Diazo-type multicolor reproduction process
US4135814A (en) * 1976-05-28 1979-01-23 Hoechst Aktiengesellschaft Process and apparatus for the production of photocopies using two-component diazotype material

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS512429A (de) * 1971-08-16 1976-01-10 Mita Industrial Co Ltd
JPS4838728A (de) * 1971-09-17 1973-06-07
JPS4838729A (de) * 1971-09-17 1973-06-07
JPS5542742B2 (de) * 1972-04-13 1980-11-01
JPS5547377B2 (de) * 1972-04-13 1980-11-29
DE3778957D1 (de) * 1986-02-03 1992-06-17 Canon Kk Bildaufzeichnungsgeraet.

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3948661A (en) * 1969-02-19 1976-04-06 Mita Industrial Company Ltd. Process for diazo-type multicolor reproduction
US3907567A (en) * 1970-05-01 1975-09-23 Mita Industrial Co Ltd Waxy crayon or ink-like diazotype developer composition comprising heat transferrable azo coupler and transfer promotor
US3918974A (en) * 1970-05-01 1975-11-11 Mita Industrial Co Ltd Process for the diazo-type multicolor reproduction
US3950171A (en) * 1970-07-27 1976-04-13 Mita Industrial Co. Ltd. Diazotype multicolor reproduction process
US3895173A (en) * 1972-02-17 1975-07-15 Matsushita Electric Ind Co Ltd Dichromatic thermo-sensitive recording paper
US3852093A (en) * 1972-12-13 1974-12-03 Minnesota Mining & Mfg Heat-sensitive copy-sheet
US3981730A (en) * 1973-04-18 1976-09-21 Mita Industrial Company, Ltd. Diazo-type multicolor reproduction process
US4135814A (en) * 1976-05-28 1979-01-23 Hoechst Aktiengesellschaft Process and apparatus for the production of photocopies using two-component diazotype material

Also Published As

Publication number Publication date
FR2037103A1 (de) 1970-12-31
DE2007690A1 (de) 1970-10-01
GB1292163A (en) 1972-10-11
DE2007690C3 (de) 1974-05-16
DE2007690B2 (de) 1973-10-18

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