US3653903A - Diazo-type multicolor reproduction process - Google Patents

Diazo-type multicolor reproduction process Download PDF

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US3653903A
US3653903A US59923A US3653903DA US3653903A US 3653903 A US3653903 A US 3653903A US 59923 A US59923 A US 59923A US 3653903D A US3653903D A US 3653903DA US 3653903 A US3653903 A US 3653903A
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coupler
diazo
original
photosensitive
acid
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Kouzi Nihyakumen
Taizo Yokoyama
Yasuo Ueda
Yasutoki Kamezawa
Tatsuo Aizawa
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Kyocera Mita Industrial Co Ltd
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Mita Industrial Co Ltd
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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

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  • DIAZO-TYPE MULTICOLOR REPRODUCTION PROCESS [72] Inventors: Kouzi Nihyakumen, I-Iirakata; Taizo Yokoyama, Osaka; Yasuo Ueda, Kobe; Yasutoki Kamezawa; Tatsuo Aizawa, both of Osaka, all of Japan [73] Assignee: Mita Industrial Company, Ltd., Osaka,
  • a process for the diazo-type multicolor reproduction which comprises (A) exposing to light a dliazo-type photosensitive material having a photosensitive layer containing at least one diazonium salt (0) and a coupler (b) having a substantially lower rate of coupling with the diazonium salt (0) than that of resorcin, said coupler being present in the photosensitive material in an amount of not greater than 1 mole per mole of said diazonium salt (c), and (B) heating a layer of at least one thermovolatile or thermosublimative coupler (a) disposed in a face-to-face contact with said photosensitive material at a predetermined portion, said steps being carried out coincidentally or in the order of(A) to (B) or (B) to (A), and then developing the exposed photosensitivematerial. photosensitive material.
  • thermovolatile or thermosublimative coupler a layer of at least one thermovolatile or thermosublimative coupler (a) disposed in a face-to-face contact with a predetermined portion of said diazo-type photosensitive material, said 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 said thermovolatile or thermosublimative coupler (a).
  • coupler a coupler having a substantially lower rate of coupling with a diazonium salt (c) of the photosensitive layer than that of resorcin and making said coupler present in the photosensitive layer in an amount of not greater than 1 mole per mole of the diazonium salt.
  • a process for the diazo-type multicolor reproduction which comprises conducting the steps of (A) exposing to light a diazo-type photosensitive material having a photosensitive layer containing at least one diazonium salt and a coupler (b) having a substantially lower rate of coupling with the diazonium salt (c) than that of resorcinol, said coupler (b) being present in the photosensitive material in an amount of not greater than 1 mole per mole of said diazonium salt (c), and (B) heating a layer of at least one thermovolatile or thermosublimative coupler (a) disposed in a face-to-face contact with said photosensitive material at a predetermined portion, said steps being carried out coincidentally or in an order of (A) to (B) or (B) to (A), and then developing the exposed photosensitive material.
  • coupler that has a substantially lower rate of coupling with a diazonium salt (c) contained in a photosensitive material than that of resorcinol, preferably that of 2,3-dihydroxynaphthalene, can be used as coupler (b) in the process of this invention.
  • Coupler (b) Typical examples of such coupler (b) are as follows Phenol Derivatives 2,5 ,6-Trimethylphenol 2-ll-lydroxymethylphenol B-( Z-Hydroxyphenyl)-propionic acid Z-(w-Phenylaminomethyl )-phenol B-(4-Methyl-2-hydroxyphenyl)-glutaric acid 2,5-Dimethyl-6-(N-dimethylaminomethyl)-phenol 1,3-Dimethyl ether of pyrogallol a-Resorcylic acid ethanolamine ,BResorcylic acid 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 2-Methyl-5-isopropyl-morpholinomethyl phenol 4-
  • any of the above-cited compounds listed on pages 4-9 may be used as coupler (b), but it is preferable to employ couplers having two or more hydroxyl or active methylene groups and being capable of forming polyazo dyes such as bis-azo dyes and tris-azo dyes, especially couplers having two or more aromatic rings containing a hydroxyl group.
  • diazonium salt (c) any of conventional photo-resoluble diazonium salts used as diazo-type photosensitive materials may be used as diazonium salt (c) in this invention, so far as it is capable of coupling with the above-mentioned coupler (b) under ordinary developing conditions.
  • diazonium salt examples are as follows:
  • X stands for an anion
  • R and R" each are aliphatic groups
  • Z and Y denote groups which can be introduced into the benzene nucleus.
  • Specific examples of the compounds of this type are as follows:
  • 4-Diazo-N,N-dimethyl aniline referred to simply as MA salt
  • 4-Diazo-N,N-diethyl aniline referred to simply as EA salt
  • 4-Diazo-N-ethyl-N-B-hydroxyethyl aniline referred to simply as EH salt
  • 4-Diazo-N,N-bis-[B-hydroxyethyl aniline 4-Diazo-N-methyl-N-B-hydroxyethyl aniline
  • Other diazonium salts of p-phenylene diamines N,N- substituted with alkyl or hydroxy-alkyl groups 4-Diazo-N-ethyl-N-(B-diethylamino)-ethyl aniline 4-Diazo-2-chloro-N,N-diethyl aniline 4-Diazo-2-methyl- N,N-diethyl aniline 4-Di
  • R, R and R" are alkyl or aryl groups and X stands for an anion.
  • X is an anion
  • 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 and examples of the R-A-R' are diarylamine (A; -NIH-), diphenyl (A; direct bond), diphenyl oxide (A; -O-), diaryl methane (A; -Cl-l stilbene (A; -CH CH-) and diaryl or dialkyl sulfide (A; -S-) Specific examples of the compounds. of the above type are as follows:
  • 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 be also 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. These diazonium salts may be used either singly or in the form of a mixture of two or more of them.
  • the above-mentioned coupler (b) is used in an amount of not greater than 1 mole per mole of such diazonium salt (0).
  • the amount of the coupler (b) is more than 1 mole per mole of the diazonium salt (c)
  • the coupling reaction between the diazonium salt (c) and the coupler (b) is also allowed to advance to some extent, which sometimes results in occurrence of undesired mingling of colors.
  • the amount of the coupler (c) in the photosensitive layer is made less than 1 mole per mole of the diazonium salt, it is possible to form a dyestuff composed of the coupler (a) and the diazonium salt (c) selectively at portions of the photosensitive layer corresponding to predetermined portions of the original.
  • this sensitizing composition for dry development is made less than 1 mole per mole of the diazonium salt, it is possible to form a dyestuff composed of the coupler (a) and the diazonium salt (c) selectively at portions of the photosensitive layer corresponding to predetermined portions of the original.
  • 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.
  • Stabilizer O-5.0 7 Coloring matter 0.00l-0.025 7r 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.
  • organic acid in the sensitizing composition there may be used citric acid, tartaric acid, oxalic acid, sulfamic acid, etc.
  • extender there may be used dextrin, gum arabic, colloidal silica, etc.
  • stabilizes there may be used 1,3,6- naphthalene, sodium trisulfonate and other aryl sulfonic acids.
  • Polyhydric alcohols such as glycerin and ethylene glycol are used as development promoter. Coloring matters are used for indicating the photosensitive face and increasing the whiteness of the back ground, and blue dyestuffs such as methylene blue and Patent Blue are used for this purpose.
  • solvent there may be used water and organic solvent such as alcohols, acetone, toluene, xylene and esters.
  • the multicolor reproduction using the diazo-type photosensitive materials of this invention is performed by conducting the steps of (A) exposing to light a photosensitive material containing at least one diazonium salt (c) and a coupler (b) in the above-mentioned amount and (B) heating a layer of at least one thermovolatile or thermosublimative coupler (a) disposed in a face-to-face contact with said photosensitive material at a predetermined portion, said steps being carried out coincidentally or in an order of (A) to (B) or (B) to (A), and then subjecting the exposed photosensitive material under developing conditions.
  • thermovolatile or thermosublimative coupler (a), coupler (b) and diazonium salt (0) to be used in this invention there should be established the following relations:
  • Thermovolatile or thermosublimative coupler (a) has a higher coupling rate under developing conditions than coupler II.
  • Dyestuff (b)-(c), dyestuff (a)(c), dyestuff (a)- (c) ..formed at the development have hues different to one another.
  • thermovolatile or thermosublimative coupler (a) Any coupler that can be volatilized or sublimated under heating conditions may be used as thermovolatile or thermosublimative coupler (a) in this invention.
  • coupler (a) there may be mentioned phenol derivatives. hydroxynaphthalene derivatives, aniline derivatives and active methylene group-containing compounds. In view of facilitation of the heat transfer operation it is preferred that these derivatives do not contain soluble groups such as a sulfonic acid group.
  • Phenol Derivatives Phenol Pyrocatechol Resorcinol Phloroglucinol o-Hydroxybenzalcohol Resorcinol monoglycol ether Resorcinol diglycol ether Hydrotoluquinone Pyrogallol-4-carboxylic acid Vanillin lsovanillic acid Vanillic acid S-Hydroxy-isophthalic acid 2-l-lydroxy-terephthalic acid 2Hydroxy-p-toluylic acid 3-Hydroxy-p-toluylic acid S-Hydroxy-o-toluylic acid -l-lydroxy-m-toluylic acid S-Hydroxy-l-naphthonic acid Para-hydroxyphenylacetic acid 2,7-Dihydroxynaphthalene 2,3-Dihydroxynaphthalene 8-Amino-2-naphthol 2,2-dihydroxyl l -binaph
  • an original for multicolor development is formed by applying at least one transparent or semi-transparent layer of a thermovolatile or thermosublimative coupler (a) onto the back surface of one or more predetermined portions of a transparent or semi-transparent original to be copied.
  • thermovolatile or thermosublimative coupler (a) is heat-transferred 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 of the original.
  • the diazonium salt (c) at the non-exposed area reacts selectively and preferentially with the coupler (a) to form a dyestuff (c) (a) and at other portion the diazonium salt (c) at the non-exposed reacts with coupler (b) to form a dyestuff (c) (b).
  • the predetermined portion is colored in a hue different from that of the other portion.
  • 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 different hue, of a transparent or semi-transparent original to be copied, or by a method comprising coating or impregnating a transparent or semi-transparent substrate with the said 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 different 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.
  • the dispersion medium there may be used water and organic solvents such as alcohol, toluene, xylene, esters and methyl ethyl ketone. 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, a sprayer or a printing machine.
  • Waxy composition for treating the back surface of an original 1. Waxy composition for treating the back surface of an original:
  • Coupler (a) 5.0-25.0 7c Wax 85.0-15.0 Oil 10.0-40.0 7: Coloring material 020.0 k
  • 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 is
  • the ink-like composition for treating the back surface of an original, which was described in (l), or a composition obtained by incorporating a binder or an extender into such inklike composition is coated on a transparent or semi-transparent sheet such as paper, plastic film or non-woven fabric.
  • 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, and then applied to the back surface of a portion of an original determined to have a different hue. It is possible to form a pressure-sensitive adhesive layer on the back surface of the coupler-transferring layer for preventing it from exfoliating from the original.
  • the so prepared original for multicolor development may be generally used 5 to times repeatedly for the multi-color development, though the applicable frequency of the repeated use varies depending on the amount coated of coupler (a), the coating method, the heating method and the developing method.
  • the heat-transferability of coupler (a) in the layer for heat-transferring the coupler is lowered, it is sufficient to supply newly an additional layer for heattransferring the coupler.
  • thermovolatile or thermosublimative coupler (a) The exposure of the photosensitive material and the transfer of the thermovolatile or thermosublimative coupler (a) to the photosensitive surface may be effected coincidentally.
  • the heat transfer of the coupler (a) may be effected coin' cidentally with the exposure by the heat conveyed through a cylinder glass of the light source maintained at a relatively high temperature.
  • the heat "transfer of the coupler (a) may be also effected by the radiation heating of an image of the original.
  • the heat transfer of the coupler (a) may be effectively performed by heating the layer for heat-transferring the coupler at a temperature above 50 C., preferably above 70 C., though a preferable heating temperature varies to some extent depending on the kind of the coupler (a) and the heating time. It is also possible to adopt a method comprising placing the above-mentioned original for multicolor development and the photosensitive material, passing the assembly through a heated roller or an infrared radiation zone to heat the layer for heat-transferring the coupler at the above-mentioned temperature and to effect the heat transfer of the coupler, and then passing the same through an exposure zone to effect the exposure of the photosensitive material.
  • the photosensitive material which has been exposed to light and on a predetermined portion of which the coupler (a) has been heat-transferred is developed by means known per se.
  • the development may be conducted by either a dry method or a wet method.
  • the development may be performed sufficiently only by exposing the light-exposed photosensitive material to a mixture of ammonia and steam.
  • the development can be accomplished by contacting the photosensitive material with an aqueous liquid developer containing an alkali.
  • multicolored reproductive copies in which the portions corresponding to predetermined portions of an original are colored selectively in different hues independently from other portions without any undesired mingling of colors. Further, multi-coloration can be accomplished by conducting the single-step development.
  • FIGS. 1 and 2 are diagrams given to illustrate the multicolor reproduction process of this invention and FIG. 3 is a CIE chromaticity diagram showing the results of Comparative Example in which the molar ratio of the coupler (b) to the diazoniurn salt was varied, which Comparative Example will be detailed hereinbelow.
  • thermovolatile or thermosublimative couplers 2 and 3 are coated on the back surfaces of images 2 and 3, respectively, of an original having images I, 2 and 3.
  • latent images 1", 2" and 3" corresponding to images I, 2 and 3 are formed on the photosensitive layer and couplers 2' and 3' are transferred on the upper surface of the photosensitive layer by the heat from the light source.
  • the diazonium salt in latent images 2" and 3" of the photosensitive layer reacts selectively with transferred couplers 2 and 3, while the diazonium salt in latent image 1 reacts with a coupler contained in the photosensitive layer.
  • a reproductive copy which has images 11, 12 and 13 colored in different hues.
  • 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 above composition is directly used as a material to be coated on the back surface of a portion of the original desired to be reproduced in yellow 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 desired to be reproduced in yellow.
  • Example B An ink-like composition of the following recipe is prepared as a red color-forming agent for treating the back surface of an original:
  • 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 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.
  • Example C An ink-like composition of the following recipe is prepared as a brown color-forming agent for treating the back surface of an original:
  • a waxy composition to be used as a yellow color-forming agent for treating the back surface of an original is prepared by heat melting Acetoacetic anilide 30 g. Stearic acid 100 g. Paraffin 50 g. Terra abla 50 g. Diatomaceous earth 20 g.
  • the above composition is molded into a crayon stick-like form and is used as a material to be coated on the back surface ofa portion of the original desired to be reproduced into a different hue.
  • Example F A waxy composition to be used as a yellowish brown colorforming agent for treating the back surface of an original is prepared by heat melting Resorcinol monoglycol ether 20 g. Paraffin 50 g. Terra abla g. Haze wax 20 g. Stearic acid 100 g. Magnesium carbonate 20 g.
  • the so formed composition is molded into a crayon sticklike 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 G A waxy composition of the following recipe is prepared as a red color-forming agent for treating the back surface of an original:
  • l-Phenyl-3-methylpyrazolone (5) 20 g. Stearic acid I00 g. Paraffin 50 g. Diatomaceous earth 30 g. Haze wax 20 g.
  • the above 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 the original desired to be reproduced in a different hue.
  • Example I-I inqnan To the composition of Example G are added 100 g. of mineral oil, 50 g. oleic acid and 20 g. of Permanent Red, 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 pressure-sensitive 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.
  • the above composition is coated on a transparent or semitransparent sheet such as polyester film by means of a rod coater and dried at a relatively low temperature (40 50 C.) to form a sheet for heat-transferring the coupler. After being cut into a desired size according to need, the sheet is used as a material to be applied to the back surface of a portion of an original desired to be reproduced in a different hue.
  • Example J A composition to be used as a red color-forming agent for treating the back surface of an original is prepared by using 1- phenyl-3-methylpyrazolone (5) instead of acetoacetic acid aniline in Example I. From this composition there is formed a sheet for heat-transferring the coupler capable of forming a red color.
  • Example K A composition to be used as a blue color-forming agent for treating the back surface of an original is prepared by using 2,3-dihydroxynaphthalene instead of acetoacetic acid aniline in Example I. From this composition there is formed a heattransferable sheet capable of forming a blue color.
  • Example 1 Multicolor-forming diazo'type photosensitive paper in use for dry development A solution of the following recipe is prepared:
  • the sheet is overlapped on an original in which the back surface of a portion is treated with the treating material prepared in Example A and the back surface of another portion is treated with the treating material prepared in Example B. Then, the assembly is heated at 70 100 C. and exposed to light by means of a mercury lamp to form a latent image of the diazonium salt.
  • Example 2 When Example 1 is repeated by using 4-diazo-N-ethyl-N- hydroxyethyl-aniline chloride-M2 ZnCl instead of 4diazo- N,N-dimethylaniline chloride-U2 ZnCl there is obtained a multicolor reproductive copy similar to that of Example 1.
  • a photosensitive paper is prepared from the above solution.
  • the photosensitive paper is placed on an original in which a portion of the back surface is treated with the waxy composition prepared in Example E and another portion of the back surface is treated with the composition prepared in Example G.
  • the assembly is exposed to light and heated by means of a mercury lamp.
  • the photosensitive paper is placed on an original, a portion of the back surface of which is treated with the coupler-heattransferring sheet prepared in Example .I and another portion of the back surface of which is treated with the treating agent obtained in Example K. Then the assembly is heated and printed by means of a mercury lamp, followed by development with gaseous ammonia and steam. Thus there is obtained a clear three-color reproductive copy in which a portion corresponding to the untreated portion of the original is colored in red.
  • Example 7 Multicolor-forming photosensitive paper for dry developresponding to the portion treated with the treating agent of ment
  • the above solution is coated on a semi-transparent paper such as tracing paper and dried to form a photosensitive paper.
  • the photosensitive paper is placed on an original, a portion of the back surface of which is treated with the inklike composition prepared in Example B and another portion of the back surface of which is treated with the composition obtained in Example D. Then the assembly is heated and printed by means of a mercury lamp, followed by development with gasepus ammonia and steam.
  • the so formed photosensitive paper is placed on an original, a portion of the back surface of which is treated with a coupler-heat-transferring sheet prepared in Example K, and the assembly is heated and printed by means of a mercury lamp, followed by development with gaseous ammonia and steam.
  • a clear two-color reproductive copy without any substantial mingling of colors, in which a portion corresponding to the portion of the original treated with the sheet obtained in Example K is colored in blue and the remaining portion cor-
  • a solution of the following recipe is prepared:
  • the assembly is heated and printed by means of a mercury lamp, followed by development with gaseous ammonia and steam.
  • a clear two-color reproductive copy in which a portion corresponding to the treated portion of the original is colored in brown and other remaining portion corresponding to the untreated portion of the original is colored in dark blue.
  • Example 8 Multicolor-forming sensitive paper in use for either dry or wet development A solution of the following recipe is prepared:
  • a photosensitive paper is prepared by conducting the coating and drying in the same manner as in Example 1. The so formed photosensitive paper is piled on an original, a portion of the back surface of which is treated with the ink-like composition prepared in Example A and another portion of the back surface of which is treated with the treating material prepared in Example C. Then the assembly is heated and printed by means of a mercury lamp, followed by development with gaseous ammonia and steam or with an alkaline liquid developer of the following recipe:
  • the solution is coated on a polyester film by a rod coater and dried at a relatively low temperature (40 50C.) by warm air to form a photosensitive film.
  • the film is placed 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 another part of the back surface of the original image is treated with the treating agent prepared in Example B.
  • 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.
  • Comparative Example This example is given to illustrate the relation between the amount of the coupler (b) (having a lower coupling rate than the thermovolatile or thermosublimative coupler (a)) and the effect of preventing the mingling of colors.
  • the color tones of the portion corresponding to the treated portion of the original and the portion corresponding to the untreated portion of the original are determined by measuring tristimulus values X, Y and Z according to colorimetric system CIE. Then the values of x and y are calculated by the following equations:
  • the dominant wavelength (A max) and excitation purity (Pe) are determined from the CIE standard chromaticity diagram, and the effect of preventing the mingling of colors is evaluated from the deviation of the dominant wavelength and the change in excitation purity.
  • TAB LE 2 Portion corresponding to untreated portion Portion corresponding tol treated portion Color ditierencc of original of origin between portions corresponding to Dominant Excitation
  • Dominant Excitation treated and wavelength purity (Pe) Sample wavelength purity (Pe)
  • Untreated portions Sample No. (A max.), in percent No. (A max), 1111.: percent of orlginul (AB) in Table l is coated by hand on a photosensitive paper sub- NOTES strate:
  • the unit of 4E is the NBS unit.
  • the coupler (b) (DS acid) is used in an amount such that: its molar ratio to the diazonium (c) (MA salt) is l or more (samples t 10), the coupler (b) (DS acid) is used in an amount such that: its molar ratio to the diazonium (c) (MA salt) is l or more (samples t 10), the coupler (b) (DS acid) is used in an amount such that: its molar ratio to the diazonium (c) (MA salt) is l or more (samples t 10), the coupler (b) (DS acid) is used in an amount such that: its molar ratio to the diazonium (c) (MA salt) is l or more (samples t 10), the coupler (b) (DS acid) is used in an amount such that: its molar ratio to the diazonium (c) (MA salt) is l or more (samples t 10), the coupler (
  • the dominant wavelength deviates toward the long wavelength area, and at the molar ratio of 2.5 (sample 7) the dominant wavelength comes to be in the range of the complementary dominant wavelength, with the result that the color tone becomes close to the color tone of the portion corresponding to the untreated portion of the original, namely the color tone becomes closer to bluish violet.
  • excitation purity Pe
  • the coupler (b) DS acid
  • the above-mentioned molar ratio is l or more (samples 4 10)
  • the distinctness of color is lowered with the decrease of the value of excitation purity to less than 25 percent, with the result that darkening of color is caused to appear and the color distinction becomes bad.
  • a process for the diazo-type multicolor reproduction which comprises conducting the steps of (A) exposing imagewise to actinic light a diazo-type photosensitive material having a photosensitive layer containing at least one photosensitive diazonium salt (c) and an azo coupler (b) having a substantially lower rate of coupling with the diazonium salt (c) than that of resorcinol, said azo-coupler being present in the photosensitive layer in an amount of from 0.1 to 1 mole per mole of said diazonium salt (0), and (B) heating at a predetermined portion a layer of at least one thermovolatile or thermosublimative azo coupler (a) which is disposed in face-toface contact with said photosensitive material to produce an azo dye image in the area of the diazotype material contiguous with the heated area of the layer containing azo coupler (a), said steps being performed coincidentally or in the order of (A) to (B) or (B) to (A), and then developing the exposed photosensitive material
  • thermovolatile or thermosublimative azo coupler (a) is applied to the back surface of a predetermined portion of a transparent or semi-transparent original and then placed on the photosensitive diazo-type material such that the photosensitive layer will be in face-to-face contact with the layer containing azo coupler (a), and both the light exposure and heat transfer of azo coupler (a) are performed when the composite structure is in the above described relationship.

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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)
US59923A 1969-08-02 1970-07-31 Diazo-type multicolor reproduction process Expired - Lifetime US3653903A (en)

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JP44060756A JPS4829059B1 (ja) 1969-08-02 1969-08-02

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US (1) US3653903A (ja)
JP (1) JPS4829059B1 (ja)
DE (1) DE2038242C3 (ja)
FR (1) FR2056955B1 (ja)
GB (1) GB1318706A (ja)
NL (1) NL154016B (ja)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3918974A (en) * 1970-05-01 1975-11-11 Mita Industrial Co Ltd Process for the diazo-type multicolor reproduction
US3944422A (en) * 1969-09-01 1976-03-16 Mita Industrial Company Limited Photosensitive material in use for diazo-type multicolor reproduction
US4062644A (en) * 1976-03-30 1977-12-13 Graphic Magicians, Inc. Transfer ink and method of using same
US4157874A (en) * 1978-04-10 1979-06-12 Freeman Transfer Printing Co. Dye marking device
US4725526A (en) * 1984-08-21 1988-02-16 Hoeschst Aktiengesellschaft Process for reducing halations using lubricant in the course of irradiating and developing reproduction layers used for preparing printing plates
US4911733A (en) * 1979-06-20 1990-03-27 Canon Kabushiki Kaisha Process for fabricating color filters

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54120803U (ja) * 1978-02-09 1979-08-24

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2541178A (en) * 1945-08-18 1951-02-13 Gen Aniline & Film Corp Photographic process for dyeing of textile materials
US2789904A (en) * 1953-09-17 1957-04-23 Gen Aniline & Film Corp Diazo print process
GB1000151A (en) * 1961-03-24 1965-08-04 Ozalid Co Ltd Improvements in or relating to methods of making facsimile copies of graphic originals
US3224878A (en) * 1961-12-01 1965-12-21 Dietzgen Co Eugene Thermographic diazotype reproduction material, method of making and method of using
US3454764A (en) * 1965-09-10 1969-07-08 Printing Arts Research Lab Inc Process of making diazo copies by sublimation of reactant materials onto a copy sheet

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2541178A (en) * 1945-08-18 1951-02-13 Gen Aniline & Film Corp Photographic process for dyeing of textile materials
US2789904A (en) * 1953-09-17 1957-04-23 Gen Aniline & Film Corp Diazo print process
GB1000151A (en) * 1961-03-24 1965-08-04 Ozalid Co Ltd Improvements in or relating to methods of making facsimile copies of graphic originals
US3224878A (en) * 1961-12-01 1965-12-21 Dietzgen Co Eugene Thermographic diazotype reproduction material, method of making and method of using
US3454764A (en) * 1965-09-10 1969-07-08 Printing Arts Research Lab Inc Process of making diazo copies by sublimation of reactant materials onto a copy sheet

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Dinaburg, M. S., Photosensitive Diazo Cpds., 1964, The Focal Press, p. 50 54. *
Landau, R. et al., J. of Photo. Sci., Vol. 13, 5/1965, p. 444 451 *
Van der Grinter, The Photographic Journal, 1952, Vol. 92B, p. 43 48. *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3944422A (en) * 1969-09-01 1976-03-16 Mita Industrial Company Limited Photosensitive material in use for diazo-type multicolor reproduction
US3918974A (en) * 1970-05-01 1975-11-11 Mita Industrial Co Ltd Process for the diazo-type multicolor reproduction
US4062644A (en) * 1976-03-30 1977-12-13 Graphic Magicians, Inc. Transfer ink and method of using same
US4157874A (en) * 1978-04-10 1979-06-12 Freeman Transfer Printing Co. Dye marking device
US4911733A (en) * 1979-06-20 1990-03-27 Canon Kabushiki Kaisha Process for fabricating color filters
US4725526A (en) * 1984-08-21 1988-02-16 Hoeschst Aktiengesellschaft Process for reducing halations using lubricant in the course of irradiating and developing reproduction layers used for preparing printing plates

Also Published As

Publication number Publication date
GB1318706A (en) 1973-05-31
DE2038242B2 (de) 1975-05-28
JPS4829059B1 (ja) 1973-09-06
DE2038242A1 (de) 1971-03-18
DE2038242C3 (de) 1976-01-08
FR2056955A1 (ja) 1971-05-07
NL154016B (nl) 1977-07-15
NL7011435A (ja) 1971-02-04
FR2056955B1 (ja) 1973-01-12

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