US3918974A - Process for the diazo-type multicolor reproduction - Google Patents

Process for the diazo-type multicolor reproduction Download PDF

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US3918974A
US3918974A US396667A US39666773A US3918974A US 3918974 A US3918974 A US 3918974A US 396667 A US396667 A US 396667A US 39666773 A US39666773 A US 39666773A US 3918974 A US3918974 A US 3918974A
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coupler
layer
original
percent
weight
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US396667A
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Kouzi Nihyakumen
Toshihiro Kouchi
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
    • G03C1/60—Compositions containing diazo compounds as photosensitive substances with macromolecular additives

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  • ABSTRACT A process for the diazo-type multicolor reproduction according to which it is possible to obtain multicolored copies in which portions corresponding to predetermined portions of an original are colored selectively in different hues without substantial mingling of colors. by conducting the heat transfer at relative!) low temperatures (for instance. at 6080C.). and a color former to be used in such process. which comprises a thermosublimative coupler and a thermosublimative. organic. solid transfer promotor having no coupling property in itself.
  • This invention relates to a process for diazo-type multicolor reproduction and to a colorfon-ner to be used in such process. More particularly, this invention relates to a process for the diazo-type multicolor reproduction according to which it is possible to obtain multi-colored copies in which portions corresponding to predetermined portions of an original are colored selectively in different hues without substantial mingling of colors, by conducting the heat transfer at relatively low temperatures (for instance, at 60 80C.), and to a color former to be used in such process.
  • a process for the diazo-type multicolor reproduction has been previously proposed based on the discovery that predetermined portions of an original can be reproduced into different hues regardless of difference or similarlity of the light transmission in the original, by conducting the steps of (A) exposingto light a diazotype photosensitive material containing at least one diazonium salt (which will be referred to as diazonium salt (c)) and (B) heating a layer of at least one thermovolatile or thermosublimative coupler (which will be referred to as coupler (a)) disposed in face-toface contact with such diazo-type photosensitive material at a portion corresponding to a predetermined portion of the original to be colored in a different hue, the steps being carried out coincidentally or in an order of (A) to (B) or (B) to (A), and then developing the lightexposed photosensitive material in the presence of a coupler having a lower coupling rate under developing conditions (which will be referred as coupler (b)”) than the thermovolatile or ther
  • thermovolatile or thermosublimative coupler is combined with the back face of an original at one or more portions predetermined to be colored in a different hue.
  • the thermovolatile coupler in the form of, for instance, an ink-like or waxy coloring composition is combined with the back face of the original by coating or transferring.
  • Most of thermovolatile and thermosublimative couplers have relatively high volatilizing or sublimating temperatures, and therefore, the heat transfer must be conducted at temperatures exceeding 100C.
  • the high heat transfer temperature results in the following disadvantages. Namely, the life of a copying machine is extremely shortened and its structure is inevitably complicated. Further, the high heat transfer temperature causes various operational difficulties.
  • thermovolatile or thermosublimative couplers when multi-colored copies are obtained by employing two or more thermovolatile or thermosublimative couplers'differing in their volatilizing or sublimating temperature, it is difiicult to determine the heat transfer temperature. More specifically, when the heat transfer temperature is determined depending on a coupler having a lower volatilizing or sublimating temperature, the amount of the coupler having a higher volatilizing or sublimating temperature transferred is very low and copies of a high color contrast cannot be obtained, whereas if the heat transfer temperature is determined depending on the coupler of a higher volatilizing or sublimating temperature, great excess of the coupler of a lower volatilizing or sublimating temperature is transferred by one transfer treatment, with the 2 result that the transfer layer is consumed by conducting the heat transfer only several times and the number of copies is extremely lowered.
  • the primary object of this invention is to provide a diazo-type multicolor reproduction process according to which the heat transfer of one or more couplers to a diazo-type photosensitive material can be effected at a relatively low temperature, and to provide a color former for use in conducting such process.
  • Another object of this invention is to provide a diazotype multicolor reproduction process according to which two or more couplers to be combined with a diazo-type photosensitive material can be heat-transferred with almost equal amounts at approximating temperatures, whereby many copies can be obtained from one original with the heat transfer layer formed thereon, while conducting the heat transfer at relatively low temperatures, and to provide a color former to be used in such process.
  • a color former for use in the diazo-type multicolor reproduction which comprises a thermovolatile or thermosublimative coupler, and a thermosublimative, organic, solid transfer promotor having no coupling property in itself.
  • thermovolatile or thermosublimative coupler a thermosublimative, organic, solid transfer promoter having no coupling property in itself is used as the coupler (a).
  • thermosublimative, organic, solid, transfer promoter it is essential that the thermosublimative, organic, solid, transfer promoter should not possess any coupling property in itself.
  • transfer promoter any organic compound that exhibits a high sublimating property at temperatures exceeding room temperature, especially at temperatures exceeding 60C. and has a meltingpoint above 60C., preferably above C. can be used.
  • the transfer promoter may be chosen from naphthalene, naphthalene derivatives, terpene compounds, halogenated benzenes and other organic solid sublimative compounds. Typical examples of such transfer promotor are as follows:
  • Thermovolatile or thermosublimative coupler (a) has a higher coupling rate under developing conditions than coupler (b).
  • Dyestuff (b)-(c), dyestuff (a)-(c), dyestutf (a')- (c) formed at the development have hues different from one another.
  • thermovolatile or thermosublimative coupler (a) Any coupler that can be volatilized or sublimated under heating conditions may be used as the thermovolatile or thermosublimative coupler (a) in this invention.
  • coupler (a) phenol derivatives, hydroxynaphthalene derivatives, aniline derivatives and active methylene group-containing compounds may be mentioned. In view of facilitation of the heat transfer operation it is preferred that these derivatives do not contain soluble groupslsuch as a sulfonic acid group.
  • Phenol Derivatives Phenol Pyrocatechol Resorcin Phloroglucin o-Hydroxybenzalcohol Resorcin monoglycol ether 4 Resorcin diglycol ether Hydrotoluquinonc Pyrogallol 5-Hydroxy-isophthalic acid Pyrogallol-4 carboxylic acid Vanillin lsovanillic acid Vanillic acid 2-Hydroxy-terephthalic acid 2-Hydroxy-p-toluylic acid 3-Hydroxy-p-toluylic acid S-Hydroxyo-toluylic acid 6-Hydroxy-m-toluylic acid Para-hydroxyphenylacetic acid Para-hydroxybenzaldehyde Ortho-hydroxybenzoic acid Ortho-hydroxybenzyl alcohol 4,4-Dihydroxybiphenol 3,5-Dichloro-salicyclic acid S-Chloro-Z-nitrophenol 2,S-Dihydroxyacetophenone 2,5-
  • the coupling rate of the coupler (b) should be lower than that of any of couplers (a). Selection of couplers (a) and (b) meeting the above requirement may be easily performed by those skilled in the art based on simple experiments.
  • Couplers having a relatively lower coupling rate may be selected among couplers recited above with respect to the thermovolatile or thermosuhlimative couplers (a) and he used as the coupler (b). In addition. the following may be used as coupler (b) in this invention.
  • an original for multicolor development is formed by apply ing at least one transparent or semi-transparent layer of a mixture of a thcrmovolatile or thermosublimative coupler (a) and a thermosublimative. organic. solid transfer promoter onto the back surface of a transparent or scmitransparent original to be copied. in one or more predetermined portions thereof.
  • thermovolatilc or thcrmosublimative coupler (a) is heat-transferred to the predetermined portion of the surface of the photosensitive material together with the transfer promoter at a relatively low temperature (60 C. and the light resolution of the diazonium salt (c) in the photosensitive material occurs depending on the light transmission of the original.
  • the diazonium salt (c) at the non-exposed are reacts selectively and preferentially with the coupler (a) to form a dy'estuff c) (a) and at other portions the diazonium salt (c) in the non-exposed are reacts 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 color former comprising the thermovolatile or thermosublimative coupler (a) and the transfer promoter 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 semitransparent substrate with a coating composition comprising the color former of this invention 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.
  • the color fonner of this invention for use in the diazo-type multicolor reproduction can be easily prepared by' dispersing a thermovolatile or thermosublimative coupler (a) and a thermosublimative. organic. solid transfer promoter in a liquid. semi-solid or solid dispersion medium.
  • Dispersion medium balance As the dispersion medium aliphatic alcohols such as methanol. ethanol. propanol. isopropanol. isobutyl alcohol and dimethyl form-amide; aromatic solvents such as benzene. toluene. xylene; esters; and neutral liquids having OH groups and boiling points of IUUZSUC. such as water. high boiling point alcohols. e.g.. n-hexyl alcohol.
  • n-heptyl alcohol 3-heptanol. 4-heptanol. and octanol. and glycols. e.g.. glycerine. ethylene glycol. propylene glycol. polyethylene glycol. l.3-butanediol. l.-l-butanediol and 2.3-butanediol may be used. These liquid substances may be used singly or in combination.
  • composition of the above recipe is applied to the back surface of an original in a portion predetermined to have a different hue by means of a brush.
  • a brush an installed felt pen. a ball pen. a coating roller. a sprayer or a printing machine.
  • Coloring material 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 heattransferable layer comprising the coupler (a) and transfer promotor 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 inklike color former composition for treating the back surface of an original. which was de scribed in l or a composition obtained by incorporating a binder or an extender into such ink'like composition is coated on a transparent or semitransparent sheet such as paper. plastic film or nonwoven 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 predetermined to have a dit ferent hue. It is possible to form a pressure-semi tive adhesive layer on the back surface of the coupler-transferring layer for preventing it from exfoli' ating from the original.
  • the so prepared original for multicolor development may be generally used 5 to l()() times repeatedly for the multicolor development. though the applicable frequency of the repeated use varies depending on the amount of coupler (a) coated. the coating method. the heating method and the developing method. Of course. when the heat-transferability of coupler a) in the layer for heat-transferring the coupler is lowered. it is sufficient to newly supply an additional layer for heat-transferring the coupler.
  • the abovementioned color former composition in use for the multicolor reproduction is applied to the back surface of a predetermined portion of an original to be copied. and is overlapped on a photosensitive material in a manner such that the heat transfer layer containing the coupler (a) and thermosublimative transfer promoter will be in face-to-face contact with the photosensitive surface of the photosensitive material. Then. the assembly is exposed to light and heated.
  • the photosensitive material containing a diazonium compound (c0 may be prepared by coating a sensitizing composition comprising (c) diazonium compound (c) and optionally the coupler (b) according to need depending on the developing method. on a substrate such as paper. plastic film. non-woven fabric and metal foil.
  • a substrate such as paper. plastic film. non-woven fabric and metal foil.
  • Azo coupling component (b) (L2 5. r Diazonium compound (c) (L2 it! i Organic acid (Ll ill r Coloring matter (Ltllll (LUIS Development promoter HI Hm I Extender (I 2.5 I Sohent 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.
  • Azo coupling component (b) (L1 5 (I Diazonium compound (c t (L2 5.11 Organic aeid tl.l H [Atender ll Stabilizer ll Coloring matter lLUtIl ll Sohent balance
  • the sensitizing composition of the above recipe is coated on a substrate such as paper and plastic film to form a photosensitive sheet.
  • the sensitizing composition of the above recipe is coated on a substrate such as paper. and dried to form 6U a photosensitive sheet.
  • R' and R" each are aliphatic groups. and Z and Y denote groups which can be introduced into the benzene nucleus.
  • R. R and R" are alkyl or aryl groups and X stands for an anion.
  • R is a divalent aryl group
  • R is a monovalent or divalent aryl or alkyl group.
  • X stands for an anion.
  • Y and Z are groups which can be introduced into the benzene nucleus.
  • A is a direct bond (phenyl pyrrolidine) or a divalent group such as O (morpholine).
  • S thiomorpholine
  • methylene phenylpipe ridine Specific examples of the compounds of this type are as follows:
  • 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 a state stabilized by an aryl sulfonate (in the form of a diazonium salt of an aromatic sulfonic acid). a diazosulfonate or the like.
  • the light exposure of the photosensitive material and the transfer of the color former of this invention to the photosensitive surface of the photosensitive material may be effected coincidentally.
  • the heat transfer of the coupler (a) may be effected coincidentally 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 at a temperature above 50C preferably C though a preferable heating temperature varies to some extend depending on the type of the coupler (a) and heating time.
  • the color former of this invention contains a thermosublimative. organic. solid transfer promotor as well as the coupler (a). in the heat transfer of the coupler (a) the heat transfer temperature can be considerably lowered by the interaction of the coupler (a) and the transfer promoter. as compared with the case where the coupler (a) is used singly. Further. when a plurality of couplers (a). (a' (a") forming colors differing in hues are coated on predetermined portions of an original to be copied and the heat transfer is conducted. the heat transfer temperatures of couplers (a). (a' ('a") can be approximated because of the presence of the thermosublimative. organic. solid transfer promoter.
  • the photosensitive material which has been thus exposed to light and on a predetermined portion of which the coupler (a) has been heat-transferred. is developed by customary known developing methods.
  • the coupler (b) may be either contained in the photosensitive material in advance or made present in the developer.
  • the development may be conducted by either a dry method or a wet method.
  • a photosensitive material containing coupler (b) as well as diazonium salt (c) it is preferred that prior to the development the photosensitive material on which the coupler (a) has been heatedtransferred is subjected to an affinity-increasing pre-treatment with a treating liquor comprising. singly or in combination. an aliphatic alcohol. an aromatic solvent. an ester.
  • the development may be accomplished sufficiently only by exposing the lightexposed photosensitive material to a mixture of ammonia and steam.
  • the development can be accomplished by dipping. roller coating or spraying methods with use of a liquid developer having. for instance. the following recipe: I
  • the development may be accomplished by contacting the lightexposed photosensitive sheet with a liquid developer containing an alkali.
  • multi-colored reproductive copies in which the portion corresponding to the predetermined portion of the original is colored with a dyestutf (a c) and other portions are colored with a dyestuff b )-(c) can be ob tained.
  • FIGS. 1 and 2 are diagrams illustrating the process for obtaining multi-colored copies with use of the color former of this invention.
  • thermovolatile or thermosublimative couplers 2' and 3' are coated on the back surfaces of images 2 and 3, respectively. of an original having im ages 1, 2 and 3.
  • latent images I". 2" and 3" corresponding to images 1, 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 ll, 12 and 13 colored in different hues is obtained.
  • 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 an other heat-transferable sheet containing coupler 3' are applied to the back surfaces of images 2 and 3, respectively.
  • the color former of this invention When the color former of this invention is used for the multicolor reproduction. it is possible to heat transfer the coupler (a) from the predtermined portion of the original to be copied in a different hue to the photosensitive material at a relatively low temperature. i.e.. a temperature only l020C. higher than the temperature adopted in the ordinary diazo-type reproduction process. and therefore. it is possible to obtain a copy in which the portion corresponding to the predetermined portion of the original is colored selectively in a different hue very distinctly without substantial mingling of colors. Further. Formation of a plurality of different colors may be accomplished by one development treatment. Once an original is treated with the color former of this invention. at least 5 multicolored copies. usu ally 2( l UU multi-colored copies.
  • the treated original used for the multicolor reproduction can be returned to the original state only by peeling off the layer or sheet of the color former applied thereto or by heating the color former-colored original at about [00C.
  • 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 2 An ink-like composition for forming a yellowish orange color is prepared by using acetoacetic-ochloroanilide instead of the acetoacetic anilide of Example 1
  • EXAMPLE 3 An ink-like composition of the following recipe is prepared as a red color-forming agent for treating the back surface of an original:
  • EXAMPLE 4 An ink-like composition of the following recipe is prepared as a brown color-forming agent for treating the back surface of an original:
  • Resorein 2H 3 ⁇ lnyl acetate resin 3 g (italic acid l5 3 Methanol hit rnl it ater balance l otai Hill ml
  • 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 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 desired to be reproduced in brown.
  • EXAMPLE 5 An ink-like composition of the following recipe is prepared as a blue color forming agent for treating the back surfaces of an original:
  • EXAMPLE 6 An ink-like composition of the following recipe is prepared as a reddish brown color-forming agent for treating the back surface of the original:
  • the above composition is directly used as a color former to be coated on the back surface of a portion of the original predetermined to be copied in reddish brown by means of a brush. a coating roller or a sprayer. or after it has been charged in a felt pen or ball pen. it is used as a color former for treating the back surface of a portion of the original to be copied in reddish brown.
  • EXAMPLE 7 A waxy composition to be used as a yellow colorformirtg agent for treating the back surface of an original is prepared by heat melting Acetoacetic acid anilide 25 g Camphor 15 g Stearic acid Hit) g Parafl'ln 50 g Terra abia 50 g and solidifying the melt.
  • the above composition is molded into a crayon sticklike or chalk-like form and is used as a color former to be coated on the back surface of a portion of the original desired to be reproduced in yellow.
  • a waxy composition to be used as a yellowish brown colorforming agent is prepared by heat melting Py rogallol Ill g Menthol l g Paraffin 5U g Terra abla 70 g Haze ax 20 g Stearic acid llll) g Magnesium carhonah: It) g 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 9 To the composition of Example S l()() g of mineral oil and 30 g of oleic acid are added. and the mixture is kneaded in a ball mill. 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 tool. Thus. the sheet is used as a material for forming a layer of the waxy color former agent on the back surface of a portion of the original desired to be reproduced in a different hue.
  • a waxy composition for forming a red color is prepared by heat melting l-Pheny l 3-methylpy ramlone l 5 l p-Dichlorohenzene Paraffin Stearic acid Diatomeceous earth Haze ax and solidifying the melt.
  • the above composition is molded to a crayon sticklike 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 1 I To the composition of Example l0 l0() g of mineral oil. 50 g oleic acid and g of Permanent Red are added. and the mixture is kneaded in a ball 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 fonned pressure-sensitive copy sheet is used as a material for forming a layer of the waxy color former composition on the back surface of a portion of the original to be copied in a different hue. in the same manner as described in Example 9.
  • a waxy color former composition for forming a blue color is prepared by heat melting -continued Stcaric acid lUtl g Paraflin ill g l)iatomaeeou- L'allh 3H g Ha/c ⁇ a ⁇ ll] g 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 l3 To the composition of Example I2 I00 g of mineral oil. g ofoleic acid 2U g of Oil Blue and 50 ml ofethanol are added. The mixture is well kneaded in a ball mill and coated on a substrate such as paper to form a pressure-sensitive copy sheet. The sheet is used as a material for forming a layer of waxy color former composition on the back surface of the original to be rcproduced in a different hue. in the same manner as de scribed in Example 9.
  • EXAMPLE l4 A composition of the following recipe is prepared as a red color-forming agent for treating the back surface of an original:
  • EXAMPLE 15 A composition of the following recipe is prepared as a brown color-forming agent for treating the back surface of an original:
  • EXAMPLE 16 A composition to be used as a brown color-forming agent for treating the back surface of an original is prepared by using pyrogallol instead of l-phenyl-3-mcthyl- 17 pyrazolone in Example 14. From this composition a sheet is formed for heat-transferring the coupler capable of forming a brown color.
  • EXAMPLE 1' A composition to be used as a blue color-forming agent for treating the back surface of an original is prepared by using l.6-dihydroxynaphthalene instead of lphenyl-3-methylpyrazolone in Example 14. From this composition a sheet is prepared for heat transferring the coupler capable of forming a blue color.
  • the sheet is overlapped on an original in which the back surface of a portion is treated with the ink-like color former composition prepared in Example 1 and the back surface of another portion is treated with the color former composition prepared in Example 3. Then the assembly is heated and light exposed by means of a mercury lamp and developed with a liquid developer of the following recipe:
  • the sheet is piled on an original in which one portion of the back surface is treated with the color former composition prepared in Example 2. Another portion of the back surface is treated with the color former composition prepared in Example 3 and still another portion of the back surface is treated with the color former composition of Example 5. Then. the assembly is heated and exposed to light by means of a mercury lamp to form a latent image of the diazonium salt.
  • Example 18 4-Diazo-N;N-dimethyl-aniline chloride'l/ZZnCl lll g Diethylene glycol -lll g Citric acid ill g 1.3-Dihydrovynaphthalene-(v sulfonic acid Ill g Zinc chloride ill g Thiourea ill g Patent Blue 0.1 g Water balance Total 1 liter
  • a photosensitive paper is prepared from the above solution by coating and drying. The photosensitive paper is piled on an Original, a portion of the back surface of which is treated with the coupler-heat-transferring sheet prepared in Example 14. Then the assembly is heated and printed by means of a mercury lamp. followed by development with gaseous ammonia and steam. As a result a clear two-color reproductive copy in which a portion corresponding to the portion treated with the treating agent of Example I4 is colored in red and another portion corresponding to the untreated portion is colored in dark blue is obtained.
  • a photosensitive paper is prepared from the above solution.
  • the photosensitive paper is overlapped on an original in which a portion of the back surface is treated with the waxy composition prepared in Example 8 and another portion of the back surface is treated with the composition prepared in Example It).
  • 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 three-color reproductive copy in which a portion corresponding to the portion of the original treated with the composition of Example 8 is colored in brown.
  • a portion corresponding to the portion treated with the composition of Example 10 is colorcd in red. and other portion corresponding to the untreated portion of the original is colored in bluish violet is obtained
  • EXAMPLE 22 Multicolor-forming photosensitive paper for dry development A solution of the following recipe is prepared:
  • the back surface of another part of the image is treated with the composition of Example 4 and the back surface of still another part is treated with the composition of Example 5.
  • the assembly is heated and printed at 70 80C. by means of a mercury lamp. and the so treated photosensitive sheet is developed with gaseous ammonia and steam.
  • a four-colored copy of a clear color contrast is obtained in which a portion corresponding to the portion treated with the composition of Example 3 is colored in red.
  • a portion corresponding to the portion treated with the composition of Example 4 is colored in yellowish brown.
  • a portion corresponding to the portion treated with the composition of Example 5 is colored in blue.
  • a portion Corresponding to the untreated portion of the original is colored in black.
  • Multicolor-forming diazo-type photosensitive paper for dry development for forming second original A solution of the following recipe is prepared:
  • a semi-transparent paper for second original such as tracing paper and dried to form a photosensitive paper.
  • the photosensitive paper is piled on an original. a portion of the back surface of which is treated with the waxy color former composition prepared in Example 12.
  • the assemly is heated and printed by means of a mercury lamp, followed by development with gaseous ammonia and steam.
  • a clear two-color reproductive copy usable as the intermediate second original is obtained in which a portion corresponding to the portion of the original treated with the composition of Example 12 is colored in red and another portion corresponding to the untreated portion of the original is colored in yellowish brown.
  • a photosensitive paper is prepared by conducting the coating and drying in the same manner as in Example l8.
  • the so formed photosensitive paper is piled on an original, a portion of the back surface of which is treated with the pressure-sensitive sheet prepared in Example 9 and another portion of the back surface of which is treated with the pressure-sensitive sheet prepared in Example ll.
  • 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 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.
  • a clear three-color reproductive copy without any substantial mingling of color is obtained. in which a portion corresponding to the part treated with the treating material of Example 3 is colored in red. a portion corresponding to the part treated with the treating material of Exampie 4 is colored in brown, and another portion corresponding to the untreated part of the original is colored in blue.
  • COMPARATIVE EXAMPLE 1 This example illustrates results of comparative experiments conducted to confirm effects attained by the in corporation of the the rmosublimative. organic. solid transfer promoter in the color former of this invention.
  • each of the above solutions is coated on the back surface of a semi-transparent original (tracing paper. Chemical No. 60) in an amount of about 0.2 g/m'-'.
  • the so coated original is dried to fonn a sample sheet original.
  • the sample sheet is piled on the photosensitive sheet prepared in Example 21 in a manner such that the treated surface of the sample is in face-to-face contact with the photosensitive layer of the photosensitive sheet.
  • the assembly is allowed to pass through hot rolls maintained at 50C., 60C.. C. and C., respectively, to effect the heat transfer of the thermovolatile or thermosublimative coupler.
  • the so treated photosensitive sheet is subjected to the development with gaseous ammonia and steam. With respect to each sample original. the number of copies of a distinct color contrast obtained at each heat transfer temperature is counted. Results are shown in Table 1 below.
  • thermovolatile coupler sample l-phenyl-3- methylpyrazolone (5) and resorcin are selected.
  • Each of the sample chemicals is sufficiently ground in a mortar and is sufficiently dried in a silica gel desiccator.
  • a precisely weighed amount (0.3 g) of each sample is charged in a vessel having a certain inner surface area and subjected to a heat treatment at 100C. ll0C. and 120C. The weight of the sample is determined at certain time intervals and the weight loss is calculated each time.
  • each sample is blended with 1.5 g of eamphor (special grade) and the blend is sufficiently mixed and ground in a mortar. Then. the blend is subjected to the same heat treatment as above to determine the weight loss of the blend. Then. the weight loss of the coupler alone is calculated by reducing the weight loss of champhor alone determined separately, from the above weight loss of the blend. Thus. the effect of eamphor for promoting the volatilization or sublimation of the sample coupler is examined. Results are shown in Tables 2 and 3 below.
  • the values in parenthesis are values obtained when d-camphor is incorporated in the sample coupler.
  • the use of the color former of this invention increases the number of copies by 7 sheets at C.. by l2 sheets at C. and by 18 sheets at C. in the case of l-phenyl-3- methylpyrazolone 5 as compared with the use of the coupler alone. Accordingly. it is construed that the heat transfer temperature may be lowered by about 10 l5C. with the use of the color former of this invention comprising the thermovolatile or therm0sublimative coupler and the thermosublimative. organic. solid transfer promoter. In the case of resorcin. the use of the color former of this invention increases the number of copies by 7 sheets at 60C. and by 22 sheets at 70C. Accordingly. it is construed that also in this case the heat transfer temperature may be lowered by about l0 15C. with the use of the color former of this invention.
  • thermosublimative. organic. solid transfer promoter when used in combination with a thermovolatile or thermosublimative coupler. the efficiency of transfer of the coupler can be greatly improved.
  • a process for multi-color reproduction which comprises:
  • said assembly consisting of (i) an original sheet having opaque image areas and transparent non-image areas on a surface and a layer containing at least one thermovolatile or sublimable azo coupler (a) and a solid organic sublimable compound selected from the group consisting of eamphor. naphthalene. bornane, menthol and p-dichlorobenzene. and said layer being located in only pre-selected areas which are contiguous with opaque image areas of said original sheet. said pre-selected area being present in only a portion of the areas contiguous with said opaque image areas of said original sheet.
  • 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 material (ii) so that the layer of the azo coupler (a) comes into face-to-face contact with the phostosensitive layer;
  • menthol and p-dichlorobenzene and said layer being located in only pre-selected areas which are contiguous with opaque image areas of said original sheet. said pre-selected area 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 said original sheet (i) being superposed on said diazo-type photosensitive material (ii) so that the layer of the azo coupler (a) comes into face-to-face contact with the ph'otosensitive layer;
  • steps A] and (B) being performed simultaneously or in the time sequence of(A) to B) or (B) to (A and C. thereafter developing the exposed photosensitive layer with an alkaline aqueous liquid developer containing 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). whereby in the unexposed latent image area of the portion to which the coupler (a) has been heat-transferred.
  • a dye (c a) having a certain hue or color is formed by the selective reaction of the heat-transferred coupler (a) with the diazonium salt (c) and at the samd time. in the anexposed latent image areas to which the coupler (a) has not been heat-transferred.
  • a dye (e)-(b) having a different hue or color from said dye (c)- (a) is formed by the reaction of the coupler (b) with the diazonium salt (c thus producing a multicolored copied image.
  • said coupler (a) is selected from the group consisting of phenol compounds, hydroxynaphthalene compounds. aniline compounds and compounds containing an active methylene group.

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Abstract

A process for the diazo-type multicolor reproduction according to which it is possible to obtain multi-colored copies in which portions corresponding to predetermined portions of an original are colored selectively in different hues without substantial mingling of colors, by conducting the heat transfer at relatively low temperatures (for instance, at 60*-80*C.), and a color former to be used in such process, which comprises a thermosublimative coupler and a thermosublimative, organic, solid transfer promotor having no coupling property in itself.

Description

United States Patent 11 1 Nihyakumen et al.
PROCESS FOR THE DlAZO-TYPE MULTICOLOR REPRODUCTION Inventors: Kouzi Nihyakumen: Toshihiro Kouchi, both of Hirakata; Taizo Yokoyama, Shinmorishoji; Yasuo Ueda, Kobe; Yasutoki Kamezawa, Hirakata; Tatsuo Aizawa. Osaka. all of Japan Assignee: Mita Industrial Company. Ltd.,
Osaka. Japan 1 1 Nov. 11, 1975 2.789.904 4/1957 Bonhrook et a1. 96/49 3.157.503 11/1964 Kosar 96/49 3.199.982 111/1965 Kashinabar'ah 96/49 3.318.699 5/1967 Lind 96/49 3.353.984 11/1967 Landau 96/49 X 3.454.764 7/1969 Collier Jo 49 X 3.469.981 9/1969 Kosar 96/49 3.653.903 4/1972 Nihyakumen et a1 96/49 3.715.213 3/1973 NlIl HlkLllTlLfl et al 96/49 3.725.066 4/1973 Nih \akumen et a1 96/49 FOREIGN PATENTS OR APPLICATIONS l.tl(|t1.l5l 8/1965 United Kingdom............... 96/49 Primary E.\'mimm'Charles L. Bowers. Jr. .-1rmrr1e Agent. or Firm-Sherman 8; Shalloway (57] ABSTRACT A process for the diazo-type multicolor reproduction according to which it is possible to obtain multicolored copies in which portions corresponding to predetermined portions of an original are colored selectively in different hues without substantial mingling of colors. by conducting the heat transfer at relative!) low temperatures (for instance. at 6080C.). and a color former to be used in such process. which comprises a thermosublimative coupler and a thermosublimative. organic. solid transfer promotor having no coupling property in itself.
10 Claims, 2 Drawing Figures I 2 3 1 2 3 i omom$ PREPARATION OF ORIGINAL FOR MULTICOLOR DEVELOPMENT TRANSFERRING COUPLER STABIL IZING TREATMENT U.S. Patent Nov. 11, 1975 3,918,974
ORIGINAL I 2 3 I 2 3 mmm $1 PREPARATION OF ORIGINAL FOR MULTICOLOR DEVELQPMENT COUPLER fig SHEET FOR EEGNSFERRING 3 LIGHT SOURCE LIGHT LIGHT EXPOSURE 1 f" 2! HEAT TRANSFER 1 N Lr/ ll STABILIZING TREATMENT iII EI2 EI3 Ell EI2 '!I3 PROCESS FOR THE DlAZO-TYPE MULTICOLOR REPRODUCTION This is a division, of application Ser. No. [39,442, filed May 3, 1973, now abandoned.
This invention relates to a process for diazo-type multicolor reproduction and to a colorfon-ner to be used in such process. More particularly, this invention relates to a process for the diazo-type multicolor reproduction according to which it is possible to obtain multi-colored copies in which portions corresponding to predetermined portions of an original are colored selectively in different hues without substantial mingling of colors, by conducting the heat transfer at relatively low temperatures (for instance, at 60 80C.), and to a color former to be used in such process.
A process for the diazo-type multicolor reproduction has been previously proposed based on the discovery that predetermined portions of an original can be reproduced into different hues regardless of difference or similarlity of the light transmission in the original, by conducting the steps of (A) exposingto light a diazotype photosensitive material containing at least one diazonium salt (which will be referred to as diazonium salt (c)) and (B) heating a layer of at least one thermovolatile or thermosublimative coupler (which will be referred to as coupler (a)) disposed in face-toface contact with such diazo-type photosensitive material at a portion corresponding to a predetermined portion of the original to be colored in a different hue, the steps being carried out coincidentally or in an order of (A) to (B) or (B) to (A), and then developing the lightexposed photosensitive material in the presence of a coupler having a lower coupling rate under developing conditions (which will be referred as coupler (b)") than the thermovolatile or therrnosublimative coupler (a). In this diaz o-type multicolor reproduction process, a thermovolatile or thermosublimative coupler is combined with the back face of an original at one or more portions predetermined to be colored in a different hue. The thermovolatile coupler in the form of, for instance, an ink-like or waxy coloring composition is combined with the back face of the original by coating or transferring. Most of thermovolatile and thermosublimative couplers have relatively high volatilizing or sublimating temperatures, and therefore, the heat transfer must be conducted at temperatures exceeding 100C. The high heat transfer temperature results in the following disadvantages. Namely, the life of a copying machine is extremely shortened and its structure is inevitably complicated. Further, the high heat transfer temperature causes various operational difficulties. Still further, when multi-colored copies are obtained by employing two or more thermovolatile or thermosublimative couplers'differing in their volatilizing or sublimating temperature, it is difiicult to determine the heat transfer temperature. More specifically, when the heat transfer temperature is determined depending on a coupler having a lower volatilizing or sublimating temperature, the amount of the coupler having a higher volatilizing or sublimating temperature transferred is very low and copies of a high color contrast cannot be obtained, whereas if the heat transfer temperature is determined depending on the coupler of a higher volatilizing or sublimating temperature, great excess of the coupler of a lower volatilizing or sublimating temperature is transferred by one transfer treatment, with the 2 result that the transfer layer is consumed by conducting the heat transfer only several times and the number of copies is extremely lowered.
Further research on the above-mentioned diazo-type multicolor reproduction process has been conducted with a view to overcoming these defects, and it has now been found that when a certain solid substance having no coupling property in itself is incorporated into the thermovolatile or then'nosublimative coupler (a) the transfer of the coupler (a) to a diazo-type photosensitive material can be effected at a relatively low temperature very easily and even if two or more couplers (a) are used, heat transfer temperatures and the amounts of the couplers transferred can be almost approximated. Based on this finding, the present invention has been developed.
Accordingly, the primary object of this invention is to provide a diazo-type multicolor reproduction process according to which the heat transfer of one or more couplers to a diazo-type photosensitive material can be effected at a relatively low temperature, and to provide a color former for use in conducting such process.
Another object of this invention is to provide a diazotype multicolor reproduction process according to which two or more couplers to be combined with a diazo-type photosensitive material can be heat-transferred with almost equal amounts at approximating temperatures, whereby many copies can be obtained from one original with the heat transfer layer formed thereon, while conducting the heat transfer at relatively low temperatures, and to provide a color former to be used in such process.
In accordance with this invention, a color former for use in the diazo-type multicolor reproduction is provided, which comprises a thermovolatile or thermosublimative coupler, and a thermosublimative, organic, solid transfer promotor having no coupling property in itself. The above objects of this invention can be at.- tained by the use of such color former.
In accordance with this invention, an improvement of the above-mentioned diazo-type multicolor reproduc tion process previously proposed, is provided wherein a color former comprising a thermovolatile or thermosublimative coupler, and a thermosublimative, organic, solid transfer promoter having no coupling property in itself is used as the coupler (a).
In this invention it is essential that the thermosublimative, organic, solid, transfer promoter should not possess any coupling property in itself. As such transfer promoter any organic compound that exhibits a high sublimating property at temperatures exceeding room temperature, especially at temperatures exceeding 60C. and has a meltingpoint above 60C., preferably above C. can be used.
The transfer promoter may be chosen from naphthalene, naphthalene derivatives, terpene compounds, halogenated benzenes and other organic solid sublimative compounds. Typical examples of such transfer promotor are as follows:
Naphthalene d-Camphor Menthol Camphene Benzoic acid Maleic anhydride Phthalic anhydride Oxalic acid Formic acid Anthranic acid Ethylboric acid Phenylhydrazine hydrochloride p-Hydroxyphenyl acetic acid Atropine Z-Aminoquinoline a-Chloroacrylic acid o-Chlorobenzoic acid p-Dichlorobenzene Chlorofumaric acid Diacetone-D-glucose l,4 Cyclohexadione 2.6-Dichlorobenzoic acid Di-a-naphthyl ketone N,N-diphenyl acetamide 2,4-Dimethyl-3-furan-carboxylic acid Dimethylphosphinic acid Cinnamylideneacetic acid Tartronic acid Thiourethane 2,3,4,5-Tetramethylpyrrol Triiodobenzene a-Naphthyl ketone l,8-Naphthylene diamine Nitrobenzonitrile Hydrochelidonic acid Pyridine carboxylic acid Pyrene Phenanthrene Phenylpropiolic acid S-Furancarboxylic acid o-Benzylbenzoic acid Bornane Meconine Mesitylenic acid S-Methyl-2-furancarboxylic acid Lapachol [t is essential that among the thermovolatile or thermosublimative coupler (a) to be used in the color former of this invention, a coupler (b) and a diazonium salt (c) the following relations should be established in conducting the multicolor reproduction according to this invention:
l. Thermovolatile or thermosublimative coupler (a) has a higher coupling rate under developing conditions than coupler (b).
I]. Dyestuff (b)-(c), dyestuff (a)-(c), dyestutf (a')- (c) formed at the development have hues different from one another.
Any coupler that can be volatilized or sublimated under heating conditions may be used as the thermovolatile or thermosublimative coupler (a) in this invention. As such coupler (a) phenol derivatives, hydroxynaphthalene derivatives, aniline derivatives and active methylene group-containing compounds may be mentioned. In view of facilitation of the heat transfer operation it is preferred that these derivatives do not contain soluble groupslsuch as a sulfonic acid group.
Examples of these derivatives usable as coupler (a) are as follows:
Phenol Derivatives Phenol Pyrocatechol Resorcin Phloroglucin o-Hydroxybenzalcohol Resorcin monoglycol ether 4 Resorcin diglycol ether Hydrotoluquinonc Pyrogallol 5-Hydroxy-isophthalic acid Pyrogallol-4 carboxylic acid Vanillin lsovanillic acid Vanillic acid 2-Hydroxy-terephthalic acid 2-Hydroxy-p-toluylic acid 3-Hydroxy-p-toluylic acid S-Hydroxyo-toluylic acid 6-Hydroxy-m-toluylic acid Para-hydroxyphenylacetic acid Para-hydroxybenzaldehyde Ortho-hydroxybenzoic acid Ortho-hydroxybenzyl alcohol 4,4-Dihydroxybiphenol 3,5-Dichloro-salicyclic acid S-Chloro-Z-nitrophenol 2,S-Dihydroxyacetophenone 2,5-Dinitrophenol 2,4-Dinitrophenol 2,4-Dinitroresorcin 4,6-Dibromo-2-nitrophenol 2,5-Dimethyl hyroquinone Aniline Derivatives Meta-aminobenzoic acid Dimethyl-meta-aminophenol 2-Amino-p-crsol Ortho-aminophenol Meta-aminophenol Para-aminophenol Para-chloroaniline 3 ,4-Diaminotoluene Active Methylene Group-Containing Compounds l-Phenyl-3-methylpyrazolene (5) l -Phenyl- 3-carboxypy razolone Acetoacetic acid anilide Acetoacetic-o-chloroanilide Hydroxynaphthalene Derivatives conducting the multicolor reproduction with use of the color former of this invention, any coupler that has a lower coupling rate with the diazonium salt (c) under the developing conditions than the rate of coupling of the thermovolatile or thermosublimative coupler (a) contained in the color former with the diazonium salt (c) can be used. When a plurality of thermovolatile or thermosublimative couplers (a) are used, the coupling rate of the coupler (b) should be lower than that of any of couplers (a). Selection of couplers (a) and (b) meeting the above requirement may be easily performed by those skilled in the art based on simple experiments.
Couplers having a relatively lower coupling rate may be selected among couplers recited above with respect to the thermovolatile or thermosuhlimative couplers (a) and he used as the coupler (b). In addition. the following may be used as coupler (b) in this invention.
Phenol Derivatives .5,6-Trimethylphenol Hydroxymethylphenol Z-hydroxyphenyl )-propionic acid m-Phenylaminomethyl )-phenol 4-Mcthyl-Z-hydroxyphenol )-glutaric acid 2.5-Dimethyl-6-( N-dimethylaminomethyl )-phenol l.3-Dimethyl ether of pyrogallol a-Resorcyclic acid ethanolamine B-Resorcylic acid N-LauryLp-aminophenol N-Acyl-m-aminophenol Meta-hydroxy-acetoanilide Ortho-N-hydroxyphenyl-monoguanidine Para-N-Hydroxyphenylbiguanidine 2.5-Dimethyl-4-morpholinomethyl phenol l-Methy'l-5-isopropyl-morpholinomethyl phenol 4-Morpholinomethylresorcinol monomcthy'l ether 3.3,S-Trihydroxydiphenyl 3 .3 ,5 .5 "Tetrahy'droxydiphenyl -Tetrahydroxydiphenvl 2,2',4.4'-Tetrahydroxydipheny'l 2.4.4-Trihydroxydiphenyl-2'-sulfonic acid Z,4.6.3'.5-Pentahydroxy'dipheny'l 2.2',4.4'-Tetrahydroxydiphenyl sulfide Naphthols .3-Dihydroxynaphthalene-o-sulfonic acid -Naphthol-3,6-disulfonic acid .7-Dihydroxynaphthalene-3-sulfonic acid .8-Dihy'droxynaphthalene-o-sulfonic acid .S-Dihydroxynaphthalene-S-sulfonic acid .8-Aminonaphthol--sulfonic acid .7-Dihy'droxynaphthalene-3,o-disulfonic acid Benzoylaminonaphthol-Z-sulfonic acid Dihydroxy'naphthalene-6sulfonic acid. vdroxy-3-naphthionic-N-B-hydroxyethyl amide ether Active Methylene Group-Containing Compounds Acetoacetic acid cyclohexylamide Acetoacetic acid benzylamide Cyanoacetoanilide Cyanoacetomorpholine Hetcrocyclic Compounds l 3 -Sulfoamide )-phenyl-3-methylpyrazolone-5 l-( 4'-Carboxy-ethylphenyl l-3-dodecy'l-pyrazolone-5 S-Hydroxyl .Z-naphthylimidazole Z-Methyl-J-hy droxyhenzimidazole 7Methy l-4hydrosy benzothiazole l .7-Dimethy l--lhydroxy-benzotriazole B-hydroxythiphene-S-carboyylic acid l-3-4-Cyclopentatrione In conducting the diazo-ty pe multicolor reproduction with use of the color former comprising the above mentioned thcrmovolatile or thermosublimative coupler (a) and thermosublimath e. organic. solid transfer promoter in accordance with this invention. at first an original for multicolor development is formed by apply ing at least one transparent or semi-transparent layer of a mixture of a thcrmovolatile or thermosublimative coupler (a) and a thermosublimative. organic. solid transfer promoter onto the back surface of a transparent or scmitransparent original to be copied. in one or more predetermined portions thereof.
The so formed original for multicolor development is overlapped on the diazo-type photosensitive material containing at least one diazonium salt in a manner such that the layer of coupler (a) will confront the photosensitive surface of the photosensitive material. and the light-exposure and heating are effected coincidentally or successively in this order or the reverse order. Thus. the thermovolatilc or thcrmosublimative coupler (a) is heat-transferred to the predetermined portion of the surface of the photosensitive material together with the transfer promoter at a relatively low temperature (60 C. and the light resolution of the diazonium salt (c) in the photosensitive material occurs depending on the light transmission of the original. When the so exposed photosensitive material is developed by' a method known per se. at the predetermined portion to which the coupler (a) has been heat-transferred. the diazonium salt (c) at the non-exposed are reacts selectively and preferentially with the coupler (a) to form a dy'estuff c) (a) and at other portions the diazonium salt (c) in the non-exposed are reacts with coupler (b) to form a dyestuff (c) (b). As a result 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 color former comprising the thermovolatile or thermosublimative coupler (a) and the transfer promoter 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 semitransparent substrate with a coating composition comprising the color former of this invention 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.
The color fonner of this invention for use in the diazo-type multicolor reproduction can be easily prepared by' dispersing a thermovolatile or thermosublimative coupler (a) and a thermosublimative. organic. solid transfer promoter in a liquid. semi-solid or solid dispersion medium.
Such color former composition will now be described by referring to some embodiments.
l. Ink-like color former composition:
('oupler (a) 5.0 Jltt) r lhcrmosuhlimatnc transfer promoter 51) 3t) H '1 ('oloring material a 1 o '1 Binder H ill I Dispersion assistant ll 1t! '1 Dispersion medium balance As the dispersion medium aliphatic alcohols such as methanol. ethanol. propanol. isopropanol. isobutyl alcohol and dimethyl form-amide; aromatic solvents such as benzene. toluene. xylene; esters; and neutral liquids having OH groups and boiling points of IUUZSUC. such as water. high boiling point alcohols. e.g.. n-hexyl alcohol. n-heptyl alcohol. 3-heptanol. 4-heptanol. and octanol. and glycols. e.g.. glycerine. ethylene glycol. propylene glycol. polyethylene glycol. l.3-butanediol. l.-l-butanediol and 2.3-butanediol may be used. These liquid substances may be used singly or in combination.
It is possible to incorporate a coloring material so as to confirm the formation of a film of the color former composition. or to use a binder for the purpose of obtaining a good fixation of the coupler (a).
The composition of the above recipe is applied to the back surface of an original in 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.
2. Waxy color former composition:
Coloring material 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 heattransferable layer comprising the coupler (a) and transfer promotor on the back surface of an image predetermined to have a different hue.
3. Coupler-transferring sheet for treating the back surface of an original:
The inklike color former composition for treating the back surface of an original. which was de scribed in l or a composition obtained by incorporating a binder or an extender into such ink'like composition is coated on a transparent or semitransparent sheet such as paper. plastic film or nonwoven 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 predetermined to have a dit ferent hue. It is possible to form a pressure-semi tive adhesive layer on the back surface of the coupler-transferring layer for preventing it from exfoli' ating from the original.
The so prepared original for multicolor development may be generally used 5 to l()() times repeatedly for the multicolor development. though the applicable frequency of the repeated use varies depending on the amount of coupler (a) coated. the coating method. the heating method and the developing method. Of course. when the heat-transferability of coupler a) in the layer for heat-transferring the coupler is lowered. it is sufficient to newly supply an additional layer for heat-transferring the coupler.
The abovementioned color former composition in use for the multicolor reproduction is applied to the back surface of a predetermined portion of an original to be copied. and is overlapped on a photosensitive material in a manner such that the heat transfer layer containing the coupler (a) and thermosublimative transfer promoter will be in face-to-face contact with the photosensitive surface of the photosensitive material. Then. the assembly is exposed to light and heated.
The photosensitive material containing a diazonium compound (c0 may be prepared by coating a sensitizing composition comprising (c) diazonium compound (c) and optionally the coupler (b) according to need depending on the developing method. on a substrate such as paper. plastic film. non-woven fabric and metal foil. The preparation of such photosensitive material will novv be described by referring to same examples.
A. Sensitizing composition for dry development:
Azo coupling component (b) (L2 5. r Diazonium compound (c) (L2 it! i Organic acid (Ll ill r Coloring matter (Ltllll (LUIS Development promoter HI Hm I Extender (I 2.5 I Sohent 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.
R. Two-component-type sensitizing composition for wet development:
Azo coupling component (b) (L1 5 (I Diazonium compound (c t (L2 5.11 Organic aeid tl.l H [Atender ll Stabilizer ll Coloring matter lLUtIl ll Sohent balance The sensitizing composition of the above recipe is coated on a substrate such as paper and plastic film to form a photosensitive sheet.
C. One-component-type sensitizing composition for wet development:
Diazonium compound lc) 0.1 5.11 '1 Organic acid t).l 511) Evtender 9 25 r Coloring matter lllltll (M125 1 Sohent balance The sensitizing composition of the above recipe is coated on a substrate such as paper. and dried to form 6U a photosensitive sheet.
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.
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-ethylN-B-hydroxyethyl aniline (referred to simply as "EH salt") 4-Diazo-N.N-bis-B-hydroxyethyl aniline 4-Diazo-Nmethyl-NB-hydroxyethyl aniline 4-Diazo-N-ethyl-N'B-hydroxypropyl aniline Other diazonium salts of p-pherylene diamines N.N- substituted with alkyl or hydroxy-alkyl groups:
4-Diazo-N-ethyl-N-( Bdiethylaminoyethyl aniline 4-Diazo-2-chloroNN-diethyl aniline I 4-Diazo-Z-methyl-NN-diethyl aniline 4-Diazo-2-iodo-N.Ndiethyl aniline 4'Diazo-2-trifluoromethyl-N,N-diethyl aniline 4-Diazo-N-ethyl-N-benzyl aniline 4-Diazo-N-methyl-N-benzyl aniline (referred to simply as methyl benzyl) Aminohydroquinone ether-type compounds of the following general formula:
wherein R. R and R" are alkyl or aryl groups and X stands for an anion.
Specific examples of the compounds of the above type are as follows:
4-Diazo-2.5-dibutoxy-N,N-diethyl aniline 4-Diazo-2,S-diethoxy-N-benzoyl aniline (referred to simply as BB salt) 4-Diazo-2.S-diethoxyN-ethyl-N-benzoyl aniline 4-Diazo-2.S-dibenzyloxyN-benzoyl aniline 4-Diazo-2-chloro-5methoxy-N-benzoyl aniline 4-Diazo-2.5diethoxy-N-benzoyl-methyl aniline 4-Diazo-2,5diethoxy-N-benzoyloxy-methyl aniline Other 4-diazo-2,5-dioxyalkyl (cr dioxyaryH-N-alkyl (or aryl) compounds and derivatives thereof Aminodiphenyl compounds, aminodiphenyl amine compounds and their analogues of the following general formulas:
wherein 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 RAR' are diarylamine (A; NH). diphenyl A; direct bond). diphenyl oxide (A: O). diaryl methane (A; CH:). stilbene (A; CH=CH) and diaryl or dialkyl sulfide (A; S).
Ill
Specific examples of the compounds of the above type are as follows:
Para-diazophenyl amine 4-Diazo'2.5.4'-triethoxy diphenyl amine 4-Diazo-2.5.4-triethoxydiphenyl 4,4'-Bis-diazo-2.2 ,5 .5 'tetrahhydroxydiphenyl methane Bis-diaxo-8,8'-dichloro-S.5dimethoxy benzidine 4-Diazo-2,S-dimethoxyphenylethyl sulfide 4-Diazo-l5-diethoxy-4'-methyl-diphenyl sulfide Heterocyclic amine derivatives of the following general formula:
wherein X stands for an anion. Y and Z are groups which can be introduced into the benzene nucleus. and A is a direct bond (phenyl pyrrolidine) or a divalent group such as O (morpholine). S (thiomorpholine) and methylene (phenylpipe ridine Specific examples of the compounds of this type are as follows:
4-Diazo-2,5-dibutoxyN-phenyl morpholine 4-Diazo-2.S-diethoxy-N-phenyl morpholine 4-Diazo-Z-methyoxy-N-thio morpholine 4-Diazo-N-phenyl piperidine 4-Diazo-N-phenyl pyrrolidine 4-Diazo-2.5di-n-butoxy-N-phenyl piperidine Other derivatives of 4-Diazo-N-phenyl heterocyclic amines.
NN-Substituted orthophenylene diamine derivatives and orthoamino-phenol derivatives.
Specific examples of the compounds of this type are as follows:
Z-Diazo4-methylmercapto-N.N'-dimethyl aniline Z-Diazo-S-benzoylamino-N.N-dimethyl aniline 2-Diazol-naphthol-S-sulfonic acid The above-mentioned 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 a state stabilized by an aryl sulfonate (in the form of a diazonium salt of an aromatic sulfonic acid). a diazosulfonate or the like.
The light exposure of the photosensitive material and the transfer of the color former of this invention to the photosensitive surface of the photosensitive material may be effected coincidentally. For instance, when a mercury lamp is used as the light source for exposure, the heat transfer of the coupler (a) may be effected coincidentally with the exposure by the heat conveyed through a cylinder glass of the light source maintained at a relatively high temperature. Of course. 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 at a temperature above 50C preferably C though a preferable heating temperature varies to some extend depending on the type of the coupler (a) and heating time.
It is also possible to adopt a method comprising piling the above-mentioned original for multicolor development and the photo-sensitive material. passing the assembly through a heated roller or an infrared radiation zone to heat the coupler layer of the original at the above-mentioned temperature and to effect the heat transfer of the coupler a). and then passing the same through an exposure zone to effect the exposure of the photosensitive material.
It is also possible to adopt a method in which the exposure and heat transfer are conducted in an order reverse to that of the above method. namely a method comprising forming an assembly of the original for multicolor development and the photosensitive material. passing the assembly through an exposure zone to of feet the expodure of the photosensitive material and then passing the same through a heating zone to effect the heat transfer of the coupler (a).
Since the color former of this invention contains a thermosublimative. organic. solid transfer promotor as well as the coupler (a). in the heat transfer of the coupler (a) the heat transfer temperature can be considerably lowered by the interaction of the coupler (a) and the transfer promoter. as compared with the case where the coupler (a) is used singly. Further. when a plurality of couplers (a). (a' (a") forming colors differing in hues are coated on predetermined portions of an original to be copied and the heat transfer is conducted. the heat transfer temperatures of couplers (a). (a' ('a") can be approximated because of the presence of the thermosublimative. organic. solid transfer promoter.
The photosensitive material which has been thus exposed to light and on a predetermined portion of which the coupler (a) has been heat-transferred. is developed by customary known developing methods. The coupler (b) may be either contained in the photosensitive material in advance or made present in the developer. The development may be conducted by either a dry method or a wet method. When a photosensitive material containing coupler (b) as well as diazonium salt (c) is used it is preferred that prior to the development the photosensitive material on which the coupler (a) has been heatedtransferred is subjected to an affinity-increasing pre-treatment with a treating liquor comprising. singly or in combination. an aliphatic alcohol. an aromatic solvent. an ester. a glycol or a liquid having OH groups and boiling at 100 200C. such as water or high boiling point alcohols. to thereby attain a uniform contact between the heattransferred coupler (a) and the diazonium salt remaining unexposed. In conducting the above pre-treatment it is desired to allow the above treating liquor to contact the photosensitive material while keeping the liquor in the liquid or vapor state. In the ease of the dry development. the development may be accomplished sufficiently only by exposing the lightexposed photosensitive material to a mixture of ammonia and steam. When a one-component-type photosen sitive sheet for wet development is used. the development can be accomplished by dipping. roller coating or spraying methods with use of a liquid developer having. for instance. the following recipe: I
Coupler (b) ILL 5 Alkali [1.5 It) '1 Reducing agent II lit: Surfactant ll (I a '1 -continued Water balance When a two-component-type photosensitive sheet for wet development is used. the development may be accomplished by contacting the lightexposed photosensitive sheet with a liquid developer containing an alkali.
Thus multi-colored reproductive copies in which the portion corresponding to the predetermined portion of the original is colored with a dyestutf (a c) and other portions are colored with a dyestuff b )-(c) can be ob tained.
The diazo-type multicolor reproduction process with use of the color former ofthis invention will now be explained by referring to the accompanying drawings.
FIGS. 1 and 2 are diagrams illustrating the process for obtaining multi-colored copies with use of the color former of this invention.
In the embodiment of this invention illustrated in FIG. 1, different thermovolatile or thermosublimative couplers 2' and 3' are coated on the back surfaces of images 2 and 3, respectively. of an original having im ages 1, 2 and 3. When the so formed original for multicolor development is overlapped on a photosensitive paper. and exposed to light emitted from a suitable light source. latent images I". 2" and 3" corresponding to images 1, 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. When this photosensitive sheet is developed. 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. As a result a reproductive copy which has images ll, 12 and 13 colored in different hues is obtained.
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 an other heat-transferable sheet containing coupler 3' are applied to the back surfaces of images 2 and 3, respectively.
When the color former of this invention is used for the multicolor reproduction. it is possible to heat transfer the coupler (a) from the predtermined portion of the original to be copied in a different hue to the photosensitive material at a relatively low temperature. i.e.. a temperature only l020C. higher than the temperature adopted in the ordinary diazo-type reproduction process. and therefore. it is possible to obtain a copy in which the portion corresponding to the predetermined portion of the original is colored selectively in a different hue very distinctly without substantial mingling of colors. Further. formation of a plurality of different colors may be accomplished by one development treatment. Once an original is treated with the color former of this invention. at least 5 multicolored copies. usu ally 2( l UU multi-colored copies. can be obtained from the original. and it is unnecessary to treat the original repeatedly every time when one copy is formed. Further. the treated original used for the multicolor reproduction can be returned to the original state only by peeling off the layer or sheet of the color former applied thereto or by heating the color former-colored original at about [00C.
EXAMPLE I An ink-like composition of the following recipe is prepared as a yellow color-forming agent for treating the back surface of an original:
Acetoacetic anilitle Ill g Alkyd resin 3 g Camphor l5 g Diethylene glycol 5 g Toly ol balance Total ilill ml 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 2 An ink-like composition for forming a yellowish orange color is prepared by using acetoacetic-ochloroanilide instead of the acetoacetic anilide of Example 1 EXAMPLE 3 An ink-like composition of the following recipe is prepared as a red color-forming agent for treating the back surface of an original:
l-Fhenyl-3-methylpyraolone (5) 25 g Hydrochloric acid (36 (i 1 5 ml Naphthalene I5 g (ii cerinc H) 3 Et anol balance Total lliti 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 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 4 An ink-like composition of the following recipe is prepared as a brown color-forming agent for treating the back surface of an original:
Resorein 2H 3 \lnyl acetate resin 3 g (italic acid l5 3 Methanol hit rnl it ater balance l otai Hill ml 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 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 desired to be reproduced in brown.
EXAMPLE 5 An ink-like composition of the following recipe is prepared as a blue color forming agent for treating the back surfaces of an original:
ZJ-Dihydrosynaphthalene Ill g Alkyd resin 3 g Bornane t Ethylene glycol in g Ethanol b dance Total ltlll ml 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 blue 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 color former for treating the back surface of a portion of the original to be reproduced in blue.
EXAMPLE 6 An ink-like composition of the following recipe is prepared as a reddish brown color-forming agent for treating the back surface of the original:
Dimethyl-m-amonophenol 21) g Naphthalene l5 g (.ilycerinc ll) g Ethanol balance Total ltill ml The above composition is directly used as a color former to be coated on the back surface of a portion of the original predetermined to be copied in reddish brown by means of a brush. a coating roller or a sprayer. or after it has been charged in a felt pen or ball pen. it is used as a color former for treating the back surface of a portion of the original to be copied in reddish brown.
Examples of Preparation of Waxy Color Former Composition for Use in Multicolor Reproduction:
EXAMPLE 7 A waxy composition to be used as a yellow colorformirtg agent for treating the back surface of an original is prepared by heat melting Acetoacetic acid anilide 25 g Camphor 15 g Stearic acid Hit) g Parafl'ln 50 g Terra abia 50 g and solidifying the melt.
The above composition is molded into a crayon sticklike or chalk-like form and is used as a color former to be coated on the back surface of a portion of the original desired to be reproduced in yellow.
EXAMPLE 8 A waxy composition to be used as a yellowish brown colorforming agent is prepared by heat melting Py rogallol Ill g Menthol l g Paraffin 5U g Terra abla 70 g Haze ax 20 g Stearic acid llll) g Magnesium carhonah: It) g 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 9 To the composition of Example S l()() g of mineral oil and 30 g of oleic acid are added. and the mixture is kneaded in a ball mill. 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 tool. Thus. the sheet is used as a material for forming a layer of the waxy color former agent on the back surface of a portion of the original desired to be reproduced in a different hue.
EXAMPLE 10 A waxy composition for forming a red color is prepared by heat melting l-Pheny l 3-methylpy ramlone l 5 l p-Dichlorohenzene Paraffin Stearic acid Diatomeceous earth Haze ax and solidifying the melt.
The above composition is molded to a crayon sticklike 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 1 I To the composition of Example l0 l0() g of mineral oil. 50 g oleic acid and g of Permanent Red are added. and the mixture is kneaded in a ball 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 fonned pressure-sensitive copy sheet is used as a material for forming a layer of the waxy color former composition on the back surface of a portion of the original to be copied in a different hue. in the same manner as described in Example 9.
EXAMPLE 12 A waxy color former composition for forming a blue color is prepared by heat melting -continued Stcaric acid lUtl g Paraflin ill g l)iatomaeeou- L'allh 3H g Ha/c \\a\ ll] g 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 l3 To the composition of Example I2 I00 g of mineral oil. g ofoleic acid 2U g of Oil Blue and 50 ml ofethanol are added. The mixture is well kneaded in a ball mill and coated on a substrate such as paper to form a pressure-sensitive copy sheet. The sheet is used as a material for forming a layer of waxy color former composition on the back surface of the original to be rcproduced in a different hue. in the same manner as de scribed in Example 9.
Examples of Preparation of Coupler-Transferring Sheets Comprising Color Former:
EXAMPLE l4 A composition of the following recipe is prepared as a red color-forming agent for treating the back surface of an original:
l-PhenylJ-methylpy ra/olone (5) 15 g Camphor 15 g Triacetate resin ll) g Methanol 51) ml Acetone 51) ml The above composition is coated on a transparent or semi-transparent sheet such as polyester film by means of a rod coater and dried at a relatively low temperature (50C.) 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 15 A composition of the following recipe is prepared as a brown color-forming agent for treating the back surface of an original:
m-Aminophenol 25 g Anthranic acid 15 g l'riacetate resin H) g Methanol ml Acetone 50 ml The above composition is coated on a transparent or semi-transparent sheet such as polyester film by means of a rod coater and dried at a relatively low temperature (40 SOC.) to form a sheet for heat-transferring the coupler. After being cut into a desired size accord ing to need. the sheet is used as a material to be applied to the back surface of a portion of the original desired to be reproduced in a different hue.
EXAMPLE 16 A composition to be used as a brown color-forming agent for treating the back surface of an original is prepared by using pyrogallol instead of l-phenyl-3-mcthyl- 17 pyrazolone in Example 14. From this composition a sheet is formed for heat-transferring the coupler capable of forming a brown color.
EXAMPLE 1'! A composition to be used as a blue color-forming agent for treating the back surface of an original is prepared by using l.6-dihydroxynaphthalene instead of lphenyl-3-methylpyrazolone in Example 14. From this composition a sheet is prepared for heat transferring the coupler capable of forming a blue color.
Application of Color-Forming Agents to Diazo-type Multicolor Reproduction:
EXAMPLE l8 Multicolor-forming diaZo-type photosensitive paper in use for wet development.
First. lll g of 4-diazo-2,5-diethoxy-benzoylaniline chloride lZnCh 8 g of citric acid, 0.1 g of Patent Blue and 10 g of dextrin are dissolved successively in water. and the amount of the solution is adjusted to 1 liter by controlling the amount water added. The so formed so lution is coated on a base paper of a photosensitive sheet by a customary coating method employing 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 ink-like color former composition prepared in Example 1 and the back surface of another portion is treated with the color former composition prepared in Example 3. Then the assembly is heated and light exposed by means of a mercury lamp and developed with a liquid developer of the following recipe:
NW acid Potassium carbonate Sodium bicarbonate Sodium thiosulfate Acti ator Water balance Total 1 liter by a customary developing method using a roller or sprayer.
As result a clear three-color copy in which a portion corresponding to the portion treated with the composition of Example l, is colored in a yellow color. a portion corresponding to the portion treated with the composition of Example 3 is colored in red and another portion corresponding to the untreated portion is colored in blueish violet is obtained.
EXAMPLE l9 Multicolor-Forming-Diazo-type Photosensitive Sheet for Dry Development A solution of the following recipe is prepared:
4-Diazo-N-ethy l-Nfi-hydrovyethy laniline 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 piled on an original in which one portion of the back surface is treated with the color former composition prepared in Example 2. another portion of the back surface is treated with the color former composition prepared in Example 3 and still another portion of the back surface is treated with the color former composition of Example 5. Then. the assembly is heated and exposed to light by means of a mercury lamp to form a latent image of the diazonium salt.
Next. the so treated sheet is subjected to development with gasified ammonia and steam. As a result a clear multicolor copy in which a portion corresponding to the portion treated with the material of Example 2 is colored in yellowish orange. a portion corresponding to the portion treated with the material of Example 3 is colored in reddish brown. a portion corresponding to the material of Example 5 is colored in bluish violet. and a portion corresponding to the untreated portion of the original is colored in dark blue is obtained.
EXAMPLE 20 Multicolor-forming diazo-type photosensitive paper in use for dry development A solution of the following recipe is prepared:
4-Diazo-N;N-dimethyl-aniline chloride'l/ZZnCl lll g Diethylene glycol -lll g Citric acid ill g 1.3-Dihydrovynaphthalene-(v sulfonic acid Ill g Zinc chloride ill g Thiourea ill g Patent Blue 0.1 g Water balance Total 1 liter In the same manner as in Example 18. a photosensitive paper is prepared from the above solution by coating and drying. The photosensitive paper is piled on an Original, a portion of the back surface of which is treated with the coupler-heat-transferring sheet prepared in Example 14. Then the assembly is heated and printed by means of a mercury lamp. followed by development with gaseous ammonia and steam. As a result a clear two-color reproductive copy in which a portion corresponding to the portion treated with the treating agent of Example I4 is colored in red and another portion corresponding to the untreated portion is colored in dark blue is obtained.
EXAMPLE Zl Multicolor-forming photosensitive paper in use for dry development A solution of the following recipe is prepared:
4-Diazo-N.N-dimethylaniline continued Vt ater balance By a customary coating method such as using an air knife coater, a photosensitive paper is prepared from the above solution. The photosensitive paper is overlapped on an original in which a portion of the back surface is treated with the waxy composition prepared in Example 8 and another portion of the back surface is treated with the composition prepared in Example It). The assembly is exposed to light and heated by means of a mercury lamp. Then. the so treated sheet is subjected to development with gasified ammonia and steam. As a result a clear three-color reproductive copy in which a portion corresponding to the portion of the original treated with the composition of Example 8 is colored in brown. a portion corresponding to the portion treated with the composition of Example 10 is colorcd in red. and other portion corresponding to the untreated portion of the original is colored in bluish violet is obtained EXAMPLE 22 Multicolor-forming photosensitive paper for dry development A solution of the following recipe is prepared:
4Di'.tzo-.\ N-diethylaniline chloride lfZZttCl Ill g 2.7-Dih drmynaphthaleneJb tlisiilloriic acid sodium salt g Diethylene glycol 51) g Tartaric acid 21) g Resorcinol monomethyl ether 10 g Zinc chloride 10 g Thiourea 5i] g l.3 hNaphthalene-trisulfonic acid sodium salt 21) g Patent Blue (H g Water balance Total l liter The above solution is applied to a photosensitive paper substrate by a customary coating method such as using an air knife coaterand the resulting photosensitive sheet is piled on an original in which the back surface of a part of an image is treated with the ink-like composition obtained in Example 3. the back surface of another part of the image is treated with the composition of Example 4 and the back surface of still another part is treated with the composition of Example 5. Then, the assembly is heated and printed at 70 80C. by means of a mercury lamp. and the so treated photosensitive sheet is developed with gaseous ammonia and steam. As a result a four-colored copy of a clear color contrast is obtained in which a portion corresponding to the portion treated with the composition of Example 3 is colored in red. a portion corresponding to the portion treated with the composition of Example 4 is colored in yellowish brown. a portion corresponding to the portion treated with the composition of Example 5 is colored in blue. and a portion Corresponding to the untreated portion of the original is colored in black.
EXAMPLE :3
Multicolor-forming diazo-type photosensitive paper for dry development for forming second original A solution of the following recipe is prepared:
-l-Diazo-NN-dimethylaniline chloride The above solution is coated on a semi-transparent paper for second original such as tracing paper and dried to form a photosensitive paper. The photosensitive paper is piled on an original. a portion of the back surface of which is treated with the waxy color former composition prepared in Example 12. Then the assemly is heated and printed by means of a mercury lamp, followed by development with gaseous ammonia and steam. As a result a clear two-color reproductive copy usable as the intermediate second original is obtained in which a portion corresponding to the portion of the original treated with the composition of Example 12 is colored in red and another portion corresponding to the untreated portion of the original is colored in yellowish brown.
EXAMPLE 24 Multi-color-forming photosensitive paper for dry development A solution of the following recipe is prepared:
4-Diazo-N -ethyl-N-hydro sy ethylaniline By a customary coating method such as using an air knife coater. the above solution is applied to a substrate of a photosensitive paper and dried. The so formed photosensitive paper is piled on an original. a portion of the back surface of which is treated with a couplerheat-transferring sheet prepared in Example l7, and the assembly is heated at C. and printed by means of a mercury lamp followed by development with gaseous ammonia and steam. As a result a clear two-color reproductive copy without any substantial mingling of colors. is obtained in which a portion corresponding to the portion of the original treated with the sheet obtained in Example 17 is colored in blue and the remaining portion corresponding to the untreated portion of the original is colored in red.
EXAMPLE 25 Multicolor-forming sensitive paper in use for either dry or wet development A solution of the following recipe is prepared:
-1Diam-2.5-dihutoxy N-pheny l From the above solution, a photosensitive paper is prepared by conducting the coating and drying in the same manner as in Example l8. The so formed photosensitive paper is piled on an original, a portion of the back surface of which is treated with the pressure-sensitive sheet prepared in Example 9 and another portion of the back surface of which is treated with the pressure-sensitive sheet prepared in Example ll. 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:
Potassium carbonate 20 g Sodium thiosulfate 40 g Sodium bicarbonate 3U g Potassium tetrahorate 5 g Water balance Total 1 liter EXAMPLE 26 Mulicolor-forming film A solution of the following recipe is prepared:
-i-Diazo-2.5-dibutoxy-N-phenyl morpholine.l/2ZnCl. g Citric acid l() g fl-Hydrovynaphthoic acid ethanol amine 7 g Triacetate resin 15 g Oil Blue 0.2 g Acetone 400 ml Methanol 701] ml The solution is coated on a polyester film by a red coater and dried at a relatively low temperature (40 50C.) by wann 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 colorforming agent prepared in Example 3 and another part of the back surface of the original image is treated with the color-forming agent prepared in Example 4. 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. As a result a clear three-color reproductive copy without any substantial mingling of color is obtained. in which a portion corresponding to the part treated with the treating material of Example 3 is colored in red. a portion corresponding to the part treated with the treating material of Exampie 4 is colored in brown, and another portion corresponding to the untreated part of the original is colored in blue.
COMPARATIVE EXAMPLE 1 This example illustrates results of comparative experiments conducted to confirm effects attained by the in corporation of the the rmosublimative. organic. solid transfer promoter in the color former of this invention.
EXPERIMENTAL PROCEDURES Four ink-like color-forming compositions of the following recipes are prepared.
Each of the above solutions is coated on the back surface of a semi-transparent original (tracing paper. Chemical No. 60) in an amount of about 0.2 g/m'-'. The so coated original is dried to fonn a sample sheet original. Then. the sample sheet is piled on the photosensitive sheet prepared in Example 21 in a manner such that the treated surface of the sample is in face-to-face contact with the photosensitive layer of the photosensitive sheet. Then. the assembly is allowed to pass through hot rolls maintained at 50C., 60C.. C. and C., respectively, to effect the heat transfer of the thermovolatile or thermosublimative coupler. Then. the so treated photosensitive sheet is subjected to the development with gaseous ammonia and steam. With respect to each sample original. the number of copies of a distinct color contrast obtained at each heat transfer temperature is counted. Results are shown in Table 1 below.
Table l Number of Copies of Distinct Color Contrast Heat Transfer Temperature 1' C.)
Table l-continued Number of Copies of Distinct Color Contrast Heat Transfer Temperature l C.) Recipe No. it) ht) 70 X COMPARATIVE EXAMPLE 2 EXPERIMENT PROCEDURES As the thermovolatile coupler sample l-phenyl-3- methylpyrazolone (5) and resorcin are selected. Each of the sample chemicals is sufficiently ground in a mortar and is sufficiently dried in a silica gel desiccator. A precisely weighed amount (0.3 g) of each sample is charged in a vessel having a certain inner surface area and subjected to a heat treatment at 100C. ll0C. and 120C. The weight of the sample is determined at certain time intervals and the weight loss is calculated each time.
Then. each sample is blended with 1.5 g of eamphor (special grade) and the blend is sufficiently mixed and ground in a mortar. Then. the blend is subjected to the same heat treatment as above to determine the weight loss of the blend. Then. the weight loss of the coupler alone is calculated by reducing the weight loss of champhor alone determined separately, from the above weight loss of the blend. Thus. the effect of eamphor for promoting the volatilization or sublimation of the sample coupler is examined. Results are shown in Tables 2 and 3 below.
Table 2 Weight Loss (mg) of l-Phenyl-3-Methylpyralolone (5) In Tables 2 and 3. the values in parenthesis are values obtained when d-camphor is incorporated in the sample coupler.
From the results of Comparative Examples 1 and Z. the following can be concluded.
As is seen from the results shown in Table l. the use of the color former of this invention increases the number of copies by 7 sheets at C.. by l2 sheets at C. and by 18 sheets at C. in the case of l-phenyl-3- methylpyrazolone 5 as compared with the use of the coupler alone. Accordingly. it is construed that the heat transfer temperature may be lowered by about 10 l5C. with the use of the color former of this invention comprising the thermovolatile or therm0sublimative coupler and the thermosublimative. organic. solid transfer promoter. In the case of resorcin. the use of the color former of this invention increases the number of copies by 7 sheets at 60C. and by 22 sheets at 70C. Accordingly. it is construed that also in this case the heat transfer temperature may be lowered by about l0 15C. with the use of the color former of this invention.
As is seen from the results of Comparative Example 2 shown in Tables 2 and 3. when comparison is made at the same treatment temperature. in the case of the color former of this invention the weight loss of l-phenyl-3-methylpyrazolone (5) is about 2.5 times as large as in the case of the color former free of eamphor. and the weight loss of resorcin in the case of the color former of this invention is about 2 times as large as in the case of the color former comprising resorcin alone. Accordingly. it is construed that the heat transfer temperature may be lowered by about 10 l5C. with the use of the color former of this invention.
In view of the foregoing. it can be readily understood that when the thermosublimative. organic. solid transfer promoter is used in combination with a thermovolatile or thermosublimative coupler. the efficiency of transfer of the coupler can be greatly improved.
What we claim is:
l. 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 a surface and a layer containing at least one thermovolatile or sublimable azo coupler (a) and a solid organic sublimable compound selected from the group consisting of eamphor. naphthalene. bornane, menthol and p-dichlorobenzene. and said layer being located in only pre-selected areas which are contiguous with opaque image areas of said original sheet. said pre-selected area 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 material (ii) so that the layer of the azo coupler (a) comes into face-to-face contact with the phostosensitive layer;
B. heating said assembly to thereby heat-transfer said layer of the coupler (a) to the corresponding position on the surface of said photosensitive layer. said steps (A) and (B) being performed simultaneously or in the time sequence (A) to (B) or (B) to (A);
25 and (C) contacting the exposed photosensitive material with a mixture of ammonia and steam or an alkalicontaining aqueous liquid developer to thereby develop said photosensitive material. whereby in the unexposed latent image area of the portion to which the coupler (a) has been heat-transferred. a dye (c J-( a) having a certain hue or color is formed by the selective reaction of the heat-transfered coupler (a) with the diazonium salt (c) and at the same time. in the unexposed latent image areas to which the coupler a) has not been heat-transferred. a dye (c H b) having a different hue or color from said dye (e)-(a) is formed by the reaction of the coupler (b) with the diazonium salt (c), thus producing a multi-colored copied image.
2. The process of claim 1 wherein said layer of coupler (a) is applied to the opposite surfaces of the original.
3. The process of claim 2 wherein said layer of coupler (a) is applied in the form of a composition consisting essentially of (LS-40.0 percent by weight of said coupler (a), 05-25 percent by weight of said solid organic sublimable compound. 80-5 percent by weight of a wax and 0-l0 percent by weight of color material.
4. The process of claim 1 wherein said layer of coupler (a) is applied in the form of a composition consisting essentially of 50-400 percent by weight of said coupler (a). 50-300 percent by weight of said solid organic sublimable compound. 0-0.3 percent by weight of a color material and 0-5.0 percent by weight of a resinous binder. said components (a). (b). (c) and (d) dispersed in a dispersion medium selected from aliphatic alcohols. aromatic solvents and neutral liquids and a layer containing at least one thermovolatile or sublimable azo coupler (a) and a solid organic sublimable compound selected from the group consisting of camphor. naphthalene. bornane. menthol and p-dichlorobenzene. and said layer being located in only pre-selected areas which are contiguous with opaque image areas of said original sheet. said pre-selected area 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 said original sheet (i) being superposed on said diazo-type photosensitive material (ii) so that the layer of the azo coupler (a) comes into face-to-face contact with the ph'otosensitive layer;
B. heating said assembly to thereby heat-transfer said layer of the coupler (a) to the corresponding position on the surface of said photosensitive layer. said steps A] and (B) being performed simultaneously or in the time sequence of(A) to B) or (B) to (A and C. thereafter developing the exposed photosensitive layer with an alkaline aqueous liquid developer containing 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). whereby in the unexposed latent image area of the portion to which the coupler (a) has been heat-transferred. a dye (c a) having a certain hue or color is formed by the selective reaction of the heat-transferred coupler (a) with the diazonium salt (c) and at the samd time. in the anexposed latent image areas to which the coupler (a) has not been heat-transferred. a dye (e)-(b) having a different hue or color from said dye (c)- (a) is formed by the reaction of the coupler (b) with the diazonium salt (c thus producing a multicolored copied image.
7. The process of claim 6 wherein said layer of coupler (a) is applied to the opposite surface of the original.
8. The process of claim 6 wherein said layer of coupler (a) is applied in the form of a composition consisting essentially of 0.5-40.0 percent by weight of said coupler (a). 05-25 percent by weight of said solid organic sublimable compound. -5 percent by weight of a wax and 0-l0 percent by weight of color material.
9. The process of claim 6 wherein said layer of coupler (a) is applied in the form of a composition consisting essentially of 50-400 percent by weight of said coupler (a). 50-300 percent by weight of said solid organic sublimable compound. 0-0.3 percent by weight of a color material and 0-5.0 percent by weight of a resinous binder. said components (a). (b). (c) and (d) dispersed in a dispersion medium selected from aliphatic alcohols, aromatic solvents and neutral liquids containing OH groups. said dispersion medium boiling at 250C.
10. The process of claim 6 wherein said coupler (a) is selected from the group consisting of phenol compounds, hydroxynaphthalene compounds. aniline compounds and compounds containing an active methylene group.
U'Nnm S'ITATES Pt '1 NT omens;
C RT F C A T E 0 F C ORE U5. 1,0131
Inventor(s) Kouzi ihyakumen, 6'13 a1 It is certified that error appears in the above-identified patent and that. said Letters Patent are hereby corrected as shown below:
Column 25, line 18, delete "surfaces", insert surface Column 25, line 20, delete "2", insert l Column 26, line 25, delete "samd", insert same Signed and Scaled this ninth Day of March 1976 [SEAL] A nest:
RUTH C. MASON C. MARSHALL DANN Arresting Officer (mnmissimwr uj'Pan'nrs and Trademarks

Claims (9)

1. A PROCESS FOR MULTI-COLOR REPRODUCTION WHICH COMPRISES: A. EXPOSING IMAGEWISE 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 A SURFACE AND A LAYER CONTAINING AT LEAST ONE THERMOVOLATILE OR SUMLIMABLE AZO COUPLER (A) AND A SOLID ORGANIC SUBLIMABLE COMPOUND SELECTED FROM THE GROUP CONSISTING OF CAMPHOR NAPTHALENE BORNANE MENTHOL AND P-DICHLOROBENZENE AND SAID LAYER BEING LOCATED IN ONLY PRE-SELECTED AREAS WHICH ARE CONTIGUOUS WITH OPAQUE IMAGE AREAS OF SAID ORIGINAL HEET SAID PRE-SELECTED AREA BEING PRESENT IN ONLY A PORTION OF THE AREAS CONTIGUOUS WITH SAID OPAQUE IMAGE AREAS OF SAID ORIGINAL SHEET, AND (II) AA DIAZO-TYPE PHOTOSENSITIVE MATERIAL HAVING A PHOTOSENSITIVE LAYER CONTAINING AT LEAST ON 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 PHOTOSENTIVE MATERIAL (II) SO THAT THE LAYER OF THE AZO COUPLER (A) COMES INTO FACE-TO-FACE CONTACT WITH THE PHOTOSENTIVE LAYER B. HEATING SAID ASSEMBLY TO THEREBY HEAT-TRANSFER SAID LAYER OF THE COUPLER (A) TO THE CORRESPONDING POSITION ON THE SURFACE OF SAID PHOTOSENTITIVE LAYER, SAID STEPS (A) AND (B) BEING PERFORMED SIMULTANEOUSLY OR IN THE TIME SEQUENCE (A) TO (B) OR (B) TO (A) AND (C) CONTACTING THE EXPOSED PHOTENSITIVE MATERIAL WITH A MIXTURE OF AMMONIA AND STREAM OR AN ALKALI-CONTAINING AQUEOUS LIQUID DEVELOPER TO THEREBY DEVELOP SAID PHOTOSENSITIVE MATERIAL, WHEREBY IN THE UNEXPOSED LATEN IMAGE AREA OF THE PORTION TO WHICH THE COUPLER (A) HS BEEN HEAT-TRANSFERED,A DYE (C)-(A) HAVING A CERTAIN HUE OR COLOR IS FORMED BY THE SELECTIVE REACTION OF THE HEAT-TRANSFERED COUPLER (A) WITH THE DIAZONIUM SALT (C) AND AT THE SAME TIME, IN THE UNEXPOSED LATEN IMAGES AREAS TO WHICH THE COUPLER (A) HAS NOT BEEN HEAT-RANSFERRED, A DYE (C)-(B) HAVING A DIFFERENT HUE OR COLOR FROM SAID DYE (C)-(A) IS FORMED BY THE REACTION OF THE COUPLER (B) WITH THE DIAZONIUM SALT (C), THUS PRODUCING A MULTI-COLORED COPIED IMAGE. 6. THE PROCESS FOR MULTI-COLOR REPRODUCTION WHICH COMPRISES: A. EXPOSING IMAGE-WISE A DIAZO-TYPE PHOTOSENTITIVE 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 A SURFACE AND A LAYER CONTAINING AT LEAST ONE THERMOVOLATILE OR SUBLIMABLE AZO COUPLER (A) AND A SOLID ORGANIC SUBLIMABLE COMPOUND SELECTED FROM THE GROUP CONSISTING OF CAMPHOR, NAPHTHALENE, BORNANE, MENTHOL AND P-DICHLOROBENZENE, AND SAID LAYER BEING LOCATED IN ONLY PRE-SELECTED AREAS WHICH ARE CONIGUOUS WITH OPAQUE IMAGE AREAS OF SAID ORIGINAL SHEET, SAID PRE-SELECTED AREA BEING PRESENT IN ONLY A PORTION OF THE AREAS CONTIGUOUS WITH SAID OPAQUE IMAGE AREAS OF SAID ORIGINAL SHEET, AND (II) A DIAZO-TYPE PHOTOSENTITIVE MATERIAL HAVING A PHOTOSENSITIVE LAYER CONTAINING AT LEAST ONE PHOTOSENTITIVE DIAZONIUM SALT (C), SAID ORGINAL SHEET (I) BEING SUPERPOSED ON SAID DIAZO-TYPE PHOTOSENTITIVE MATERIAL (II) SO THAT THE LAYER OF THE AZO COUPLER (A) COMES INTO FACE-TOFACE CONTACT WITH THE PHOTOSENTITIVE LAYER B. HEATING SAID ASSEBMLY TO THEREBY HEAT-TRANSFER SAID LAYER OF THE COUPLER (A) TO THE CORRESPONDING POSITION ON THE SURFACE OF SAID PHOTOSENTITIVE LAYER SAID STEPS (A) AND (B) BEING PERFORMED SIMULTANEOUSLY OR IN THE TIME SECQUENCE OF (A) TO (B) OR (B) TO (A) : AND C. THEREAFTER DEVELOPING THE EXPOSED PHOTOSENTITIVE LAYER WITH AN ALKALINE AQUEOUS LIQUID DEVELOPER CONTAINING 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), WHEREBY IN THE UNEXPOSED LATEN IMAGE AREA OF THE PRTION TO WHICH THE COUPLER (A) HAS BEEN HEAT-TRANSFERRED, A DYE (C)-(A) HAVING A CERTAIN HUE OR COLOR IS FORMED BY THE SELECTIVE REACTION OF THE HEAT-TRANSFERRED COUPLER (A) WITH THE DIAZONIUM SALT (C) AND AT THE SAME TIME, IN THE UNEXPOSED LATENT IMAGE AREAS TO WHICH THE COUPLER (A) HAS NOT BEEN HEAT-TRANSFERRED, A DYE (C)-(B) HAVING A DIFFERENT HUE OR COLOR FROM SAID DYE (C)-(A) IS FORMED BY THE REACTION OF THE COUPLER (B) WITH THE DIAZONIUM SALT (C) THUS PRODUCING A MULTI-COLORED COPIED IMAGE.
2. The process of claim 1 wherein said layer of coupler (a) is applied to the opposite surfaces of the original.
3. The process of claim 2 wherein said layer of coupler (a) is applied in the form of a composition consisting essentially of 0.5-40.0 percent by weight of said coupler (a), 0.5-25 percent by weight of said solid organic sublimable compound, 80-5 percent by weight of a wax and 0-10 percent by weight of color material.
4. The process of claim 1 wherein said layer of coupler (a) is applied in the form of a composition consisting essentially of 5.0-40.0 percent by weight of said coupler (a), 5.0-30.0 percent by weight of said solid organic sublimable compound, 0-0.3 percent by weight of a color material and 0-5.0 percent by weight of a resinous binder, said components (a), (b), (c) and (d) dispersed in a dispersion medium selected from aliphatic alcohols, aromatic solvents and neutral liquids containing OH groups, said dispersion medium boiling at 100*-250*C.
5. The process of claim 1 wherein said coupler (a) is selected from the group consisting of phenol compounds, hydroxynaphthalene compounds, aniline compounds and compounds containing an active methylene group.
7. The process of claim 6 wherein said layer of coupler (a) is applied to the opposite surface of the original.
8. The process of claim 6 wherein said layer of coupler (a) is applied in the form of a composition consisting essentially of 0.5-40.0 percent by weight of said coupler (a), 0.5-25 percent by weight of said solid organic sublimable compound, 80-5 percent by weight of a wax and 0-10 percent by weight of color material.
9. The process of claim 6 wherein said layer of coupler (a) is applied in the form of a composition consisting essentially of 5.0-40.0 percent by weight of said coupler (a), 5.0-30.0 percent by weight of said solid organic sublimable compound, 0-0.3 percent by weight of a color material and 0-5.0 percent by weight of a resinous binder, said components (a), (b), (c) and (d) dispersed in a dispersion medium selected from aliphatic alcohols, aromatic solvents and neutral liquids containing OH groups, said dispersion medium boiling at 100*-250*C.
10. The process of claim 6 wherein said coupler (a) is selected from the group consisting of phenol compounds, hydroxynaphthalene compounds, aniline compounds and compounds containing an active methylene group.
US396667A 1970-05-01 1973-09-13 Process for the diazo-type multicolor reproduction Expired - Lifetime US3918974A (en)

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Publication number Priority date Publication date Assignee Title
US2653091A (en) * 1950-01-31 1953-09-22 Rca Corp Photographic diazotype composition and heat development thereof
US2789904A (en) * 1953-09-17 1957-04-23 Gen Aniline & Film Corp Diazo print process
US3157503A (en) * 1963-03-19 1964-11-17 Keuffel & Esser Co Diazotype reproduction materials
US3199982A (en) * 1963-03-19 1965-08-10 Keuffel & Esser Co Diazotype reproduction material
US3318699A (en) * 1963-10-12 1967-05-09 Keuffel & Esser Co Process and material for the development of diazotype copies
US3353984A (en) * 1963-04-18 1967-11-21 Landau Raphael Method for the preparation of lightsensitive diazotype materials and improved materials prepared by such method
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
US3469981A (en) * 1963-03-19 1969-09-30 Keuffel & Esser Co Diazotype reproduction materials
US3653903A (en) * 1969-08-02 1972-04-04 Mita Industrial Co Ltd Diazo-type multicolor reproduction process
US3715213A (en) * 1969-02-19 1973-02-06 Mita Industrial Co Ltd Diazo-type multicolor reproduction
US3725066A (en) * 1969-09-01 1973-04-03 Mita Industrial Co Ltd Diazo-type multicolor reproduction process

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2653091A (en) * 1950-01-31 1953-09-22 Rca Corp Photographic diazotype composition and heat development thereof
US2789904A (en) * 1953-09-17 1957-04-23 Gen Aniline & Film Corp Diazo print process
US3157503A (en) * 1963-03-19 1964-11-17 Keuffel & Esser Co Diazotype reproduction materials
US3199982A (en) * 1963-03-19 1965-08-10 Keuffel & Esser Co Diazotype reproduction material
US3469981A (en) * 1963-03-19 1969-09-30 Keuffel & Esser Co Diazotype reproduction materials
US3353984A (en) * 1963-04-18 1967-11-21 Landau Raphael Method for the preparation of lightsensitive diazotype materials and improved materials prepared by such method
US3318699A (en) * 1963-10-12 1967-05-09 Keuffel & Esser Co Process and material for the development of diazotype copies
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
US3715213A (en) * 1969-02-19 1973-02-06 Mita Industrial Co Ltd Diazo-type multicolor reproduction
US3653903A (en) * 1969-08-02 1972-04-04 Mita Industrial Co Ltd Diazo-type multicolor reproduction process
US3725066A (en) * 1969-09-01 1973-04-03 Mita Industrial Co Ltd Diazo-type multicolor reproduction process

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