JPS6057060B2 - Diazo multicolor copying method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a diazo multicolor copying method, and more specifically, a multicolor copying master having images of a plurality of types of azo coupling components produced by electrophotography is used. Concerning a diazo multicolor copying method.

Conventional methods for copying color images include a silver halide method and an electrostatic photograph method.

In addition, the diazo type multicolor copying method was published in Japanese Patent Publication No. 47-4365.
As described in No. 8, a step of exposing a diazo photosensitive material having at least one diazonium salt, a layer of at least one heat volatile or heat evaporable coupler is applied to the diazo photosensitive material. are heated in selected areas simultaneously or in this order or in the reverse order, and then the exposed photosensitive material is coupled under developing conditions by the volatile or sublimable coupler. It consists of developing in the presence of a slow coupler, thereby producing a multicolor copy in which selected parts of the original are colored in different hues, regardless of the difference in light transmittance of the original. It will be done. This known diazo copying method is
In order to repeatedly produce a large number of copies, it is inconvenient to use a transparent or translucent original and to repeat exposure, transfer, and development for each copy. 1 Furthermore, in the diazo copying method, in order to obtain a color diazo copy, couplers with different colors must be applied by hand to the back of the original, corresponding to the images that require different colors. There are some difficulties in preparing originals for color copying.

The present inventors have proposed that heat-volatile or heat-sublimable azo-coupling components can be produced as solid powders or by mixing them with resins, pigments, dyes, etc. and grinding them into fine particles, or by abrading them into fine particles. It can be easily charged by dispersing it in an electrically resistive liquid; when charged particles of this azo coupling component are applied to the surface of an electrostatographic photosensitive layer having an electrically latent image, electrically latent images can be generated. An image of an azo coupling component corresponding to the image is formed, and the format of the image of the azo coupling component is that the image of the azo coupling component is formed on the same electrostatographic photosensitive layer multiple times using different azo coupling components. Repeatability: The imaged master of multiple azo coupling components is heated by facing it with a sheet material containing a diazonium compound.
The application is based on the fact that images of multiple types of azo coupling components are easily transferred to the sheet material, and by developing the images, a large number of copies with clear and fast azo dye-dyed images can be obtained. Furthermore, in this case, multiple types of azo◆ coupling components are selected so that when they react with a common diazonium compound, they develop different hues and the temperature ranges at which thermal transfer is possible are close to each other. We have completed a diazo color copying method that faithfully reproduces color originals or selectively colors selected parts of color originals in different hues.

An object of the present invention is to easily prepare a master having images of a plurality of types of azo coupling components, and to transfer images of the azo coupling components from a single master onto a sheet containing a diazonium salt. By thermal transfer,
It is an object of the present invention to provide a new diazo multicolor copying method capable of forming a large number of diazo multicolor copies (including diazo color copies).

Another object of the present invention is to provide a diazo multicolor copying master for use in the above novel diazo multicolor copying method.

Another object of the present invention is to remove even one page of a hidden document, such as a manuscript or book, which has images on both sides, without requiring human intervention.
A master for multicolor copying can be obtained directly and easily, and by using this master, a large number of diazo color copies or multicolor copies can be formed. To provide a new diazo type multicolor copying master having the following features.

Another object of the present invention is to provide a method which is much cheaper than conventional electrophotography, silver halide photography, etc. used for color copying, and which can easily produce a large number of copies. .

According to the present invention, an electrostatic image is formed on an electrostatographic photosensitive layer, and the electrostatic image is developed with charged particles of a heat-volatile or heat-sublimable azo coupling component. In a copying method that consists of superimposing a photosensitive layer having an image and a copying layer containing a diazonium compound, thermally transferring an azo coupling component to the copying layer, and developing and developing color, a static copying layer for a single photosensitive layer is used. In the electro-image forming step and the developing step, each of a plurality of types of azo coupling components, which develop different hues when reacted with a common diazonium compound, but whose thermal transferable temperature ranges are close to each other, is used. This process is repeated multiple times to create a multicolor copy master in which images of multiple types of azo coupling components are formed on a single photosensitive layer, and the images of multiple types of azo coupling components on this multicolor copy master are A diazo multicolor copying method is provided, which is characterized in that images of the above images are simultaneously transferred onto a copying layer to form a multicolor copy image.

As is conventionally known, when color copying is performed using color toner, the original image is separated using a color filter according to the hue of the original image, and a corresponding monochromatic color toner image is once formed. A color image is obtained by repeating a series of steps of sequentially transferring this to a transfer medium three or four times.

Therefore, when forming an electrostatic latent image, a process in which a toner image is formed on the surface of a photoreceptor and a latent image is formed in an overlapping manner is not adopted. The reason for this is that since toner is insulative, the toner image formed in the first step is charged during the second charging process, and a toner image including this portion is formed during the second development process, which is an inconvenience. This is because it occurs. In the present invention, such disadvantages are overcome by using an azo coupling component for image formation.

That is, while commercially available insulating toners have a volume resistivity on the order of 1014 Ω-0, the azo coupling component used in the present invention alone has a low volume resistivity of 1010 to 1011 Ω-0. This seems to be related to the fact that the azo coupling component itself necessarily has a polar group such as a phenolic hydroxyl group in one molecule, as will be exemplified later. Thus, the azo coupling component used in the present invention has electrical properties close to those of a conductive toner rather than an electrically insulating toner, and it can be used on the image formed by the first electrodeposition process. It can be seen that the phenomenon of residual charges after the second charge is prevented. Next, when uniform charging and image exposure are performed on the photosensitive layer after the electrodeposition treatment of the azo coupling component, the portion where the image of the azo coupling component is formed is exposed through the photosensitive layer. There is a problem as to whether static electricity is removed.

Regarding this point as well, the azo coupling component used in the present invention is substantially transparent, and static elimination is effectively performed by exposure through the photosensitive layer. As shown in the example below, this phenomenon also occurs when fine particles such as carbon black are used together with the azo coupling component for the purpose of improving the conductivity and coloring the azo coupling component. This occurs in the same way because it is carried out up to . Thus, according to the present invention, by repeating a series of steps of charging, exposing, and electrodeposition using an azo coupling component multiple times on a single photosensitive layer, colors can be differentiated according to each exposure. It is understood that more than one type of azo coupling moiety can be imaged.

The principle of the present invention will be explained in detail below based on specific examples shown in the accompanying drawings.

As shown in Figure 1-a of the attached drawings, an electrode 1 that generates a corona discharge with a high voltage is moved along the surface of the electrostatic photosensitive layer 2 on the conductive layer 3 in the dark. be charged.

This imparts photosensitivity to the electrostatographic photosensitive plate. Next, as shown in FIG. 1-b, when the original 5 is exposed to light using an optical system 6 equipped with a green filter (three-color separation filter, e.g., Kodaku No. 58), electrostatic photography is performed depending on the amount of light received. The resistance of the layer 2 is reduced, the charges are discharged, and an electrostatic latent image 2a corresponding to the green image 5a of the original is formed on the surface of the photosensitive layer. Next, on the photosensitive sheet having this electrostatic image 2a, a fine powder 4a (referred to as a toner) containing a sublimable coupler that has an opposite polarity to this charge and couples with a diazo compound to develop a magenta color is added. When you touch the
A first coupler image 4a attached to the charge image 2a is formed. Again, as shown in Figure 1-a, this photosensitive layer 2 is subjected to corona discharge in the dark to uniformly charge its surface, and then a red filter is applied to the original 5 as shown in Figure 1-b. (For example, Kodatsu No. 25) When exposed to light using the optical system 6, the electric resistance of the photosensitive layer is felt depending on the amount of light received, and the charge is discharged, resulting in an electrostatic latent image 2b corresponding to the red image 5b of the original. is formed on the surface of the photosensitive plate. Next, as shown in FIG. 1-c, the photosensitive sheet having the electrostatic latent image 2b contained a sublimable coupler which has an opposite polarity to this charge and couples with the diazo compound to develop a cyan color. When the fine powder 4b is brought into contact, a coupler image 4a attached to the charge image 2b is formed. Furthermore, it is charged as shown in Figure 1-a above, and a blue filter (No. 47A manufactured by Kodak) is applied.
An electrostatic latent image 2c corresponding to the blue image 5c of the original is formed by exposure through the wafer, and then a sublimable coupler 4c which develops a yellow color by coupling with a diazo compound is applied to form a coupler image 4c. In this way, the above three times of charging,
Three types of coupler images 4a that couple with a diazo compound and develop three primary colors by repeating exposure and electrodeposition processing
, 4b and 4c, a master for diazo type multi-sheet color copying or multi-sheet multicolor copying is manufactured. Also, 3
Colors other than primary colors appear through the following combinations. Red can be created by mixing magenta and yellow, blue can be created by mixing magenta and cyan, green can be created by mixing cyan and yellow, and black can be created by mixing cyan, yellow, and magenta. During multicolor copying, as shown in Figure 1-c, when a diazo multicolor copying mask is placed facing the color forming layer 8 containing a diazo compound and heated with an appropriate heat source such as a heating roller or an infrared heater 7, the diazo multicolor copying master is heated. Sublimation couplers 4a, 4b, 4
c is transferred to the surface of the diazo coloring layer 8 by heat (1
At the same time, the alkali generating substance contained in the diazo coloring layer creates conditions where the diazo compound and coupler tend to react, forming azo dye 10 and dyeing it on base 9 (1
In the case of copy paper that does not contain an ammonia-generating substance, azo dye 10 can be obtained by making the surface alkaline after coupler transfer.

According to the present invention, first, an electrical latent image is formed on the surface of an electrostatographic photosensitive layer capable of substantially retaining the electrical latent image.

For example, inorganic photoconductors such as zinc oxide, selenium, zinc sulfide, and titanium oxide, or organic photoconductors such as polyvinyl carbazole, polyvinyl nitrocarbazole, polyoxazole, and anthracene, or these photoconductors A photoconductive surface made of a photoconductive composition dispersed in an organic or inorganic binder known per se is charged by corona discharge or friction, and the electrostatic latent is irradiated with a light beam pattern on the charged surface. An image can be formed. Alternatively, the photoconductive surface of the photoconductor can be irradiated with a pattern of light beams without being previously charged, thereby forming an electrostatic latent image. The surface on which the electric latent image is formed may be, for example, a sheet-like or foam-like substrate such as paper, a metal plate, or a film coated with the above-mentioned photoconductor, or a cylindrical body made of metal or glass. It may be coated with the photoconductor described above. In addition, the means for forming an electrostatic latent image in the method of the present invention is as follows:
It is understood that any known means can be used in addition to those described above, which are known per se.

According to the invention, charged particles of a thermovolatile or thermosublimable azo coupling component are applied to the surface having the electrical latent image described above.

Heat-volatile or heat-sublimable a,zo-
Examples of the coupling component include phenol derivatives, oxynaphthalene derivatives, aniline derivatives, and compounds containing active methylene groups.

These derivatives generally contain soluble groups, such as sulfonic acid groups, to facilitate thermal transfer! It is desirable not to have one. A few examples will be described below. Phenoyl, pyrocaticol Phloroglycin, resorcin, birogallol Orthohydroxybenzalcohol Resorcin monoglycol ether Resorcin glycol ether Hydrotruquinone Pyrogallol-4-carboxylic acid Vanillin 5-oxyisophthalic acid 2-oxy-terephthalic acid 2-oxy-p-toluic acid 3-oxy-para-toluic acid 5-oxy-ortho-toluic acid 6-oxy-methatoluic acid 5-oxy-1-naphthoic acid para-oxydiphenylacetic acid para-oxybenzaldehyde Salcyl alcohol (0) Salicylic acid (0) 4,4 ″-Dioxydiphenyl 5-chloro-2-nitrophenol 2,5-dinitrophenol 2,5-dioxyacetophenone 2,4-dinitrophenol 2,4-dinitroresorcin 4,6-difurom -2-Nitrophenoyl 2,5-dimethylhydroquinone toxinaphthalene derivative 2,3-dioxynaphthalene β-naphthol α-naphthol 1,6-dioxynaphthalene 2,6-dioxynaphthalene 1,5-dioxynaphthalene 8 , amino-2-naphthol 2,2'-dioxy-1,1''-binaphthyl 4,4''-
Dioxy-1,1″-binaphthyl 3-carboxy-2-
Naphthol 2,3-Dioxynaphthalene resoprimate Niline derivative Metaaminophenol Orthoaminophenol N,N-diethylmethaminophenol N,N-dimethylmethaminophenol N,N-dibutylmethaminophenolmetaphenylenediamine paraphenylenediamine 2-amino-para cresol 3-amino-ortho-cresol 3-amino-para-cresol 3-amino-para-cresol 5-amino-ortho-cresol para Chloraniline meta-aminobenzoic acid 3,4 diamino para toluene Compound with active methylene group 1-phenyl-3-methylpyrazolone (5) 1-phenyl-3-carboxypyrazolone 3-methylpyrazolone acetoacetate acid anilide acetoacetate 0 - Chloroanilide p-Carboxyacetoacetanilide A method for electrodepositing an electrostatic latent image to produce a copy master having a thermally transferable image includes a dry electrodeposition agent containing an azo coupling component as described above, a wet method. An electrodeposition agent is used.

Dry electrodeposition agents are a mixture of triboelectrically charged fine particles called toner and carrier particles such as iron or glass, or electrostatic latent particles of carrier-free fine particles mainly made of iron oxide and resin. It is something that brings it into contact with the image. A few examples will be described below.

Resin 0-70% Pigment 0-20% Dye 0-9% Heat-volatile or heat-sublimable azo coupling component 100%-1% The above homogeneous mixture is atomized to a particle size of about 1 to 20μ. 2
00~500μ glass or iron balls at a weight ratio of 1:60.
The mixture is mixed to about 1 to 1% and brought into contact with the electrostatic latent image.

Polystyrene, Sierra Tsuk, copal, pine resin, gilsonite, rosin-modified maleic acid resin, rosin-modified phenol resin, petroleum-based polyolefin resin, cumaron resin, styrene-acrylic copolymer resin, polyvinyl butyral, phenol formaldehyde resin; carbon as pigment. Black, phthalocyanine blue, asphalt gilsonite, monolite red, Hanser yellow, etc.; spirit nigrosine, nigrosine, oil black triiron tetroxide, and other oil-soluble dyes can be used as dyes. A liquid electrodeposition agent is a composition in which the above-described coupler is dispersed or suspended in a highly insulating liquid such as petroleum. Colorant: 0-8.0% Dispersant: 0-2.0% Resin
0-5.0% heat-volatile or heat-sublimable coupler 2%-25
．． 0% Solvent Residue The above uniform slurry liquid is diluted with an insulating liquid to suit the appearance of the image and used.

Carbon black, Monolite Red, Monolite Yellow, Phthalocyanine Bricot, Hansa Yellow, Nigrosine, Zinc oxide, Triferric tetroxide, Asphalt, Gilsonite, Cadmium sulfide, etc. as a colorant; Oil-soluble surfactant as a dispersant, Higher fatty acids, etc.; as resins (dispersants, fixing agents), linseed oil, alkyde resins, polyethylene, shellac, polyamide resins (versamide), styrene, polyolefins, methacrylic acid copolymers, etc.; as solvents, those that dissolve the above resins For example, mineral spirit, toluene, etc.; gasoline, kerosene, terpene, benzene, carbon tetrachloride, isoparaffin hydrocarbon, freon, cyclohexane, etc. can be used as the highly insulating liquid.

According to the present invention, the steps of forming an electrostatic image on an electrostatographic photosensitive layer and applying charged particles of a thermally volatile or thermally sublimable azo coupling component to the electrostatic latent image are performed. , repeating the same electrophotographic photosensitive layer multiple times, and selecting the multiple types of azo coupling components applied at this time so that they develop different hues when reacted with a common diazonium compound. do. For example, as explained in the accompanying drawings, an electrostatic photosensitive layer is imagewise exposed through a color separation filter, and an image of an azo coupling component that develops the same hue as the light transmitted through the color separation filter is formed using an electrostatic charge. When formed on a photosensitive layer, a master is obtained which provides a copy with an image of the same hue as the original.

Of course, if the above image exposure and image formation of the azo coupling component are repeated three times for the three primary colors, a natural color copying master for producing a copy with a natural color image equal to that of the original can be obtained. is obtained. In addition, the hue of the color separation filter and the hue developed by the azo coupling component can be selected and combined differently. For example, a blue or yellow image can be created corresponding to the red image of the original, and the hue of the color separation filter can be selected and combined differently. A multicolor reproduction master can be prepared that gives a correspondingly red image. Instead of establishing a one-to-one correspondence between an image of a specific hue on the original and a specific coupler image on the master in one original and one master, multiple types of originals can be used. can be used to establish a one-to-one correspondence between a single document and a particular coupler image on the master.

For example, when preparing a color-coded integrated drawing that shows various types of piping in different colors according to their use, a coupler image that should be colored blue is formed on the master substrate (electrostatic photosensitive layer) from the original drawing showing the water pipes, and then A coupler image that should be colored yellow can be formed on the same substrate from an original drawing showing a water pipe, and a coupler image that should be colored red can be formed on the same substrate from an original drawing showing a gas pipe. This latter method of preparing masters for multicolor reproduction is extremely useful for applications such as preparing color-coded drawings. In the electrodeposition process of the azo coupling component, a coupler that develops a desired hue is selected from the couplers listed above and used.

In this case, it is necessary for the multiple types of couplers to be assembled to develop different hues, but at the same time, because the thermal transfer of images of the multiple types of couplers is performed simultaneously, the temperature ranges at which thermal transfer is possible are similar to each other. It is important that Examples of suitable combinations are shown in the examples below. According to the present invention, by applying the above-mentioned electrostatic photographic process, it is possible to accurately correspond to images that require color separation on the original, and develop the desired hue through subsequent thermal transfer and development. An image of the azo coupling component can be formed on the electrostatographic photosensitive layer, and this image of the azo coupling component has excellent fixability to the photosensitive layer and durability over repeated thermal transfer.

Surprisingly, an electrostatographic photosensitive layer on which an azo coupling component has been electrodeposited forms an electrostatic image with good contrast even when it is subjected to a charged exposure process again. By electrodepositing different azo coupling components on the image again and repeating this operation as many times as necessary, a master with any combination of coupler images can be easily obtained. Thus, according to the present invention, there is no need for complicated means such as manually applying a coupler to the back side of a document, and there is also no risk of staining the document itself with the coupler. From the color copy master, master 1 is created by thermal transfer.
It is easy to obtain diazo multicolor copies of 20 to 10 losses per sheet. According to the present invention, the above-described diazo multicolor copying master and a sheet material containing diazonium,
Heating is performed in a state where the image of the thermally transferable Kaboola and the diazo compound coating layer of the sheet material containing the diazonium compound face each other.

By this heating, the image of the thermally transferable coupler on the copy master is thermally transferred to the diazo compound coated surface of the copy sheet.
This thermal transfer can be easily carried out by using any heating mechanism such as thermal radiation paper such as infrared rays or a heating roll. For example, thermal transfer can be carried out by direct infrared irradiation of a laminate of master sheet and diazo copy sheet, or by passing it through a heated roll, or if the diazo copy master is itself cylindrical. Alternatively, the copy master may be preheated and the heat may be used to transfer the thermal transfer coupler to the copy sheet. In order to effectively perform thermal transfer of heat-volatile or heat-sublimable couplers, it is preferable to maintain the temperature of the copy sheet lower than that of the master and to create a temperature gradient between the two surfaces.

Alternatively, an acidic substance such as citric acid may be present in the diazo compound coating layer of the copying sheet in an amount of at least 5 mol or more per 1 mol of diazonium salt to increase the thermal transfer efficiency of the thermal transferable coupler to the diazo compound coating layer. You can also. According to one preferred embodiment of the invention, the thermal transfer and development of the image of the thermally volatile or thermally transferable coupler to the diazo copying sheet occurs simultaneously.

In this case, an alkali generator such as urea, thiourea, urea derivatives, ammonium salts such as ammonium carbonate, etc., in an amount of 5 to 20% per diazonium salt is applied to the copy surface of the diazo copy sheet material to generate ammonia gas by heating. and organic acids such as acetic acid, formic acid, oxalic acid,
Use volatile acids such as chloroacetic acid and hydrochloric acid. When the master and the diazo copy sheet material are laminated and the laminate is heated to a temperature of, for example, 80 DEG to 150 DEG C., the image of the thermally transferable coupler on the master is thermally transferred to the diazo compound coating layer of the diazo copy sheet material. , and at the same time, the thermally volatile acid in the diazo compound coating layer is volatilized and the alkali generator is decomposed into ammonia, forming a multicolor azo dye image corresponding to the image of multiple types of thermally volatile couplers. . In addition, when using a diazo derivative that can develop color on the acidic side, such as antidiazotate, diazoamino compound, or diazosulfonate, as the diazonium compound, acetic acid, A hot volatile acid such as formic acid, oxalic acid, or hydrochloric acid is contained in advance, and the hot volatile acid is thermally transferred to the diazo compound coated surface of the diazo copying material at the same time as the coupler, and simultaneously developed on the spot. You can also have them do this. According to another aspect of the invention, thermal transfer of the image of the heat-volatile or heat-sublimable coupler to the diazo copy sheet and development are performed in separate steps.

The diazo copying sheet material onto which the heat-volatile or heat-sublimable coupler has been thermally transferred as described above is developed by wet or dry development methods known per se. for example,
For wet development, an aqueous developer containing an alkaline agent and
For dry development, the sheet material is brought into contact with ammonia vapor.
In addition, when the above-mentioned antidiazonate, diazoamino compound, or diazosulfonate is used as the diazo compound, the diazo type copying material onto which the coupler has been thermally transferred may be brought into contact with an acidic aqueous solution or acidic monovapor to perform development. . Depending on the type of diazonium compound used, sheet materials containing diazonium compounds can be applied to paper, translucent paper, plastic film, fiber cloth, metal film, etc. together with organic acids or basic substances. is used.

An example of this composition is shown below.

Composition for diazo copying materials Diazo compound 0.2-10.0% Organic acid or alkali agent 0-5.0 Stabilizer
0-10.0 extender
0-2.5% dye 0-0.025y solution
Medium Remaining Amount A solution having the above composition is applied to a substrate such as translucent paper, wood-free paper, or base paper for photosensitive paper, and dried at a relatively low temperature (50 to 70°C) to form a copy sheet.

The diazo compound may be any diazonium compound that couples with the coupler described above under normal development conditions.

Examples of such diazo compounds are as follows.
◎ Paraphenylenediamine N,N-substituted compound system - General formula Diazo N,N-diethylaniline (abbreviated as supracostal A salt) 4-DiazoN-ethyl-N-β-hydroxyethylaniline (abbreviated as EH salt) 4-diazoN,N-bis-β-hydroxyethylaniline 4-diazo N-methyl-N-β-hydroxyethylaniline 4-diazo N-ethyl-N-β-hydroxypropylaniline N-mono- or N,N-substituted paraphenylenebuamine diazonium salt with other alkyl or hydroxyalkyl ) 4-DiazoN-ethyl-N-(β-diethylamino)-monoethylaniline 4-diazo2-chloroN,N-diethylaniline 4-diazo2-methyl-N,N-diethylaniline 4-diazo2-iodoN,N- Diethylaniline 4-diazo2-trifluoromethyl-N,N-diethylaniline 4-diazoNethyl-N-benzylaniline 4-diazoNmethyl-N
-Benzylaniline (abbreviation methylbenzyl)) Aminohydroquinone ether system General formula 4-diazo2,5-dibutoxy-N,N-diethylaniline 4-diazo2,5-diethoxyN-benzoylaniline (abbreviation W3B salt) 4-diazo2, 5-diethoxyN-ethyl-N-benzoiteaniline 4-
Diazo2,5-dibenzyloxy-N-benzoylaniline4-diazo2-chloro5-methoxyN-benzoylaniline4-diazo2,5-diethoxy-N-benzoylmethylaniline4-diazo2,5-
Diethoxy-N-benzoyloxymethylaniline and others, 4-diazo 2,5-dialkoxy (or diallyloxy)-N-alkyl (or aryl) compounds and derivatives thereof ◎ Aminodiphenyl, aminodiphenylamine and similar compounds General formula and . 1). \1ノ\↓ノ4125〜r1AV2VV! 1
Diarylamine [A: -NH-]diphenyl [A:
Single bond] Diphenyl oxide [A:-0-] Diarylmethane [A:-CH2-] Stilbene [A:-CH=CH-] Diaryl or arylalkyl sulfide [A:S
] Baladiazodiphenylamine 4-diazo 2,5,4″-triethoxydiphenylamine 4-diazo 2,5,4″-triethoxydiphenylamine 4,4″-bisdiazo 2,2′,5,5 ″-tetrahydroxydiphenylmethane bisdiazo8
,8″-dichloro5x5″-dimethoxybenzidine 4
-Diazo 2,5-dimethoxyphenylethyl sulfide 4-Diazo 2,5-diethoxy 4''-methyl-diphenyl sulfide Phenylpiperidine] Single bond [Phenylpyrrolidine type]) 4-Diazo 2,5-dibutoxy N-phenylmorpholin 4-diazo 2,5-diethoxy N-phenylmorpholin 4-diazo 2-methoxy N-thiomorpholin 4-diazo N-phenylpiperidine 4-diazoN-phenylpyrrolidine 4-diazo2,5-d-n-butoxyN-phenylpiperidineOther 4-diazoN-phenyl, derivatives of heterocyclic amine◎ N,N-substituted compounds of orthophenylenediamine and derivatives of orthoaminophenol 2-diazo 4-methylmercapto N,N''-dimethylaniline 2-diazo 5-benzoylamino N,N'-dimethylaniline 2-diazo 1-naphthol-5-sulfonic acid The diazo compound is used as a relatively stable diazonium salt as a sulfate or hydrochloride, or as a double salt with zinc chloride, tin chloride, aluminum sulfate, etc.

Further, stabilization methods such as allylsulfonate (diazonium salt of aromatic sulfonic acid) and diazosulfonate can also be used. ◎ Diazoamino compound 4-[(2-sodeoxycarbonyl-5-sodeoxysulfonylbenzene (1))diazoamino]-2-chloro-5-methyl-benzene 4-diazoaminosarkoxy 1
, 3-Methyl-5-benzoylaniline 4-diazoaminosarkoxy 2-chloro-5-methoxybenzoylaniline ◎ Antidiazotate Neutralize the solution of the diazonium salt mentioned above to neutral to slightly alkaline, and add 50 to 70% 100 for strong alkaline
Addition obtained at ~125°C.

General formula, k-N=N-ONa (, Ar': aromatic group).
◎ Diazosulfonate Diazosulfonate is obtained by reacting the aforementioned diazonium salt with sodium sulfite in neutral or slightly alkaline conditions.

--- According to the method of the present invention, images of multiple types of thermally transferable azo coupling components that develop different hues when coupled with a common diazonium compound can be made to accurately correspond to the original image. All at once, it is thermally transferred onto a diazo copying material, thereby making it possible to easily prepare diazo multicolor copies.

Moreover, in manufacturing diazo multicolor copies, only the manufacturing process of the diazo multicolor copying master requires an exposure process. A large number of diazo multicolor copies, as many as 20 to 10 copies, can be prepared without the need for an exposure step. The multicolor copying method of the present invention using the above-mentioned diazo multicolor copying master is different from the conventional diazo multicolor copying method using a multicolor copying original with a layer of coupler provided on a selected portion of the back side of the original. It offers significant advantages over copying methods.

In the conventional diazo multicolor copying method, during development, the coupling between the basic color coupler and the diazonium compound existing in the diazo photosensitive layer or the developer, and the coupling between the twist transfer coupler and the diazonium compound are caused by a racing reaction. Therefore, color separation between basic color images and color-specific images becomes an important issue, and when diazo copies are prepared from the same multicolor copy original, the color separation of the copies decreases as the number of copies increases. shows a tendency to Furthermore, since it is practically difficult to provide a layer of thermal transfer coupler on the back side of a document in exact accordance with the ring edge of the original image, the heat transfer coupler that protrudes from the original image ring may be removed after exposure. It reacts with the remaining traces of diazonium salt and gives unpleasant smearing to diazo multicolor copies. According to the present invention, all the couplers are applied onto the master in accurate response to the original image, and the images of the plurality of couplers on this master are thermally transferred onto the diazo copying material at once, so that the above-mentioned color Defects such as poor separation and bleeding can be effectively eliminated. It is particularly suitable for copying complex line drawings, crossed line drawings, etc. Note that when using a diazo copying material with a diazonium compound layer provided on the entire surface, there will be undecomposed diazonium compounds in the white area, but this remaining diazonium compound can be decomposed by exposing the entire surface to light. Or, by taking advantage of the property of the diazonium compound being water-soluble compared to the dye image formed by using a fixing method such as washing and removing it, a clear multicolor copy that is prevented from discoloring can be obtained. be able to.

In addition, a transparent or semi-transparent material is used as the electrostatic photosensitive substrate for the master, and substantially light-opaque pigments, dyes, etc. are used in the charged particles of the azo coupling component applied to the electrostatic image. When the master and the diazo copying material are layered and heated, exposure can be performed from the back side of the master. According to this method, the diazonium compound in the white background portion is decomposed simultaneously with the thermal transfer of the heat-volatile or heat-sublimable coupler, which is advantageous for the purpose of the present invention. In the present invention, the azo on the master
Since the image of the coupling component and the image of the diazo copy are inversely related to each other, the image of the azo coupling component on the master, and therefore the electrical latent image, can be optically inverted. Alternatively, consideration must be given to making the base material of the diazo copy a transparent material so that it can be viewed from the back.

The diazo multicolor copies produced by the method of the present invention have excellent color separation and clear colored images, and have outstanding fixing properties and fastness against heat, friction, water, and other organic solvents. ing.

Furthermore, this multicolor copy has far less stain on the white background than conventional diazo copies. The diazo multicolor copying method of the present invention includes:
Because of these characteristics, ordinary natural color copies: color-coded drawings such as maps, civil engineering plans, architectural plans, plans for ships, vehicles or other machinery, flow sheets for chemical plants; copies of original design drawings, etc. It is useful for many purposes. The present invention will be explained using the following examples.

Example 1 Photoconductive zinc oxide (Sazex4OOO manufactured by Sakai Chemical Industry Co., Ltd.)...
100y toluene...
80f acrylic modified resin (Lastrazol 6-1036 manufactured by Dainippon Ink & Chemicals Co., Ltd./40y fluorescein) is dissolved in 10 ml of methyl alcohol and added.

12m9 fluorescens
12m9 bromophenol blue
Stir and mix 12 mg of the above mixture in a homomixer,
The obtained uniform photosensitive solution was heated to 0.3? A zinc oxide photosensitive paper was prepared by applying the coating to a thickness of 15 μm on tracing vapor whose back side was made conductive using a percoater wrapped with piano wire and drying. The photosensitive paper obtained has full visible sensitivity.

Next, the photosensitive layer is charged by a minus 6 kV corona discharge in a dark place, and the image of the color original is exposed through a Kodak green filter NO58 to form a first electrostatic latent image. Electrodeposition obtained by dispersing 0.5y of 1-phenyl-3-methyl-5-pyrazolone, a heat-sublimable coupler, in Isovar G (product of Etsu Stard Oil Co., Ltd.) 1e, an isoparaffinic hydrocarbon, for 3 minutes using ultrasonic waves. The first electrodeposition process is completed by immersing it in the liquid.

Next, the above-mentioned photosensitive paper was again subjected to a minus 6 kV corona discharge in a dark place, and the image of the color original was transferred using Kodatsu's red filter No. 1. 25 to form a second electrostatic latent image.

0.5 of 2,3 deoxynaphthalene, a heat sublimable coupler, is added to Isopar Gle, an isoparaffinic hydrocarbon.
y is dispersed by ultrasonic waves for 3 minutes and immersed in the obtained second electrodeposition solution, thereby completing the second electrodeposition treatment. Furthermore, the above-mentioned photosensitive paper was again subjected to a minus 6 kV corona discharge in a dark place, and the image of the color original was transferred using Kodatsu's blue filter No. 1. 47A to form a third electrostatic latent image.

0.5f of acetoaceta anilide, a heat sublimable coupler, is added to Isopar Gll, an isoparaffinic hydrocarbon.
is immersed in a third electrodeposition solution obtained by dispersing it with ultrasonic waves for 3 minutes to complete the third electrodeposition process. In this manner, by repeating the above-mentioned three times of charging, exposure, and electrodeposition, a multi-sheet multicolor copying master having three types of coupler images that develop three primary colors by coupling with the diazo compound described below can be obtained.

A three-color reverse image can be obtained by bringing the surface of the obtained diazo copying master into close contact with the surface of the following thermosensitive copying sheet and contacting it with a heated roller or heat conductive plate at 110 to 130 DEG C. for 2 to 5 seconds.

The diazo copying master can be used repeatedly and can reach more than 5 losses. Thermal copying sheet 4-Diazo 2,5-diethoxybenzoylaniline chloride 11㎡Ncl2 double salt
10V citric acid
4y dextrin
10y patent blue
Add 0.1y urea and 70y water to make a total volume of 11.

This solution was applied to translucent paper such as tracing vapor using a general coating method such as an air knife coater, and heated to 100°C.
Dry at the following temperature to make a copy sheet.

Since this reverse image copy is transparent tracing vapor, it can be interpreted as a normal image when viewed from the back of the copy.

Example 2 When the electrostatic latent image formed by exposing the zinc oxide photosensitive paper used in Example 1 to form a reverse image is immersed in the developer used in Example 1, a reverse image diazo master is obtained. .

Next, using the solution of the thermal copying sheet formulation shown in Example 1, a copying sheet using opaque paper instead of tracing vapor was used, and the coated side of the copying sheet and the reverse image side of the diazo master were connected. When they are placed face-to-face in close contact and transferred and developed by the method of Example 1, a color normal image is obtained.

Example 3 Polyvinyl carbazole 4f Monochlorobenzene 60f Trinitrofluorenone 6.4f The above viscous liquid was coated on art paper with conductive treatment on the back side using a coating parser wrapped with 0.37 m of piano wire and dried to a thickness of 5 to 10 μm. do.

The organic semiconductor photosensitive paper obtained is fully visible or sensitive. This photosensitive paper was subjected to a minus 6 kV corona discharge to make its surface photosensitive, and as in Example 1, the color original was passed through it and separated into three colors, and the first to third electrostatic latent images formed on each were separated. Process with the following dry electrodeposition agent to obtain a multicolor copy master. Red coloring electrodeposit m-aminophenol (thermal sublimation coupler) 1y iron content
200V blue coloring electrodeposit 2,3 dioxynaphthalene 1f iron content
200y yellow coloring electrodeposit acetoacetanilide 1V iron content
The surface of the obtained 200y diazo copying master is brought into close contact with the surface of the diazo photosensitive paper shown below, and after contacting with a heated roller at 80 to 100°C or a heat conductive plate for 2 to 5 seconds, the color becomes red or yellow when developed with ammonia gas. , a blue image is obtained.

It should be noted that the diazo copying master is used repeatedly.
0! F9. The above can also be copied. Note that the above 2,3-dioxynaphthalene alone was used with an inter-electrode distance of 0.5 CTft.
When the volume resistivity was measured using a commercially available electrometer under no load by tapping lightly between each electrode area of 4.5 cIt, it was 1.5×10 10 Ω−0.

Diazo copy paper 4-Diazo 2,5-dimethoxybenzoyl aniline chloride 112 ZnC 1210y Citric acid 8y Dextrin
This solution, which is prepared by adding 10y of water to make 1e, is coated on translucent paper such as tracing vapor using a general coating method such as an air knife coater and dried to form a copy sheet.

Example 4 Add 6k of the photoconductor-containing photosensitive paper obtained in Example 3.
The surface of the paper is exposed to a corona discharge of v to give photosensitivity, and as in Example 1, the color original is exposed to three-color separated light, and the three types of electrostatic latent images formed respectively are Process with liquid to obtain multi-color copy masters.

Electrostatic liquid (a) for the latent image obtained through a green filter, electrodeposition liquid (a) for the latent image obtained through a red filter, and electrodeposition for the latent image obtained through a blue filter. Apply liquid (c) respectively.

Electrodeposition liquid (a) Shellsol T, which is an isoparaffinic hydrocarbon (a product of Shell Oil Co., Ltd.) 1e carbon black (Cigale 600) (a product of Tokai Electrode Co., Ltd.)
1V linseed oil
1.3y3-methylpyrazolone (sublimable coupler)
0.5 g of the above mixture is milled in a ball mill for 5 hours and diluted into Schersol Tl9OOcc, an isoparaffinic hydrocarbon.

Electrodeposition liquid (0) Scherzol T, an isoparaffinic hydrocarbon (product of Shell Oil Co., Ltd.) 100cc carbon black (Segal 600) (product of Tokai Electrode Co., Ltd.) Asphaltene extracted from 1y straight asphalt with Schierzol T
2'2,3 deoxynaphthalene (sublimable coupler)
0.5y The above mixture is ground in a ball mill for 5 hours and diluted into Scherzol T9OOcc, an isoparaffinic hydrocarbon.

Electrodeposition liquid (c) Scherzol TlOOCC, an isoparaffinic hydrocarbon Carbon Black Seagull 6001y Asuraartene, extracted from straight asphalt with Scherzol T 2y Aceto Acetanilide (yellow coloring sublimation coupler)
0.5y The above mixture is ground in a ball mill for 5 hours and diluted into Scherzol T9OOcc, an isoparaffinic hydrocarbon.

The surface of the obtained diazo copying master and the surface of the diazo copying sheet described below are brought into close contact with each other and brought into contact with a 110 to 1200 C heating roller or heat conductive plate for 2 to 5 seconds to transfer the sublimation coupler onto the diazo photosensitive paper. The obtained copy is an invisible image, but when it is brought into contact with ammonia gas or an alkaline aqueous solution, the part electrodeposited by the electrodeposition liquid in (a) turns red, and the part electrodeposited by the electrodeposition liquid in (b) turns red. The parts are shown in blue (
The part electrodeposited by the electrodeposition solution in c) develops a yellow color. Diazo photosensitive paper ammonium citrate 6.6y citric acid 6.6y ammonium sulfate 9.2f thiourea
12y4-diazo N-ethyl N-
Benzylaniline chloride 1122'NCl2lO
Add 0.15y of methylene blue water to make a total volume of 1e. Apply this solution to translucent paper such as tracing vapor using a general coating method such as an air knife coater and dry at a temperature of 120°C to create photosensitivity. .

The diazo copying master can be used repeatedly and can be used more than 7 times. If the diazo copy master onto which the sublimation coupler has been transferred is a reverse image, opaque photosensitive paper may be used. Example 5 Photoconductive zinc oxide (Seido Kagaku Kogyo Co., Ltd. SCX5OO... 10
0y toluene 90y acrylic modified resin (E-1048 manufactured by Desoto CO)
20y acrylic modified resin (Desoto CO E-041) 2
0y Fluoretcene 12m9 Bromophenol Blue 12WL9 Brilliant Blue FCF4mg The above mixture was decomposed by ultrasonication for 5 minutes, and the resulting uniform photosensitive solution was 0.3? Using a percoater wrapped with piano wire, the film was coated to a thickness of 15 μm on art paper, the back side of which was conductive, and dried to create zinc oxide photosensitive paper.

The photosensitive paper obtained has sensitivity in the entire visible range.

Next, a -6kV corona discharge is applied in a dark place to make the surface photosensitive, and the image of the color document, which is made up of only red, yellow, and blue, is transferred to the Kodatsu green filter NO.
58 to form a first electrostatic latent image, and treated with an electrodeposition liquid (a) shown below. Next, the above-mentioned photosensitive paper is again subjected to a minus 6 kV corona discharge in a dark place to make its surface photosensitive, and the image of the above-mentioned color original is exposed through a red filter NO25 made by Kodatsu, and a second electrostatic latent Form an image and use the following electrodeposition liquid (0)! Treated with a trowel.

Furthermore, the photosensitive paper was again subjected to a minus 6 kV corona discharge in a dark place to impart photosensitivity to its surface, and the image of the color original was transferred to Kodak's blue filter No. 1. 47A to form a third electrostatic latent image, and apply the following electrodeposition liquid (c).
Processed at.

Electrodeposition liquid (a) Carbon black (carbon #50 manufactured by Mitsubishi Kasei Corporation) 10y acrylic resin 45% solids (MS manufactured by Teikoku Kagaku Sangyo Co., Ltd.)
-11Resin) 23Vβ naphthol
2y toluene
After dispersing the mixture consisting of 170y using an ultrasonic dispersion machine for uniform dispersion, Isopar H is added to the mixed paste, washed and filtered, and the residue is made into a pigment-treated cake-like product, and toner is manufactured according to the following recipe.

The above treated cake-like material 30y Alkyd resin 50% solid content...40y (Betucosol J-537 manufactured by Dainippon Ink & Chemicals Co., Ltd.) Isopar H...285y Toner obtained by uniformly kneading this blended mixture in a ball mill 10 cc is dispersed in Isopar Gle (isoparaffinic hydrocarbon manufactured by Etsuso Standard Oil Co., Ltd.).

Electrodeposition liquid (1) In the electrodeposition liquid (a), 1-phenyl-3-methyl-5-pyrazolone is used instead of β-naphthol.

Electrodeposition liquid (c) In the electrodeposition liquid (a), instead of β-naphthol, 2,6
- Using dioxynaphthalene.

In this way, by repeating the above-mentioned three times of charging, exposure, and electrodeposition, a multi-sheet multicolor copying master that can be coupled with the diazo compound described below to develop three colors can be obtained.

Next, as a thermal copying sheet, 4-diazo N-naphthalene-1,5-disulfonate N,N-dimethylaniline 15 fI caustic sorter 1 f Aqueous ammonia (2.5%) 5 ml 1 Add water to the above to dissolve and dissolve the entire amount. This solution (1000 ml) was applied to semitransparent paper that had been treated with a neutral sizing agent such as tracing vapor using a general coating method such as an air knife coater, and dried at a relatively low temperature to form a sheet for thermal copying. shall be.

Thus, when the surface of the diazo copying master having the image formed by the heat-sublimable coupler and the diazo compound-coated surface of the heat-sensitive copying sheet are brought into contact with a heat donor such as a heated roller, a three-color image is formed. A copy was obtained.

This copying master can be used repeatedly (4) or more times.

The same result can be obtained by transferring to the following diazo paper instead of heat-sensitive diazo paper and developing with ammonia gas. Diazo photosensitive paper 4-
Diazo 2,5-dibutoxy N-phenylmorpholin 11㎡ NCl 2l 5g citric acid
30f diethylene glycol 20f thiourea
40y zinc chloride
30y patent blue 0
．． 1f water is added to make the total amount 1e, and this solution is coated onto photosensitive paper base paper using an air knife coater to obtain a diazo photosensitive paper sheet.

The diazo copying master can be used repeatedly and can be used more than 5 times.

Example 6 Photoconductive zinc oxide (Special number Asia for electrophotography manufactured by Hakusui Chemical Co., Ltd.)...100
y toluene 90y acrylic modified resin (manufactured by Desoto Co., Ltd. E-1048, S0Iid
50% 20y acrylic modified resin (manufactured by Desoto Co., Ltd. E-041, S011d50%
20y fluorescein
121!9 Bromophenol blue
12m9 Brilliant Blue FCF4m9 The above mixture was dispersed with ultrasonic waves for 5 minutes, and the resulting photosensitive liquid was spread on art paper that had been subjected to conductive treatment to have an electrical resistance of 1CPΩd or less.
3w! This photosensitive paper, which is coated with a coating material of 23 to 27 y/y using a bar coder and dried, has sensitivity in the entire visible range.

Next, a minus 6 kV corona discharge is applied in a dark place to make the surface photosensitive, and the image of the text color document, which is divided into red, yellow, and blue, is exposed through a green filter NO58 made by Kodatsu. If an electrostatic latent image is formed and treated with the color electrodeposition liquid (a) shown below, a red image can be obtained on the zinc oxide multicolor copying master. Next, the above-mentioned photosensitive paper was again subjected to a minus 6 kV corona discharge in a dark place to impart photosensitivity to its surface, and the image area of the above-mentioned color original was removed using a Kodatsu red filter No. 1. 25 to form a second electrostatic latent image, which is then treated with the following electrodepositing solution to form a red image obtained in the first development and the red image obtained this time on the zinc oxide multicolor copying master. Two types of blue images are obtained.

Furthermore, the photosensitive paper was again subjected to a -6 kV corona discharge in a dark place to make its surface photosensitive, and the image of the color original was exposed through a Kodak blue filter 47A to form a third electrostatic latent image. Formed and treated with the following electrodeposition liquid (c).

Electrodeposition liquid (a) Brilliant carmine 6B (red pigment)...1.0y1
-Phenyl-3-methyl-5-pyrazolone (sublimable coupler for red coloring)...2.0y
Soybean oil modified alkyd resin (Betsukosol p-470 manufactured by Nippon Reichhold Co., Ltd.) 6f styrene-butadiene copolymer resin 6f Isopar H (isoparaffin hydrocarbon solvent manufactured by Etsuso Standard Co., Ltd.) 50ml electrodeposition liquid ( b) Riflex Blue AMF' (blue pigment)...0.8y2
,3-dioxynaphthalene (blue coloring sublimable coupler)
...2.0y soybean oil modified alkyd resin ...6.0f styrene-butadiene copolymer resin ...6.0V Isopar H
...50ml electrodeposition liquid (c) ZA-6
06 (yellow lake pigment manufactured by Dainichiseika Co., Ltd.)
...1.0y aceto●acetaanilide (yellow coloring sublimation coupler)
...2.0y chloroform
...50mt nigrosine base ・
...0.1y The above mixture was dispersed and mixed using ultrasound for 3 minutes,
Wash with Isopar H and form a cake.

The above cake...3.0f Soybean oil modified alkyd resin...6.0y Styrene-butadiene copolymer resin...6.0y Isopar H...50ml After kneading each of these blended and dissolved mixtures in a ball mill for 24 hours ,
Take 7 to 8 ml of the master and make the total volume 1e using Reisopar H to make a developer. Place the resulting three-color copying master closely against plain paper and bring it into contact with a heat donor such as a heated roller, and the sublimation coupler will be transferred. .

After that, apply the following coloring liquid and bring it into contact with ammonia gas to obtain a three-color copy image on plain paper (preferably, it is better to photodecompose the non-coloring area, since the ground will be 66% less 99%) Coloring liquid citric acid 6. 0y aluminum sulfate 9.0y thiourea
12.0y4-diazo N-ethyl-N-penzole aniline chloride 11゜NCl. 5. Of methylene blue 0.15y of water is added to make the total amount 1e. The diazo multicolor copying master can be used repeatedly and more than one copy can be obtained.

Example 7 Photoconductive zinc oxide (Sakai Chemical Industry Co., Ltd. Sazex4OOO) 100
g Silicone resin (Shin-Etsu Chemical Co., Ltd. KR-254:
SOlld5O%) 40y toluene
100y bromophenol blue (dissolved in methyl alcohol 107IL1)
20' Stir and mix the above mixture in a homomixer, and apply the resulting uniform photosensitive liquid to a thickness of 15 μm on tracing vapor whose back side has been subjected to conductive treatment using a percoater wrapped with 0.3 mm piano wire. Dry to create zinc oxide photosensitive paper.

The obtained photosensitive paper was subjected to a minus 6 kV corona discharge in a dark place to make it photosensitive, and the color original was passed through a Kodatsu blue filter No. 1. 47A to create a first electrostatic latent image, which is then immersed in the following electrodeposition solution (a) to form a yellow copy master.

Electrodeposition solution (a) Dissolve 50 ml of chloroform and 0.1 y of nigrosine base, then add 2 ml of sublimable coupler (acetoacetanilide).
．． After adding 0y and dissolving it, 0.5d of ZA-606 (yellow pigment: Dainichiseika Co., Ltd.) was added and dispersed for 2 to 3 minutes using an ultrasonic disperser.
(manufactured by Etsuso Standard Co., Ltd.) is added to the same amount or twice the amount of chloroform and further dispersed in a disperser for 2 to 3 minutes, and then the contents are filtered using a Nutsuchie filter and the resulting cake is taken out.

And soybean modified alkyd resin (
Dainippon Ink & Chemicals Co., Ltd. P-470: SOll
d5O%), 6.5y1 acrylic resin (LR-472 manufactured by Mitsubishi Rayon Co., Ltd.) and titanium tetraprofoxide, a dispersant 6.5y1 Isopar H, was added to 50ml.
In addition, 7 to 8 ml of the condenser obtained by dispersing with an ultrasonic disperser for 2 to 3 minutes is added to solvent (Isopar H) 1e, and dispersed with a disperser for 2 to 3 minutes.The resulting mixture is used as a yellow developer. do.

After drying the surface of the electrophotographic photosensitive paper on which the yellow image obtained by development was formed, it was then subjected to a -6 kV corona discharge to impart photosensitivity, and the color original was exposed through a Kodatsu red filter No. 25. A static latent image of the blue image area is formed by performing this process, and a blue image is obtained by immersing it in the following electrodeposition solution (mouth). Electrodeposition liquid (mouth) Isopar H5Oml, an isoparaffinic hydrocarbon
Add 6.5y of linseed oil-modified alkyd resin (J534 manufactured by Dainippon Ink & Chemicals Co., Ltd.) and dissolve it to obtain Denol 2.0f, a sublimation coupler, and Flex Blue A.
After adding MF'0.5y and dispersing for 2 to 3 minutes using an ultrasonic disperser, the dispersibility obtained by reacting soybean-modified alkyd resin (P-470 manufactured by Dainippon Ink & Chemicals Co., Ltd.) with titanium tetraprofoxide Add 6.5 J of resin and disperse again for 2 to 3 minutes using an ultrasonic disperser to form a condenser.

7 to 8 ml of this condenser was mixed with rear isopar H to make the total volume 11, and used as a starting liquid. When immersed in this developer, the blue image portion forms a blue image on the copying master. After drying this copying master, a corona voltage of -6 kV was applied to the photosensitive paper again in a dark place to make it photosensitive, and the color original was exposed through a green filter NO58 manufactured by Kodatsu to reduce the electrostatic potential of the red image area. The surface of the master paper for diazo multicolor copying, which forms an image and forms a red image when immersed in the electrodepositing solution (c) of Example 6, and the surface of the following thermal copying sheet are brought into close contact with each other at 110 to 130
A reverse color image can be obtained by contacting it with a heating roller or heat conduction plate at ℃ for 2 to 5 seconds.The diazo type multicolor copying master can be used repeatedly, and more than one color copy can be obtained. It was done.

thermal copy sheet 4-Diazo 2,5-diethoxyben Zoylaniline chloride 11゜NCl.

Double salt 10y citric acid 4y dextrin
10y patent blue
0.1y urea
This solution, made up to 1 f by adding 70 f of water, is applied to translucent paper such as tracing vapor using a general coating method such as an air knife coater, and dried at a temperature of 100° C. or lower to form a copy sheet.

Since this reverse image copy is a tracing vapor, it can be interpreted as a normal image if viewed from the back of the copy. Example 8 The electrophotographic photosensitive paper shown in Example 3 is electrically charged, an electrostatic latent image is created through a three-color separation filter, and then developed through the developer shown below, and the charging exposure is repeated three times, resulting in thermal sublimation. A diazo multicolor reproduction master with couplers is obtained.

That is, developer (a) yellow image toner activated carbon (Dynablack SH. manufactured by Mitsubishi Kasei Corporation)
1y acetoacetanilide (sublimable coupler) 4
After dissolving and dispersing in 50 ml of chloroform and stirring in a ball mill for 4 to 5 hours, the same amount to twice the amount of chloroform was added to Isobar H (manufactured by Etsuo Standard Co., Ltd.), which is an isoparaffinic hydrocarbon, and the mixture was further dispersed in a disperser for 2 hours. After dispersing for ~3 minutes, filter the contents using a Nutsche filter to obtain a cake.

Cake 2.5y isophthalic alkyd resin (0DE-188 manufactured by Dainippon Ink & Chemicals Co., Ltd.) 6.5y pure alkyd resin (J53 manufactured by Dainippon Ink & Chemicals Co., Ltd.)
4) Make a compactor with 4.0y isopar H5Omt and add this 7~8ml and rear isopar H
Make the total volume 1f and use it as the starting solution.

(b) Activated carbon toner for blue images (Dynamic SH. Mitsubishi Kasei Corporation) 1
g Sublimable coupler (2,3-dioxynaphthalene)
3f chloroform
After dissolving and dispersing the solution in 50ml and stirring in a ball mill for 4 to 5 hours, the isoparaffinic hydrocarbon is obtained.

Add Isopar H (manufactured by Etsuo Stardard Co., Ltd.) to the same amount to twice the amount of chloroform, and then use a disperser to
After dispersing for ~3 minutes, the contents were filtered using a Netstier filter and the resulting cake was taken out for the following formulation. cake
2.5y isophthalic resin (0DE- manufactured by Dainippon Ink and Chemicals Co., Ltd.)
188) 6.5
V pure thick resin (manufactured by Dainippon Ink and Chemicals Co., Ltd.)
-534) 4.0V isopar H5
Make a compactor with Omt and add 7 to 8 ml of this to a rear isopar H to make a total volume of 1f and use it as a starting liquid.

(c) Toner carbon black for red images (Diablack SH. Manufactured by Mitsubishi Kasei Corporation) 1y
1-phenyl-3-methyl-5-pyrazolone
3y chloroformy
Dissolve and disperse in 50ml and use a ball mill for 4
After stirring for ~5 hours, the same amount to twice the amount of chloroform was added to Isopar H (manufactured by Etsuo Standard Co., Ltd.), which is an isoparaffinic hydrocarbon, and the mixture was further dispersed for 2 to 3 minutes using a disperser. The contents are filtered and the resulting cake is taken out and used as a developer in the next formulation.

Cake 2.5f1 Isophthalic Alkyd Resin (0DE-188)
6.5q pure alkyd resin (J534)
Make a compactor with 50ml of 4.0y Isopar H, collect 7~8ml of this, add 1e to the total amount using Isopar H.
Use this as the starting solution.

These three colors of image toner developer are charged, exposed and developed. By developing yellow, blue, and red in this order, a black diazo multicolor copying master with good heat absorption can be obtained. By bringing the surface of this diazo type multicolor copying master into close contact with the surface of the thermal copying sheet described below and contacting it with a heating roller or thermal conductive plate at 110 to 130°C for 2 to 5 seconds, a true image with colors close to natural colors will be produced. can get.

The diazo multicolor copying master can be used repeatedly. And I was able to get more than one color copy of the diazo style.・Thermal copying sheet 4-diazo 2,5-diethoxy 4″-methyl-diphenyl sulfide 112 ZnC 1215 g Monochloroacetic acid 30y Dextrin 10f Urea
Add 100y of water to make a total volume of 1e.

This solution is applied to translucent paper such as tracing vapor using a general coating method such as an air knife coater and dried at a relatively low temperature to form a copy sheet.

[Brief explanation of drawings]

Figures 1-a to 1-e are explanatory diagrams for explaining the principle of the diazo multicolor copying method of the present invention, in which Figure 1-a is a charging process and Figure 1-b is an exposure process. , FIG. 1-c shows the electrodeposition process, FIG. 1-d shows the thermal transfer process, and FIG. 1-e shows the developing process. 1 is a corona discharge electrode, 2 is a photosensitive layer, 3 is a substrate, 2
a, 2b, 2c are electrostatic images, 4a, 4b, 4c are images of azo coupling components, 5 is an original, 7 is a heat source, 8 is a diazonium compound layer, 9 is a substrate, 10a, 10b, 10c are dye images are shown respectively.

Claims (1)

[Claims] 1 An electrostatic image is formed on an electrostatographic photosensitive layer, and the electrostatic image is developed with charged particles of a thermally volatile or thermally sublimable azo coupling component to form a photosensitive layer having an image of the azo coupling component. and a copying layer containing a diazonium compound are superimposed, an azo coupling component is thermally transferred to the copying layer, and the azo coupling component is developed and colored. are carried out multiple times using each of a plurality of types of azo coupling components that develop different hues when reacted with a common diazonium compound, but whose thermal transferable temperature ranges are close to each other, As a result, a multicolor copy master in which images of multiple types of azo coupling components are formed on a single photosensitive layer is created, and images of multiple types of azo coupling components on this multicolor copy master are transferred onto the copy layer. A diazo multicolor copying method characterized by simultaneous transfer to form a multicolor copy image.