DE2165665A1 - Process for producing images - Google Patents

Description

MTENTANWXLTE

DR. E. WIEGAND DIPL-ING. W. NIEMANN DR. M. KÖHLER DIPL-ING. C GERNHARDT

MÖNCHEN HAMBURG

TELEPHONE: 55 547 * TELEGRAMS: CARPATENT

8000 MONKS 15,

NUSSBAUMSTRASSE 10

December 30, 1971

V / 40 922/71 - Ko / DE

Fuji Photo Film Co. Ltd., Ashigara-Karaigun, Kanagawa / Japan

Process for producing images

The invention relates to a method for producing images and, in particular, to an imaging method using the reaction of compounds that lead to a specific reaction with macromolecular substances are capable.

In the drawings represents

Pig. 1 is an enlarged cross-sectional view of a Embodiment of a photosensitive element for use according to the invention,

Pig. 2 a method for imagewise exposure of the photosensitive element,

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Pig. 3 shows a method of electrolytic treatment the photosensitive elements after imagewise exposure,

Fig. 4 shows a method of treating with warm water on the photosensitive member according to the electrolytic treatment ,.

Pig. Figure 5 shows a method of removing the photoconductive layer from the photosensitive member according to treatment with warm water,

Pig. 6 the procedure for removing the electroconductive layer,

Pig. 7 the metal image obtained according to the invention,

Pig. 8 the method for thermographic copying according to the invention,

Pig. 9 the polymer image obtained by thermographic copying according to the invention;

Pig.10 a mimeographic plate material according to the invention ,

Pig.11 a mimeographic one made according to the invention Plate,

Pig.12 a method for transferring the invention obtained polymer image on a metal plate,

Pig.13 a method of etching the surface of the metal plate after the transfer and

Pig.14 after the removal of the polymer image and after the printing plate obtained from the etching

209829/11 * 1

The formation of images from macromolecular substances is already part of the tanning process Gelatin and silver halide are known. A method using a silver halide and a by Addition polymerizable. Materials is previously described in U.S. Patent 3,194,661. Also the US patent No. 2,927,002 discloses a process not using a silver halide, an addition polymerizable Substance and a photoactivatable addition polymerization initiator together with a cellulose derivative can be used. Various photosensitive resins bind already in a number of Patent specifications indicated and technically available, for example Dycril from Du Pont, Uyloprint from Badischen Aniline and Soda Factory, A.P.R. from Asahi Chemical, T.P.R .. from Tokyo Oka Industries, K.P.R. from Eastman Kodak and similar materials. The earliest masses known in the art consisted of one Combination of polyvinyl alcohol with dichromate. The above specified processes or materials for obtaining macromolecular images have disadvantages, such as difficult handling, insufficient storage stability, low sensitivity and the like.

Another method of making macromolecular Images on the surface of electrolytic photosensitive Layers is described in US Pat. No. 3,106,516, according to which method a obtained by an electrolytic photographic process Hardener or plasticizer sample against a sheet with a macromolecular substance for post-treatment is pressed to achieve the macromolecular image. However, a transfer stage is used in the method so that the images obtained are a Possess a lack of sharpness. Also in the US patent

209 8 29 / T U1

3 172 827 describes a method in which a polyamide resin contained in an electrolyte bath is imagewise is made insoluble and on the photosensitive layer by means of increasing the pH of the cathode during the electrolysis is deposited.

It has been found, however, that with these methods it is difficult to obtain an image of sufficient mechanical strength Maintain strength and solvent resistance.

Furthermore, there are methods for forming a polymer image by passing an electric current through it already in the'US patents 3 409 413, 3 436 215, British Patent 1,178,552 and 1,136,209. In this process, a polymerizable Monomer used and therefore there are often difficulties in terms of storage time.

Furthermore, a method for controlling the enzymatic Activity in the passage of an electric current given in Japanese Patent No. 549,870, however, considerable precautions are required with this process in order to obtain a stable gelatin image to obtain.

The use of a polymer as a toner in an electrophotographic process is also already known. A fine obtained by crushing a polymer material by, for example, a jet mill powdered polymer is mixed with carrier particles to make an electrophotographic cascade developer obtain. Electrophotographic liquid developers can also be produced by using a powdery polymer is dispersed in an insulating liquid that does not dissolve the polymer. This allows polymer images can be obtained by developing electrostatic latent images with these developers. In general liquid developers produce better image quality

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"D-

as a dry developer. However, it is quite difficult to get a stable dispersion when using the polymer is hydrophilic. For example, the ones specified in German Offenlegungsschrift 2 004 817 and 2005 180 In the process, there is a disadvantage that complicated processes for preparing the developer are necessary. On the other hand, the dry developers are the toner composed of finely powdered hydrophilic polymers contained, associated with the disadvantage that moisture is easily absorbed by the aggregates.

Furthermore, it is known that protein against water by various organic compounds, for example aldehydes such as lOrmaline, chlorotriazine, mucochromic acid and the like is made insoluble. In addition, it is known that protein is caused by certain metal ions, such as chromium ions, is made insoluble. These compounds are important in the photographic industry, however the effect is the insolubilization is extremely low or the stability of the compounds themselves is insufficient.

As a result of extensive research into reaction conditions between hydrophilic macromolecular substances and various organic compounds was under of the invention found that cyclic compounds that have the following bonds

-S-O-S- -Se-C-S-

i · ι

Ν "'or N

A / A

included, for an extremely rapid solidification of hydrophilic macromolecular substances, such as gelatin, at pH en are not lower than 8 and are suitable in the presence of metal ions. On this basis, the

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2165865 '

Invention found a new and valuable imaging process, wherein at least one component is selectively imagewise of a system from A) a hydrophilic macromolecular Substance, B) of a metal ion of groups 6A, 7A, 8, 1B or 2B of the periodic table ITIPAC Comptes Rendus XXIII Conference, 183, 1965, C) a compound to maintain the pH of the water or the water-containing solvent a value of not less than 8 when in contact with this or any substance that makes such a connection upon decomposition, and D) a compound represented by the following general formula

where Z and Z ^{1 are} a non-metal atom grouping necessary to complete a heterocyclic ring, X is an anion and Y is an atom of Group 6B of the periodic table, are subtracted or added from or to this system, so that an image containing a water-insoluble macromolecular substance, is obtained.

The reaction between the polymer of the compound and the metal ion is considered as follows:

The primary amino group of the polymer reacts with the compound and bonds to a carbon atom bonded to -S and -Y to form a Schiff base, and at the same time ring Z _{1 is opened} to form an -SH group, while the ring Z usually remains. Then the two are thereby formed

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-SH groups through the metal ion by forming a complex bound.-This terminates the crosslinking reaction.

Model:.

Polymer ■ - compound - metal ion - compound - polymer

As indicated above, the connection with the primary amino group react and form an SH group, which reacts with the metal ion. In view of this are the compounds with the in the introductory two formulas specified bindings. These compounds easily react with a primary amino group and cause a ring opening reaction to form an -SH group.

A preferred subclass of heterocyclic rings is limited by the fact that Z and Z ¹ . Not represent meta 11atoms which form a 5-membered or 6-membered heterocyclic ring which can have further substituents including attached rings.

According to the invention, all four components be present to form an image. It is clear that the image can only be formed on the parts where all components are available. For example, if the gelatin layer A, the metal ion B and the Compound D contains, is contacted with the alkaline solution C, the image is formed and this constitutes an addition process On the other hand, from a system in which all four components are present, one or multiple components can be removed image by image. This is an elimination process or a subtraction process.

The invention can thus be carried out by at least one component / from a system, which includes all contains four components A, B, C and D is removed. For example, an alkali C is removed by adding an acid.

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A preferred embodiment according to this method ren is that a substance is introduced into a system which contains all four components, which can release a compound that acts as an acid through exposure to electromagnetic radiation, image-wise the system to electromagnetic radiation with the formation of this acid, which neutralizes the alkali, which corresponds to the removal of the alkali C, is exposed so that an image is formed.

As the substances releasing an acid, organic halogen compounds are exemplified. Carbon tetrabromide, Iodoform, hexachloroethane, polyvinyl chloride and polyvinylidene chloride are typical examples of such substances. These compounds set a halogen radical or -radically released by exposure to electromagnetic radiation. The halogen radical catches the hydrogen atom the system and forms a hydrogen halide, which is a strong acid.

According to the invention, the image-wise subtraction or addition of the components of the system by different Processes such as electrolytic, electroconductive processes, electrophotographic processes, electroconductive recording methods, thermal recording methods and the like, or by direct manual ones Addition can be effected.

The image obtainable according to the invention is composed of a macromolecular substance and therefore cannot only for ordinary recording and copying, but also for the production of printing plates for spirit printing, Offset printing, intaglio printing, letterpress printing and mimeographic Printing and used to make gelatin reliefs for perfume transfer prints. According to the Invention image can also be used to make printed circuit boards, braille prints and slides for overhead pro j ection can be used. According to the invention it is too

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possible to obtain electron beam drawing materials.

The hydrophilic macromolecular substance A in the context of the invention preferably contains a primary amine radical. Such macromolecular substances can, for example, be natural proteins such as lysine or arginine contained as amino acid units, such as gelatin, glue, casein, albumin, protamine, globulin and the like. Even various synthetic macromolecular substances containing primary amino groups can be used for this purpose will.

Examples of such synthetic macromolecular substances are the polymers that are composed of • amine-containing monomers were obtained, for example aminoethyl vinyl ether (Liebigs. Annalen der Chemie, 601, Page 81, 1956), aminostyrene (Chemical Abstract, Volume 34, page 389, 1940), p-aminophenyl vinyl ether (Chemical Abstract, Volume 56, 12781, 1962) or vinylbenzylamine (reports of the German Chemical Society, Volume 56, page 2154, 1923). Also copolymers containing the above Containing listed monomers, can for the present Purpose to be used.

Those from are also applicable for this purpose macromolecular reactions obtainable polymers, for example between polymethyl acrylate and diamines (Die macromolecular chemistry, Volume 22, page 31, 1957) or reduction of polyacrylamide by lithium aluminum hydride (The Journal of Organic Chemistry, Volume 26, Page 1274, 1961). Polymerized primary amines such as polyvinylamines, Polylysins and the like also belong to this class.

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The main object of the invention is an image of a macromolecular substance and a method therefor.

The minimum number of primary amino groups in the polymer is 2. The preferred amounts can be more than two units for every 1000 repeating units of the polymer.

There is no particular restriction on the position of the primary amino groups in the polymer. A terminal position of the polymer groups is not essential for the invention.

The following table gives examples of synthetic polymers with primary amino groups:

Polymer 1 2 3 4th 5 6th 7th -CH ₂ -CH-
-CONHg 70
Mol- # 90
MoI-Jf 80 95
Mon I-56 90
MoI-Jb 80
Mon I-55 98
M0I-5S —CHp — CH-
COOCH ₅ 27
Mol- # 8th
.Mol-Ji 18th
Mol-jG 4th
Mol-jS 9
Mol- # 19th
M0I-7S -CH ₂ -CH-
CONH (CHg) _n N 3
_T mol- # 2
Mon I-36 2 1
Mon 1- $ 1
Mon I-56 1
Mol-? S -CHg-CH-
CHgNHg - - - - - - - 2
Mol-f _c η 3 3 3 3 2 2 - ⁺ A730 °
1 fo NaCl 2.60 1.85 1.88 1.83 1.54 1.62 3.07

⁺ Intrinsic viscosity at 3O ⁰ C in 1 $ aqueous sodium chloride solution

20982971121

These polymers can be prepared by conventional methods be-as in the following. Examples given.

Preparation of polymer 1:

76 g of a copolymer of methyl acrylate (30 mol $) and acrylamide (70 mol $) were dissolved in 2 liters of water and 25 g of 1,3-propanediamine were added with stirring. Daa system was maintained at 40 to 5O ⁰ C for 4 hours. The aqueous solution of the primary amine-containing polymer was then subjected to dialysis with distilled water overnight and then freeze-dried. As a result of the titration with 0.05 η-hydrochloric acid, the polymer obtained contained amino residues in an amount of 3 mol ~ $. The polymer had an inherent viscosity / hI ^ ₀ ^ _a Qj_ ^of 26 °

Polymers 2 through 6 can be prepared using similar procedures produce.

Copolymers 2 to 6 were made according to the manufacturing method of polymer 1, but the starting copolymers given in the table below were used and reaction conditions applied:

Polymer 2 3 4th 5 6th Starting copolymer
Dimensions: Acrylamide 90 80 95 90 80 Methyl acrylate 10 20th 5 10 20th Response time (hours) 4th 4th 3 3 3 Reaction tempera door 40-50 40-50 30-40 30-40 30-40

209829/1 12.1

Production of polymer 7:

14 "2 g (0.2 mol) of powdered polyacrylamide (molecular weight about 100,000) 1 dioxane were dispersed in 1, then added to 4 g of lithium aluminum hydride and heated with stirring for 6 hours at reflux (about 100 ⁰ C).

Then 5% hydrochloric acid was gradually added to the reaction mixture to inactivate the unreacted lithium aluminum hydride. The dioxane was then removed until the reaction product solidified. The solid was dissolved in 100 ml of a 5% aqueous solution of sodium hydroxide and a homogeneous aqueous solution of the polymer was obtained. The solution was placed in a cellophane bag, dialysis, over-fold against distilled water, and then freeze-dried. Yield 13.0 g, ßlj ^ jJ _aC1 = 3.07. The titration with 0.05 η-hydrochloric acid showed an amino residue content of 2 mol $. The macromolecular substance A to be used according to the invention is preferably soluble in cold or warm water or in a mixed solvent containing water. Preferably the mixed solvent contains more than 20% by volume of water. The solvents must be miscible with water and typical examples are alcohols, ketones, dioxane and the like.

The macromolecular substance A can with one or more other macromolecular substances with are miscible with substance A, for example polyacrylic acid, polyvinyl alcohol, polyacrylamide, polyvinylbenzenesulfonic acid, Polyamides and the like or copolymers !! be united from this. Appropriate proportions of the other macromolecular substance are according to the following formula

macromolecular substance. A. _:> 0.1.

another macromolecular substance
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The metal ion B to be used in the context of the invention "preferably consists of one element of the groups 6A, 7A, 8, 1B, 2B of the periodic table such as chromium, manganese, Iron, cobalt, nickel, copper, zinc, palladium, silver, cadmium, mercury, gold and the like and especially ■ The ions of manganese, cobalt, nickel, copper, zinc, silver and cadmium are suitable for this purpose. These metal ions can be used in the imaging process as water-soluble salts or as salts sparingly soluble in water can be used in the case of the particularly preferred metals indicated above. Also complex salts of these metals of course fulfill this purpose. According to the invention, these metal ions can be used individually or in combination will. In addition, it is possible to use various compounds which form the clays given above by decomposition, oxidation, reduction and the like are able to use. These ions are particularly preferably divalent, however, ions with other valency states, for example, Cr 3+ or Pe 3+ can be used depending on the conditions for forming the image. Certain types of the metal ions listed above can, as such, make gelatin insoluble, however the effect that can be achieved according to the invention is far stronger than when these ions are used alone. It was also found that the amount of metal ions necessary to make the gelatin insoluble is considerably lower in comparison to the pail of the sole use of the metal ions.

The compound to be used in the context of the invention C can be an organic or inorganic compound, which becomes alkaline when brought into contact with water or a hydrous solvent and Examples these include inorganic materials such as oxides, hydroxides, carbonates and the like of alkali metals and alkaline earth metals. Water-soluble organic bases

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can also be used for this purpose and examples include piperidine, morpholine and triethanolamine. The use of is also preferred. Compounds, which the medium in the decomposition with alkaline with electric current or by heating. An example of such a ■ connection is water, which makes the vicinity of a cathode alkaline when it is electrolyzed. Urea, thiourea, ammonium carbonate and the like can also be used in the invention since these compounds are easy decompose when heated and make the environment alkaline due to the ammonia formed. It is also possible to use substrates that are used to generate a basic material under electron beam irradiation. are capable, for example polyacrylamide, poly-F-methylol, Acrylamide, polyvinylpyridine, polyvinylamidazole or copolymers containing these components. As part of the According to the invention, a pH value not lower than 8 is required for the formation of the image.

The compound D corresponding to the above general formula I is particularly effective when Y here denotes a sulfur or selenium atom. For the radical X, examples are anions such as Cl "*, Br", I ^- and CH ^ - © —SO, ". Particularly preferred examples of types of compounds D are given below:

Connection 1

Br melting point

2 0 9629/1121

Connection 2

Br melting point 288 ^° C

Connection 3

S ^ ^ S

Br melting point 26O ⁰ C

Connection 4

CH ₃

Melting point 267 ^° C

Connection 5

H ₃ CS

Br "melting point 275 ^° C

Connection 6

-Se. > -S

"+ N

Br melting point 288 ^° C

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Connection 9

Connection 10

- 16 -

Connection 7

.NJ

Connection 8

Br melting point 235 ^° C

Cl melting point 291 ^° C

CHo-CN
³ II. I
0 H

Melting point 305 ⁰ C

Cl "· 2HoO melting point 95 ⁰ C

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Connection 11

S - ^ - S II.

CH,

ClO ₁

Connection 12

ΊΓ

Connection 13 p

CH,

ClO ₁

Connection 14

CH,

HSO ₁ melting point 196 ^° C. melting point 220 ^° C. melting point 185 ^° C. melting point 255 ^° C.

209 829/1121

Compounds D can generally be easily obtained by heating a Azο! Establishing a connection, as is apparent from the following examples with a Methylmercaptorest and ethylene bromide or 1,3-dibromopropane to about 160 ⁰ C. ■

Establishing the connection 1:, ·

20 g of ethylene bromide and 16 g of 2-methylthiobenzothiazole was heated to 16O ⁰ C for 4 hours. After cooling, the precipitated crystals were filtered off and recrystallized from ethanol and 17 g of compound 1 with a melting point of 258 ^° C. were obtained.

Establishing connection 6:

20 g of 2-Methylthiobenzoselenazol and 20 g of ethylene bromide were heated at 160 ⁰ C for 4 hours. After cooling, the precipitated crystals were filtered off and urakristallisiert from ethanol-water and obtained 18g of the compound 6 as needles having a melting point of 288 ⁰ C.

The compounds 8, 9 and 10 can be prepared according to the method according to Chemical Abstract, Volume 72, .31666,. 1970 and ibid., Vol. 63, 11569, 1965.

It was found that the compound D when added to the hydrophilic macromolecular substance A. shows an effect of lowering the solubility thereof in hot water due to a crosslinking reaction, and that this ex · effect in the presence of a Metal ion and is increased under alkaline conditions.

When an aqueous one containing the compound D, the hydrophilic macromolecular substance A and the metal ion B. Solution is made alkaline, the solution immediately shows a crosslinking reaction and gives a gelled one

209829/1121

Condition or a noticeable increase in viscosity, albeit without gelation, in certain cases. Gelling occurs when there are more network connections occur than in the viscosity increased state. The metal ion B was found to be effective even in trace amounts. and did not show any adverse effect so far it is completely soluble in the system.

Regarding the crosslinking reaction between the substance A and the compound D, the amount of the compound should D not less than 0.2 part, the amounts being given here as parts by weight, preferably not be less than 2 parts per 1000 parts of macromolecular substance A. As indicated, the amount of the metal ion can be B to be very low and amounts of 0.002 parts with respect to 1000 parts of the compound D 'have already been found effective, however, the ion is preferably in an amount of 0.01 part or more with respect thereto before.

The quantitative ratios given above result exclusively from the requirements for the crosslinking reaction and the amounts to be used in the Cases of practice vary according to the exact embodiment.

The method according to the invention requires, as indicated above, the presence of A) a hydrophilic one macromolecular substance, B) a metal ion, C) one to maintain the pH of the medium when not less than 8 suitable compounds and D) a compound of the general formula I, but these are four components. are not necessarily different from one another overall. In particular, a connection with two or more functions of these four components. In particular, it is possible that a connection both as Component A as well as component C can act. At-

2 0 9 8 2 9/1121

For example, certain synthetic polymers show with primary amino radicals as listed above pH higher than 8 in aqueous solution and can therefore be used as component A as well as component C. will.

It is of course also possible to subsequently use the polymer image obtained using known ones Strengthen hardeners.

The following applications of the invention are explained with reference to the accompanying drawings.

Application I:

Use in electrolytic-electrophotographic processes

The method according to the invention can be applied to electrolytic electrophotographic Method applied to an image due to the decrease in electrical resistance due to exposure to a photoconductive material to obtain. Known electrolytic-electrophocographic Processes include the steps of projecting a light image onto a photoconductive layer consisting of a powdery photoconductive material such as cadmium sulfide titanium oxide, zinc sulfite, zinc oxide and the like as a unit Dispersion is built up in an insulating resin and which is present on an electroconductive carrier material and. treatment the layer with electrolysis simultaneously with or following this projection in an electrolytic Bath containing a material suitable for forming an image on the layer by means of reduction or oxidation, thereby causing an electrolytic reaction according to the due to the difference in electrical conductivity the pattern formed on the photoconduction is caused and a visible image is obtained.

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As an example of such an electrolytic electrophotographic Procedure is in US patent. 3 010 883 a method for achieving a Copy through treatment of a recording material, which is equipped with a photosensitive layer of zinc oxide, in an electrolyte bath, which Metal salts that are suitable for the formation of a colored metal image during the reduction, for example silver nitrate, Nickel chloride, copper sulfate and the like or an organic compound which is suitable for producing a color in the reduction process. There is also known a modified method in which e.g. B. indium oxide alone or together with zinc oxide the photoconductive layer is added, while the electrolyte bath only an addition of salts relative contains basic metals which reduce the indium ion contained in the photoconductive layer. Also known is a process in which water-soluble metal salts are used to achieve a metal image during the reduction are able to work with a hydrophilic binder, such as G-elatine, .mixed and previously on the surface of the photosensitive layer can be applied together with other electrolytes.

The invention produces extremely favorable results when applied to such electrolytic-electrophotographic Procedure. In this application it becomes possible to use ordinary photosensitive elements to be used for electrolytic-electrophotographic processes, namely those made of a carrier material equipped with suitable mechanical properties and a photosensitive layer provided thereon, which consists of a powdery photoconductive material and a electrically insulating binders are made.

209329/1121

In order to apply the electrical potential required for the electrolytic reaction, it is necessary to that the interface between the substrate and the photosensitive layer is strongly electrical is conductive. As a result, it is necessary if the carrier material is made of a plastic material and the like consists of equipping the surface of the same with a thin layer of aluminum or of another metal. Although vacuum deposited layers of aluminum are commonly used, examples are for other available carrier materials electrically conductive glass, which is made of a thin layer Zinc oxide, paper containing carbon black, paper containing fine metal fibers, with aluminum foils and like coated paper and like materials. It goes without saying that a metal plate can also be used cheap as a carrier.

The photosensitive layer consists of a thin layer of an intimate mixture of, for example, photoconductive Zinc oxide and an electrically insulating binder. The zinc oxide is preferably prenched manufactured. The binder material has a significant influence on the electrophotographic properties and examples styrene-butadieh copolymers (Pliolite S-5D and S-7, G-oodyear Tire and Rubber). Fatty acid epoxy ester, Vinyl chloride-vinyl acetate copolymers, polyvinyl acetate and the like can also be used for this purpose will. The binder can contain additives of plasticizers, inactive pigments, for example colloidal silica, Talc, titanium dioxide and the like, lubricants and the like, if desired. The addition of surfactants Means is often beneficial to the coating properties to regulate. Sensitizing dyes are often added to reduce the light-sensitive wavelength

209829/1121

to expand the rich zinc oxide, which in principle is limited to the range from ultraviolet to blue. Other sensitizing materials can also be used are added as additives in smaller amounts.

The teaching of the invention can be applied to electrolytic-electroconductographic Process by adding component A) a hydrophilic macromolecular. Substance, B) a metal ion and D) the above compound to the surface of the photosensitive layer or applied to the electrolyte bath. The alkali-generating compound C) is in this Pail V / water, which makes the area around the cathode alkaline during electrolysis. In this case it is possible to use all add three components A), B) and D) to the electrolyte bath or the three components in layers on top of the light-sensitive layer to be deposited. In addition, is it is possible to apply components A) and B) or A) and D) in layers on the photosensitive layer and add components D) or B) to the electrolyte bath,

It is also possible to apply component A) and the components to the photosensitive layer B) and D) to be added to the electrolyte bath. Another possibility of using components A) and B) or A) and D) and the addition of components B) and D) to the electrolyte bath is also given. There is also a Possibility of using the three components A), B) and D) in layers on the light-sensitive layer and in the addition of components B) and / or D) to the electrolyte bath.

In Fig. 1 is an enlarged cross section of the thereby produced light sensitive element 10 shown, which consists of a transparent or opaque Support material 11, an electrically conductive layer 12 and an insulating photoconductive layer 13 consists.

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whereupon a hydrophilic macromolecular layer 14 is formed which consists, for example, of gelatin and compound 1 above. This macromolecular Layer 14 preferably has a thickness of 0.1 to 500 microns when dry.

In IPig. 2 is the stage of image-wise light projection shown on the photosensitive element according to FIG. 1, wherein a slide original 21 of opaque areas 22 and transparent areas 23 distributed according to the image. The uniform light from above (indicated by arrows) is through the permeable area 23 of the original plate 21 and the macromolecular Layer passed and reaches the photoconductive layer 13 and forms one or more areas of low Resistance (a) and of high resistance (b). The layer 14 can beforehand with an addition of a dye or pigment. If such a dye or pigment has an absorption within des.sensitive wavelength range of the layer it is also possible to remove the macromolecular layer 14 after imagewise exposure to the photoconductive layer 14 to train in light.

In Fig. 3 is the stage of performing the electrolysis shown on the photoconductive element 10 after imagewise exposure, wherein at 31 a container for the electrical. Lytlösung 32 is designated, which consists for example of an aqueous solution of the metal ions B. It was at found at this stage that a weakly acidic electrolyte bath is beneficial for the formation of sharper images. The light sensitive After imagewise exposure, material 10 and a counter electrode 33 are each connected to the cathode and Anode, connected to the electrical power source 34, which has a voltage of 0.3 to 100 volts direct current sur electrolysis supplies. During the electrolytic treatment

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the gelatin is in the area (a) of the macromolecular Layer in the warm water due to a 'crosslinking reaction with the metal ions B and the compound D. the alkalinity achieved by the electrolysis of the water made insoluble, d. H. the networking between of gelatine A takes place via D and B. This reaction takes place in the unexposed areas (b) of the macromolecular ones Layer 14 does not come off due to the lack of an increase in pH. It also turned out to be possible a colored macromolecular image by adding a formazan dye upon reduction to form a suitable connection, d. H. very generally reduction products of triphenyltetrazolium salts, such as Triphenyl tetrazolium chloride, in an electrolyte bath. In a simpler way, it is also possible to use a coloring component, which does not cause any adverse effects on the crosslinking reaction in the electrolyte bath by adding the colored component is incorporated into the macromolecular image to make this image more easily visible. The development by electrolytic treatment can be achieved by applying an electrical potential to the photoconductive surface through an electrode connected to it, the cathode being connected, if zinc oxide is used as the photosensitive material, in the electrolyte bath is applied immediately after or during the imagewise exposure. The electrolyte bath can be filled with absorbent materials, which are suitable for holding the electrolyte solution, in sufficient Amount supplemented to effect electrolyte treatment such as brushes, sponges, porous papers and the like. The contact between the electrolyte bath and the photosensitive layer can either cover the entire surface of the same at once or progressively take place in small portions of the same, for example

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by a roller covered with a sponge.

In Pig. 4 is the step of treating the photosensitive material after the electrolytic treatment of the same with warm water, the uncrosslinked areas through the from the nozzle 41 supplied hot water 42 are removed and thereby the area (a) remains as a water-insoluble macromolecular image 43 on the light-sensitive layer 13, so that a negative image of the original image 21 is obtained.

The macromolecular image 43 obtained in this way can be used for various printing processes. For example can make the image for ink transfer printing by impregnating the image with a water-soluble Dye can be used. The arch having the macromolecular image 43 can be used as a Qelatin relief for color transfer printing can be used. In this case, it is possible to use hardening treatment for reinforcement of the image. Palis the photosensitive material is made up of zinc oxide, it turned out as preferred to remove the zinc oxide with acid and the like in order to obtain a clearer transfer image. The image can also be transferred in spirit by impregnating the image with a sufficient amount of one in water and "alcohol soluble parbe be obtained.

Furthermore, the macromolecular image can be used for offset printing, since the image 43 is hydrophilic, while the photoconductive layer 13 is hydrophobic. Furthermore, it is possible to have a strong molecular image layer 43 obtained by applying the macromolecular layer 14 to a dry thickness greater than 10 microns of an electrolytic Treatment is suspended. Such an image represents a relief of considerable height in the water-containing state and can therefore be used for Braille printing or for letters

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printing with an aqueous ink can be used.

It is also possible to create a metal image by further treating the one equipped with the macromolecular image 43 Obtain bow. This treatment can, as shown in Fig. 5, in the application of a solvent 52 for the binder of the photoconductive layer 13 excepted from a nozzle 51 for removing the photoconductive layer of the area 53, which is protected by the macromolecular image 43, as well as subsequent spraying an etching solution 62 consist of a nozzle 61, so that the thereby exposed electroconductive layer is removed becomes, as can be seen in FIG. In this case, the electroconductive layer 12 and the etching solution 62 each composed of copper chloride or iron chloride solutions. The successive removal of the macromolecular Image 43 and the remaining photoconductive layer 53 results in a metal image 63 on the carrier material 11 as shown in FIG. The metal image obtained in this way can be used as a printing cha It ung if the carrier material consists of an electrically insulating material. This metal picture can also be used as a letter printing plate be used.

Furthermore, it is possible to obtain a printing plate by the method in which the macromolecular image is pressed against a metal plate 120, as shown in FIG. 4, with the image-bearing surface is directed towards the metal plate as shown in Fig. 12 and the macromolecular image thereon is directed towards the Metal plate is transferred and a permanent image is obtained on this plate, the plate for example can be made of copper. The pressing can be effected by means of a roller 121. A subsequent etching treatment, as shown in Fig. 13, with subsequent removal of the macromolecular image gives the in Fig. 14 shown

2 0 9 8 2 9/1121

Printing plates. Area f shows the unetched surface of the plate.

It is also possible to use a mimeographic Printing plate according to the invention by an electrolytic electroconductivity Process to manufacture. The sensitive element for making the mimeographic Printing plate is in Pig. 10 consisting of a carrier material 11, an electrically conductive layer 12, a photoconductive layer 13 and a porous sheet 101 shown, the z. B. from a with a hydrophilic macromolecular Material 100 impregnated Japanese paper and the above compound D can be constructed. These Japanese paper layer can be applied to the photoconductive layer before or after imagewise exposure thereof however, it is preferred to apply the layer after the imagewise exposure for mimeographic purposes Obtain higher quality plate. Area (d) shows the unexposed area of the photosensitive Shift on. The electrolyte bath to be used in this case is preferably weakly acidic and contains the metal ions B. Those in Pig. 11 mimeographic printing plates shown can be obtained by ashing this element with hot water after the electrolyte treatment so that the unexposed areas are thereby removed, and the Japanese paper layer is peeled off from the element all in one Solvent for the binder of the photosensitive layer 13 can be obtained. The plate is made of a non-networked one Area 111, which is permeable to the printing ink, and a cross-linked area 112, which is a barrier layer for the Represents printing ink, built up.

Should be in the Pail of applying the present invention to an electrolytic-elektrokonduktographisches \ ^r orfahren the temperature of the Elektrolytbad.es preferably a

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Do not exceed a value of 45 ^° C., since a temperature exceeding this limit results in a drop in the photoconductivity retention obtained during light irradiation and makes a complete crosslinking reaction impossible.

Application II:

Application for electrophotographic processes

The teachings of the invention can also be applied to electrophotographic processes that are carried out in the uniform Charging a photoconductive insulating layer in a dark place, then exposing it image-wise ■ this layer and development of the resulting electrostatic latent image with an electroscopic powdery Material (toner). The development can, for example, be carried out with a developer that of fine powders obtained by breaking the compound D and a salt containing the above metal ion B obtained fine powder and carrier particles for cascade development consists.

On the other hand, a layer of a hydrophilic macromolecular substance A, which is on a water-resistant substrate is present, moistened with an alkaline aqueous solution and against a xerographic plate, which the having developed toner image thereon is pressed. After pressing, the one equipped with the macromolecular layer is used Sheet peeled from the xerographic plate and treated with hot water. The macromolecular layer after the treatment showed up only in the areas insolubilized where it was in contact with the toner image. Generally in this case at least one of the four components A, B, C and D is incorporated into the toner so that the four are present in the image area Components are made electrophotographically and the

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Crosslinking reaction is caused. The hydrophilic macromolecular image obtained in this way is obtained exclusively in the area where the four components are all available. In theory it is possible to use all and at least one of these four components in the toner, but in practice it will it is preferred not to use the hydrophilic macromolecular substance A in the toner but to use it in the layer to apply to the carrier material in order to facilitate handling.

The electrophotographic processes used in connection with the invention can be used with any of the common development processes are used, e.g. cascade development, magnetic brush development, Powder cloud development, liquid development, donor arc development, and the like. In addition, it is also possible obtain a macromolecular image by using an aqueous alkaline solution contained in a porous material, for example a sponge, is impregnated for a short period of time with which the electrostatic latent To bring the image-bearing surface into contact, so that the distribution pattern of the alkaline material on the xerographic plate is formed and then one with a moist layer containing components A, B and D contains equipped sheets to be pressed against the surface of the xerographic plate.

Application III:

Application for electroconductive recording processes

The teaching of the invention can also easily be applied to electroconductive recording methods and it is doing a macromolecular image by means of a through the in the vicinity of the cathode through the electrical Current formed alkalinity initiated cross-linking

BATH ORIGINAL

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reaction received. For example, in this EaIl a recording layer made of a hydrophilic macromolecular substance A containing the compound D and the Contains metal ion B on the electroconductive carrier material moistened with water or steam before recording and a metal needle is moved while she is in contact with this. An electrical voltage modulated by means of an electrical signal is applied to the metal needle to form the alkalinity on the layer in accordance with the electrical signal. The alkalinity causes the crosslinking reaction of the macromolecular layer according to the amount of the electric current. A water-insoluble macromolecular image can therefore by treatment the recording layer is maintained with hot water. The resulting image can be used for multiple Copies applied by means of the color transfer process will.

The metal ion B can be supplied from the metal needle instead of being a water-soluble salt in the Recording layer is incorporated. For this purpose, the metal needle can be made of silver, nickel, Cobalt, zinc and the like. The metal - ions are formed from the metal needle connected to the anode of the electric power source and into the recording layer delivered. The excess metal ions are again reduced to the metallic state and deposit on the surface of the recording layer to give a colored macromolecular one Picture in this case. The metal needle can be used individually or in the form of a thorn matrix. According to the According to the invention it is thus possible to obtain printing plates from a cathode ray tube of the mandrel matrix type.

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Application IV:

Application to thermographic copying processes

The teaching of the invention can also be applied to thermal copying processes according to FIG. wherein a base material 81 having a low thermal conductivity and a thermally sensitive recording layer 82 are shown. In this package, the thermally sensitive recording layer 82 is made of hydrophilic macromolecular substance A, a metal ion B, one for the formation of an alkali upon decomposition suitable connection C and the connection D established. The alkaline material C can e.g. B. from urea, thiourea, Ammonium carbonate and the like exist which liberate alkali upon decomposition with heating.

In this method, the recording layer 82, which is closely contacted with an original 83, is exposed to uniform irradiation of infrared light for a short period of time. The image area 84 of the Originals, which absorbs the infrared light, shows a local temperature rise, so that a local Temperature rise by thermal conduction forms in the corresponding region (c) of the recording layer. In the area (c), the compound C is thermally decomposed and makes this area alkaline, so that a reaction between the hydrophilic macromolecular substance A, the metal ion B and the compound D to make the macromolecular substance A is achieved over water. This creates a macromolecular image 91 on the carrier material 81 obtained by treating the recording layer with hot water after exposure to infrared light. The sheet carrying the image produced in this way can be used as a gelatin relief for dye transfer printing, as an offset printing plate, as a spirit printing plate and the like.

BATH ORIGINAL

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same used v / earth.

Recording layers representing the macromolecular Substance A, a metal ion B, the raw material for alkali C, the compound D and colored powder such as Pigments or dyes contained are suitable for direct recording with laser beams. if the surface of such a recording layer is scanned with a signal-modulated laser light, the colored powdery material absorbs the light while increasing its temperature, so that a Decomposition of the alkali starting material C ceases and the crosslinking reaction is initiated.

Other uses:

The teachings of the invention can of course also be applied to direct visual writing recording methods. In such a case, a recording layer containing the hydrophilic macromolecular substance A is the metal ions B and the compound D contains, present on a transparent carrier material and the recording is applied directly to the layer with a pencil, felt-tip pen, ballpoint pen and the like, which contains an aqueous solution of the alkali C. If so desired the aqueous solution can also be colored. The recording layer becomes compartment of this inscription hot water to remove the unpaved areas treated so that a macromolecular image on the transparent Bearer remains behind. The sheet produced in this way can be used as a slide for slide projection, as an original plate for the production of several slides using the color transfer process and the like can be used.

Furthermore, the teaching according to the invention can also be applied to electron beam recording. If z. B. a recording element composed of a recording layer

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with the hydrophilic macromolecular substance A, the Metal ion B, the compound D and the one for the generation of alkali on decomposition under irradiation with electron beams suitable compound and a carrier material for irradiation with an electron beam is exposed, the compound C is decomposed in the irradiated area and causes a hardening reaction.

It is also possible to use a hydrophilic macromolecular Image created by attaching pressure breakable microcapsules containing the alkaline material C contained, on the bottom surface of a sheet of paper, Underlaying another sheet of paper, which is equipped with a layer of components A, B and D. and breakage of the microcapsules due to lettering printing and the like.

The method according to the invention is by coexistence in the image formation of the above four components A, B, C and D.

The following examples are provided for further explanation the invention. The information given in the examples is of course subject to variations and Modifications by those skilled in the art with regard to the composition or combination of the components, the order of the method and the like, so that the invention is not limited thereto. Parts are by weight.

example 1

The following mass was placed in a porcelain ball mill for 20 hours kneaded;

Photoconductive zinc oxide

(Sakai Chemical, Saζex) 1GÖ parts

Pliolites S-5D (Goodyear Tire and Rubber) (styrene-butadiene copolymer

Molar ratio 85:15) 25 parts

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Toluene 75 parts

Methyl ethyl ketone 25 parts

The "white paste thus obtained was with Toluene diluted to a suitable viscosity of about 50 cp and then diluted to a previous one with a vacuum deposited aluminum layer coated polyethylene terephthalate film with a thickness of 1000 pounds to a coating thickness of 16 microns after drying raised.

The light-sensitive manufactured in this way Arc was sometimes at about 10,000 lux for 5 seconds using a slide projector exposed to a tungsten lamp.

After this exposure, the sheet was subjected to an electrolyte treatment in an electrolyte ^{bath of the following composition, which was kept at 30 °} C. in order to prevent the bath from solidifying:

Gelatin (photographic quality) 6th parts Compound 1 0.4 parts

Nickel chloride hexahydrate 9 parts

distilled water 100 parts

The perimeter of the arch was covered with an insulating tape before immersion in the electrolyte bath, to prevent direct contact between the bath and the aluminum layer. The electrolysis was done performed by using a Mckelplatte as an anode in a Distance of 1.5 cm from the sheet with the aluminum layer, which acted as a cathode, was brought. A direct current potential of 4 volts was applied. The electrically conductive layer (aluminum) of the photosensitive sheet was connected to a cathode of an external electrode.

209829/1 121

As a result, the exposed part of the photosensitive layer acts as a cathode. The sheet was removed from the bath after the electrolysis for 10 seconds. In this condition, the sheet was damp only in the exposed areas which were pale gray in color. The sheet was then washed with water, dried and finally wiped with a sponge impregnated with an aqueous solution of a blue dye (CI. Acid blue 54, 0.2 fo) and a blue negative image was obtained. The optical density of the image was 0.57.

Example 2

The procedure of Example 1 was repeated, but added 0.1 part to the electrolyte bath Glacial acetic acid added. The electrolyte treatment and the subsequent coloring as in Example 1 gave a sharper result Higher density image. The optical density of the image was 0.57.

Example 3

In this example, a 5 % aqueous solution of a photographic gelatin was coated on the photosensitive layer of Example 1 and cooled and dried, and a gelatin layer 1.9 microns thick was obtained after drying. The photosensitive layer was then subjected to imagewise exposure to the same light source as in Example 1 at about 10,000 lux for 8 seconds.

The composition of the electrolyte bath was as follows:

209829/1 121

Nickel chloride hexahydrate 3 parts

Cobalt (II) chloride hexahydrate 2 parts of compound 1. 0.4 parts

distilled water 1GO parts

The sample was washed with hot water after the electrolyte treatment as in Example 1. After The sample was dried with an aqueous lOrmalin-r solution for hardening the gelatin image coated and immersed in an aqueous solution of O.I. Acid blue 54 as in example 1 immersed. Then the sample was pressed against a sheet provided with a gelatin layer, which had previously been subjected to a pickling treatment so that a blue transferred image is on the Bow was obtained. It was found that the gelatin in the exposed areas was in hot water was insoluble at a maximum thickness of 0.2 microns.

Example 4

The following mass was applied to the photosensitive " Layer of the material according to example 1 drawn up:

Gelatin (photographic grade) 5 parts Compound 1 0.5 parts

Compound 4 0.1 parts

distilled water 100 parts

The thickness after drying of the gelatin layer was 2.0 microns. The electrolyte bath used had the following composition:

Fickel chloride hexahydrate 3 parts

Cobalt (II) chloride hexahydrate 2 parts

Hydrochloric acid (30 fi) O ₉ 02 parts

distilled water 100 ropes

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After exposure and electrolysis as in Example 1, the photosensitive surface was ^{washed with hot water at 45 °} C. and a pale gray gelatin image layer remained thereon, the sharpness of which was so increased that the image could be felt with the fingers.

The temperature of the water usually used is in the range between about 30 ^° C. and about 98 ^° C.

After drying, the sample was further treated with formalin to harden the gelatine image and into an aqueous solution of C.I. Acid blue 54 immersed. The transfer method given in Example 3 gave a dark blue transferred image. It was found that the gelatin layer in hot Water was completely insoluble in the areas subjected to maximum exposure.

Example 5

The procedure of Example 4 was repeated, but the electrolyte bath had a further addition of 0.2 parts of compound 1. The results obtained were comparable to those obtained in Example 4.

Example 6

In this example, the photosensitive layer was dye-sensitized by adding a dye solution of the following composition to the photosensitive composition of Example 1 after diluting it with a solvent. The following table also shows the sensitivities obtained for white light (tungsten lamp, color temperature about 3000 ^° K).

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The quantities in the table are based on 100 g of zinc oxide.

No." Sensitizing dye solvent
for the coloring
material relative
Sensation
opportunity 1 without (photosensitive
Layer according to example 1) without 1 2 Rose bengal 50 mg Methanol
15 ml 18th

Fluorescein 30 mg Erythrosin B 30 mg Brilliant Blue FCF 30 mg

Methanol
20 ml

3,3'-di-β-carboxyethylthiadicarboeyanine bromide Methanol

30 mg 15 ml

The photosensitive layer no. 3 was further provided with a gelatin layer according to Example 4 and imagewise exposure through photographic negative film mounted in a photographic enlarger was exposed (enlarger for 35 mm film from Fuji Photo PiIm Co.). The exposure took place during 3.5 seconds with a maximum luminance on the exposed surface of 75 lux. An electrolytic treatment corresponding to Example 4 gave a satisfactory positive gelatin image.

Example 7

The procedure of Example 1 was repeated using an electrolyte bath of the following composition:

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-Polymer 1 5 ropes

Compound 1 0.4 parts

Klckelchlöarid Hexahydrate 9 parts

distilled water -. 100 parts

Results comparable to those of Example 1 could be obtained.

Example 8

The procedure of Example 1 was repeated using an electrolyte bath of the following composition:

Polymer 3 6 parts

Compound 2 '0.3 parts cobalt chloride hexahydrate 9 parts

distilled water 100 parts

Following the procedure of Example, results comparable to those of Example 1 were obtained.

Example 9

In this example, the gelatin layer according to Example 4 was applied to the photoconductive layer in such a way that that a thickness of 0.6 microns instead of 2 microns was obtained after drying. The electrolyte bath and the procedure according to Example 4 provided a gelatin image which, after washing the photosensitive layer with a Offset plate treatment agent (Puji Photo PiIm, Piano Developing Ink 801) was wiped off. The printing ink 801 adhered exclusively to the exposed photosensitive Layer and left the gelatin image completely in tact. The image treated in this way could be used as an offset printing plate be used.

20 98 29/1121

Example 10

The following mass was kneaded for 20 hours in a porcelain ball mill:.

Photoconductive zinc oxide (Sakai

Chemical, Sazex) 100 parts

Pliolite S-5D (Goodyear Tire

and Rubber) 28 parts

Toluene 80 parts

Methyl ethyl ketone 20 parts

The white paste thus prepared was mixed with toluene to a suitable viscosity of about 50 cp diluted and then coated on the copper surface of a Plate for printed circuit boards (Matsushita Electric Co.), which consists of an * epoxy resin carrier plate and a copper layer attached to it was built up. The coating thickness after drying was 16 microns. The photosensitive layer produced in this way was further coated with the following composition:

Gelatin (photographic grade) 5 parts Polymer 3 x 2 parts

Compound 1 0.8 parts

distilled water 100 parts

The coating thickness after drying was 3 microns. The following electrolyte bath was used:

Cobalt (II) chloride hexahydrate 9 parts glacial acetic acid 0.02 parts

distilled water 100 parts

The photosensitive member thus obtained became subjected to imagewise exposure from a negative printed circuit original, electrolytically

209829/1121

is, washed with hot water (45 ⁰ C) and hardened with formalin according to Example 4 and further washed with ligroin to remove the free light-sensitive layer in the unhardened areas. The element was then ⁽⁰ 4O Be) immersed in an acid aqueous solution of iron (IIl) chloride for 15 minutes at 45 ⁰ C, and then washed with water. A sharp printed circuit was obtained by vigorously wiping the hardened areas with benzene to remove the photosensitive layer and the hardened image formed thereon. The hardened image parts were removed with the photosensitive layer.

Example 11

The procedure according to Example 10 was repeated, each however, a layered printed circuit board continues to have a vacuum deposited aluminum layer of 750 S thickness used on the copper layer and a sharp printed circuit, corresponding to the in Example 10 obtained. In this example, the aluminum layer could be washed in a 1N sodium hydroxide solution removed. The insertion of the aluminum layer between the photosensitive layer and the Copper coating reduced the exposure time required to a value from one-half to one-third that Time in example 10.

Example 12 The following mixture was dried and broken:

Connection 1 '5 parts

Nickel acetate 0.1 part

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The practically white powder obtained became well Mt. 100 parts of Xerox ** 914 ~ carrier (Puji Xerox Co. «) mixed and an electrophotographic dry developer. One with an asaorphic selenium layer of 80 microns The starch-equipped xerographic plate was subjected to a positive corona discharge in the dark to charge the Layer exposed to a potential of +500 ToIt. The xerographic plate was then image-wise exposed and an electrostatic latent image is formed which. then developed with the above dry developer by the cascade method, and a white one Toner image was obtained on the xerographic plate.

The following mass was drawn up separately on a sheet of polyethylene terephthalate, the previous one had been irradiated with ultraviolet light (thickness 120 microns) :

Gelatin 5 parts

Sodium dodecylbenzenesulfonate "

(Wetting agent) 0.05 parts

distilled water 100 parts

The coated layer was first solidified by cooling and then dried by exposure to hot air. The gelatin layer was swelled in a 0.1 N lTatriumhydroxidlösung of 15 ⁰ C and pressed tightly against the surface of the toner-image bearing xerographic plate. The sheet was then peeled off and washed with water at 4-5 ⁰ and G receive gelatin image corresponding to the toner image on the sheet.

Example 13

The following mass was placed on a sheet of polyethylene terephthalate of 120 microns thick, which had previously been irradiated with ultraviolet light, so

2 0 9 8 2 9/1121

that a coating thickness of 3 microns was obtained after drying:

Carbon black 0.8 parts

Gelatin '8 parts

Cadmium sulfate 0.1 part

Connection 2 0.6 parts

distilled water 100 parts

Direct manual writing was carried out on the layer obtained by means of a mushroom pen impregnated with a 0.1 N potassium hydroxide solution. The sheet was then treated with hot water at 5O ⁰ C for removing the areas not described wherein a sharp black image remained on it, which was suitable as a slide for projection.

It was also possible to make this slide by dipping it in a dye solution and transferring the dye onto it reproduce other transfer sheets,

Example 14-

The following mass was applied to a sheet of polyethylene terephthalate 60 microns thick, previously exposed to ultraviolet radiation was grown to a dry thickness of 2 microns:

Gelatin · 5 parts

Compound 1 0.5 parts

Nickel chloride hexahydrate 0.01 part

Urea 0.8 parts

distilled water 100 parts

. After solidification, the coating was dried using ^{an air blower of 30 ρ ΰ.} The recording layer thus produced was compared to the original with a

BATH ORIGINAL

2 0 9 8 2 9/1121

pressed black image, exposed to infrared radiation from the back of the recording sheet and immediately immersed ^{in warm water of 40 0 C.} After drying, the recording layer was immersed in an ink-off solution and a positive reproduction of the original image was obtained.

Example 15

The photosensitive layer according to the example. 1 was subjected to imagewise exposure by positive line image. Separately, a sheet of thin Japanese paper was immersed in the following solution, which was kept at 28 ^° C.:.

Gelatin 4 parts

Compound '1 0.3 parts

Manganese chloride hexahydrate. 0.01 parts

distilled water 100 parts

The moist Japanese paper sheet was placed on the photosensitive layer according to Example 1 immediately after the imagewise exposure and firmly adhered to it by the solidification of the gelatin by blowing cold air. The photosensitive layer was then electrolyte treatment according to Example 1 in the electrolyte bath according to Example 4 subjected, then washed with hot water, immersed in toluene and the sheet of Japanese paper peeled off from the photosensitive layer. After drying, it was found that the gelatin in the unexposed areas (areas of the line formation) had been removed from the sheet of paper thus treated paper sheet showed a satisfied \ dens splitting behavior as Stammsohablone (miraeographisohe

209829/1121

■ ■ - '- 46 -'

Printing plate). With a thin synthetic cloth Comparable results were obtained with pasting in place of the Japanese paper. . ...

. Example 16

An epoxy resin-zinc laminated plate for use as a letter printing plate was coated with the white photosensitive paste of Example 10. Subject to drying, the plate was further coated with the composition according to Example 10 to a thickness corresponding to Example 10. The photosensitive member thus produced was imagewise exposed, washed with warm water (45 ⁰ C) and cured with formalin as described in Example 4, and further treated with ligroin to remove the uninterrupted portion of the photosensitive layer. The top gelatin layer on this unexposed part had already been removed by the washing. The plate was then immersed in an etching solution (Itoh Chemical Co.) containing iron (III) chloride at 45 ^° C. for 15 minutes to dissolve the zinc present in the unhardened areas. After washing with water, the photosensitive layer in the hardened parts was removed together with the hardened image by wiping with benzene, and a zinc letter press plate was obtained. ^l

■ Example 17 | A crowd out.

Gelatin 5 parts

Acrylamide. 0.4 parts

Hiokelorid Hexahydrate 0.02 parts

Compound 1 0.1 parts

Equipped Waastr 100 parts

20 * 121/1 * 2 V.

became 2 microns thick as a dry slide on a polyethylene terephthalate film for manufacture an electron beam recording material. The recording material thus obtained was exposed to an electron beam image in a vacuum and treated with warm water to obtain the gelatin image.

Example 18
A crowd out

Gelatin. 5 parts

red pigment (Brilliant Carmine 6B) 1 part Compound 2 0.3 parts

Urea 0.8 parts

Ferric chloride 0.01 part

distilled water 100 parts

was coated to a thickness of 4 microns as a dry layer on a polyethylene terephthalate film to prepare an electron beam recording material. The recording material thus obtained was exposed to an argon ion laser light, which has been modified by a signal, and treated with warm water of a temperature of 40 ⁰ C and erhitlten a red gelatin image.

Example 19

The following mass was ^{heated to 40 °} C. to form a uniform solution:

Gelatin 6 parts

Compound 1 0.2 parts

Eobalt chloride 0.01 part

distilled water 100 parts

209829/1 121

2165S65

To the solution kept at 7O ⁰ C solution of 10 parts of a 5 $ solution of carbon tetrabromide in acetone were added under stirring. The carbon tetrabromide was dispersed as fine particles of about 2 microns. The solution was applied to a 100 micron thick cellulose triacetate film. The dry thickness of the layer was 7 microns. The PiIm was then immersed in a 0.05 N Ealiumhydroxidlösung at 15 ⁰ C for 2 seconds and dried. By treatment with alkali, the layer is cured and insolubilized in hot water at 6O ⁰ C. The above procedures were carried out under darkened light with exclusion of ultraviolet radiation.

The thus formed PiIm, in contact with a transparent original, was exposed to light from a high pressure mercury lamp of 100 W at a distance of 35 cm for 3 minutes. Then, the Piim was washed with warm water of 60 ⁰ C. The exposed parts of the layer were washed out, while the unexposed parts remained. The PiIm was immersed in a mixed solvent of acetone and water (volume 1: 1) to remove the carbon tetrabromide present in the unexposed parts.

209829/1121

Claims (1)

2185665 Claims Imaging method, characterized in that at least one component is selectively imagewise a system of a hydrophilic macromolecular substance, a metal ion, one for maintenance the pH of the surrounding medium is not less than 8 when in contact with water or when decomposed suitable compound and a compound corresponding to the general formula I ρ " wherein Z and Z ^{T are} nonmetallic atoms forming a heterocyclic structure, X is an anion and Y is an atom from Group 6B of the periodic table, subtracted or added to a system or from this system, and an image containing a water-insoluble macromolecular substance , is obtained. .2. Method according to claim 1, characterized in that a hydrophilic macromolecular substance which Contains amino acids. Is used. 3. The method according to claim 1 or 2, characterized in that a hydrophilic macromolecular substance, containing primary amino groups is used. 4. The method according to claim 1 to 3, characterized in that at least one ion of Metallatoraen as metal ions from groups 6A, 7A, 8, 1B or 2B of the periodic table is used. 209829/1121 ♦ ■. 5. The method according to claim 1 to 4, characterized in that the metal ion is at least one ion of chromium, manganese, iron, cobalt, nickel, copper, zinc, palladium, silver, cadmium, or mercury Gold is used; " 6. The method according to claim 1 to 5, characterized in that as a compound that controls the pH of the surrounding medium keeps at not less than 8, water,. what alkali in the vicinity of the cathode forms when an electric current is applied while maintaining the pH value at not less than 8, is used. 7. Method according to claims 1 to 5, characterized in that as a connection for maintaining the pH value if not less than 8, at least one oxide, hydroxide, carbonate or organic base of elements of groups 1A or 2A of the periodic table are used will. 8. The method according to claim 1 to 5, characterized in that ' that as a compound for maintaining the pH at not less than 8, a compound is used which forms alkali when it is thermally decomposed. 9. The method according to claim 1 to 8, characterized in that a compound is used in which Y represents a selenium atom or a sulfur atom. 10. imaging method, characterized in that projects a light image onto a photosensitive element which consists of an electrically conductive support and a photoconductive layer applied thereon and selectively applying an electric current through the exposed areas of the photoconductive layer in one aqueous solution passed at a time not earlier than or at the same time as this exposure becomes and thereby an image formation reaction in the presence; a hydrophilic macromolecular substance, a meta11- 209829/1121 ions, a compound used to maintain the pH in the surrounding medium at no less than 8 upon contact with water or upon decomposition and a compound according to that in claim 1 given formula is formed. 11. The method according to claim 10, characterized in that the electroconductive image by removal of the photosensitive layer and the electrically conductive support in the photographic image areas after Training of the image is obtained. 12. Electro-conductive recording method, characterized in that a recording layer made of the hydrophilic macromolecular substance, a Metal ion, a material that causes alkalinity when decomposed by the electric current and the compound formed according to the formula given in claim 1 on an electrically conductive carrier material and one modulated by an electrical signal. Voltage is applied to the recording layer. 13. Electroconductive recording method, characterized in that a recording layer consisting of the hydrophilic macromolecular substance A, the alkaline material C and the compound D according to the Formula according to claim 1 with the metal ion B together with the passage of the electric current corresponding to the electrical signal is supplied or formed. 14. Electrophotographic process, characterized in that an electrostatic latent image, which on a photoconductive insulating layer with a finely powdered material which is developed from at least one of the above materials A, B, C or D, and the powder image obtained with the remaining materials is implemented and the image is preserved. 209829/1 121 15.! Eherinographic copying process, characterized in that a recording layer is used which contains the hydrophilic macromolecular substance A, the metal ion B, a compound C suitable for releasing alkali on decomposition by heating and the compound I) according to the general formula 1 contains is used. · ^; *. 16. Procedure for. Laser beam recording, characterized in that a recording layer which is the hydrophilic high polymer A, a metal ion B, one for decomposition upon exposure Compound 0 suitable for laser light with formation of an alkaline product and a compound D correspondingly of the general formula in claim 1, is used 17. Method for electron beam recording, characterized in that a recording layer comprising a hydrophilic high polymer A, a metal ion B, one to decompose upon exposure to electron beams to form an alkaline product suitable compound C and a compound D corresponding to the general formula in claim 1 is used will. 2 0 9 8 2 9/1121 eerseite