DE2131865A1 - Recording and reproduction of colored colloid patterns - Google Patents

Description

A G- FA-GEVAEET AG IlEVEEKUSEN

Recording and reproduction of colored colloid patterns * .--- '

Priority: Great Britain, June 30, 1970, note no. 31.623 / 70.

This invention relates to a recording and reproducing method for the generation of colored colloid patterns that correspond to information-wise modulated electromagnetic radiation. In particular, this invention relates to a method for producing direct positive, multicolored, polymeric halftone and line images and the materials used therefor.

The production of halftone color images is of interest in the design field, e.g., in the production of decorative ones Color samples, colored wiring and circuit diagrams in the Cartography, the production of colored proofs and the production of slides.

Especially in the field of colored graphics, a requires a simple and fast process that provides colored proofs of high quality and good reproducibility.

Color proofs are used to make a proof that gives the printer and his customer an idea of a multicolor halftone reproduction like her through successive, precisely fitting printing with the individual Standard inks of yellow, purple, teal and black are produced.

The test color print makes it possible to determine whether the grid separation transparencies, with the help of which the printing plates are to be made, corrections still have to be made,

Previously known methods for making colored test prints can be divided into two classes, namely those in which positive copies of the image to be printed are obtained and in which one assumes Rast he draws negatives (production colored proofs by negative processing), and on the other hand

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in those "where you have to make positive copies of the image to be printed is based on positive raster extracts (production colored proofs by post processing).

Whether negative or positive for the production of a printing plate Separation slides must be used depends on the photochemical properties (hardening or solubilization by Exposure) of the cover of the printing plate and of the type of Processing that results in a positive printing plate.

According to previously known photo-curing processes, colored, hardened colloid samples made, the samples electromagnetic Radiation, and are then developed into relief patterns with the aid of an aqueous liquid using a non-photosensitive hydrophilic colloid or ™ polymer which is made insoluble with the help of a compound or is crosslinked by irradiating a photosensitive Connection is created. For example, when making colored test prints through the so-called negative processing, in which one works with negative grid separation transparencies, dichromated, hydrophilic colloid layers used, e.g. layers containing dichromated gelatin or dichromated gum arabic (see P.Glafkides, "Photographic Chemistry",! Fountain Press, London, Vol. II (1960), pp. 669/674).

In the photographic process of making colored Proofs described in British Patent 879,049 is, a positive working color film is used, which is based on the image-wise color coupler diffusion is working. The processed films can be used individually or stacked on top of each other. ·

The use of superimposed images enables a less good imitation of the final results of the printing, because the monochrome raster slides have to be precisely placed and checked diascopically or against an opaque background. Furthermore, known diffusion method can not guarantee a very Groose sharpness because there find "always -fc lateral diffusion of the transferred connections instead. _V

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Einon dor goals diesel? Invention is to record and Reproduction process to obtain that is suitable for making j'arbifjer colloid patterns are suitable which have the same image valuesc have, v / ie the original applied during exposure.

Thus, this invention is particularly useful for fabrication monochrome positive copies of positive originals.

Another object of this invention is to produce multicolored proofs that are cheap, reproducible and easy to build up on colored colloid reliefs based on one and the same permanent carrier are superimposed.

The present invention is based on the manufacture of Photosensitive, colored positive colloid reliefs on the use a diazonium compound, which in combination with a basic compound a hardening of a hydrophilic colloid that contains active hydrogen atoms, as is the case, for example, with hydrophilic colloids of the protein class.

The method of the present invention for making a colloidal pattern comprises the following steps:

(1) Informational exposure of a hydrophilic colloid layer, which contains a photosensitive diazonium salt, with electromagnetic radiation capable of decomposing the diaconium as the hydrophilic colloid layer contains a hydrophilic colloid which has the property of being subjected to an aqueous alkaline treatment in the presence of the unexposed diazonium salt is less water-soluble to become.

(2) The treatment of the information-wise exposed colloid layer in the presence of water with an alkaline substance, which in conjunction with that in the unexposed parts left over from the recording layer. Diazonium salt a selective hardening of the colloid layer in the unexposed Sharing results.

(3) Removing the "exposed parts of the colloid layer through." a washing treatment that leaves a relief pattern that corresponds to the undeveloped parts of the colloid layer.

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According to one embodiment of this invention, multicolored pattern colored, electromagnetic radiation sensitive, hydrophilic colloid layers on one provisional carrier "used. The casting composition contains "A diffusion-resistant, coloring substance even in the application state and a desired amount of a radiation sensitive diazonium compound. In other words, there won't be any • coloring or light-sensitive ingredients through diffusion * or impregnation introduced, i.e. through processes that are difficult to regulate and result in less easily reproducible results. Furthermore, the exposure of the colloid layers can proceed in a practically dry state, whereby chemical Corrosion of the exposure device is avoided and thus represents a real advantage for the staff.

According to a characteristic aspect of the preferred embodiment of this invention, colored colloid patterns consisting of several superimposed layers are prepared by Transfer of the unexposed, colored colloid layers to a same permanent support, "each of the transferred Colloid layers - after they precisely fit the visual impact effective electromagnetic radiation - what is hardened in the unexposed areas has the consequence that the hardened colloid parts of underlying colloid parts or parts of an underlying, colloid-containing layer, e.g. a hydrophilic adhesive layer. In this way any danger is avoided that the colored colloid coating changes during washout development by crimping what is otherwise very much in processes with a wash-out treatment of transferred colloid coatings common difficulty is.

According to another aspect of the preferred embodiment for the production of multicolored patterns, each transferred, differently colored colloid layers individually in register on the same, permanent carrier through the extract positive exposed, which was specially selected for each colloid layer.

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The production of multi-colored patterns, built up by superimposed, colored colloid relief patterns, happens preferably through a process that includes the following steps:

(1) Transfer of a colored hydrophilic colloid layer that contains the diazonium compound and the hydrophilic colloid, from a preliminary carrier which is compared to the permanent support to which the layer is to be transferred is relatively hydrophobic, on this permanent support, by placing it against the Colloid layer presses and removes the temporary support so that the layer remains on the permanent support,

(2) Exposure of the transferred colloid layer in a mainly dry state with information-wise modulated, electromagnetic Radiation that decomposes the diazonium compound;

(3) Treatment of the exposed colloid layer in the presence of water with ammonia or an organic amine, which causes hardening of the unexposed parts of the colloid layer;

(4-) removing the exposed parts of the colloid layer by washing treatment; and

(5) the repetition of steps (1), (2) and Q) as well as (4-) with the hydrophilic colloid layers having an arbitrary Have color, and their transfer to the same, permanent support in superimposed position to the already formed colloid relief patterns (or the pattern).

Examples of diazo compounds useful in practicing the invention are derivatives of 1,2- and 2,1-aminonaphthols, 1,4-aminonaphthols, and benzene series aromatic p-diamines, particularly p-hienylenediamines which are an one of the amino groups are mono- or di-substituted. These light-sensitive diazo compounds are commonly used in making diazotype images. Suitable diazo compounds are: p-Diazo-diphenyleneamine sulfate
p-Diazo-dimethylaniline chloride. Zinc chloride

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ρ — Biazo-diethylaniline chloride. Zinc chloride p-Biazo-ethyl-hydroxyethyl-aniline chloride .% Zinc chloride ρ- © iazo-methyl-hydroxyethyl-aniline chloride. #> Zinc chloride p-Biazo-2,5-dietho: xy-benzoylaniline chloride. 3 £ Zinc chloride p-Biazo-ethyl-benzylaniline chloride. ^ Zinc chloride p-Diazo-dimethylaniline-boron fluoride

p- © IazQ-2,5-dibutoxy-benzoylaniline chloride.) £ Zinc chloride p-Biazo-i-morpholine benzene chloride. ^ Zinc chloride p-Biazo-2,5-dimetb.oxy-1-p-toluyl-mercaptobenzene chloride. ^ Zinc chloride p- Diazo-3-ethoxy-diethylaniline chloride. Yz zinc chloride 2.5 9 * "-" fcriäthoxy-diphenyl-4-diazoniutnoxala-t p-BiazQ-diethylaniline chloride.) £ zinc chloride p-biazo-2,5-dibutoxy-1-morpholino- benzene chloride.Zinc chloride p-Dia.KO-2,5-dimethoxy-i-morpholino-benzene chloride. Zinc chlorid ™ p-Mazo-2,5-cLiäth.oxy-i -morpholino-benzene chloride. Zinc chloride p-Diazo-2-chlorodiethylaminobenzene chloride.) ^ Zinc chloride p-Diazo-diethylaniline boron fluoride
p-Diazo-2-chloroacetaniline chloride.) i Zinc chloride p-Diazo-2-methyl-diethylaminobenzene chloride. Zinc chloride. 1H-Di.azo-2-methyl-ethylamine.obeiizol chloride. Zinc chloride p-iDiazo-3-methyl-diethylaniinobenzenechlorid -K'-hydroxyethyl-m-toluidine.chloride . ¹ A zinc chloride

The preferable diazo compounds are used in κ us & T form of their salts stJabilisierten - for which p-diphenylamine

diazonium sulfate as an example - or in the form Zinc chloride, cadmium chloride or boron trifluoride double

The selectivity of the hardening of the colloid layer increases with the stei concentration photosensitive diazonium compound too.

Diazonium compound, which can be added, is that concentration at which the crystallization is limited this connection begins in the colloid layer. Man

therefore the most water-soluble diazonium compounds or mixtures of these compounds that are not easy tocisitaXlize. Preferably, the photosensitive,

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colored colloid layer 15 to 40 percent by weight of the diazonium compound, divided by the weight of the dry, hydrophilic colloid, preferably gelatin.

The alkaline substance used in conjunction with the diazonium as causing hardening of the hydrophilic colloid is preferred applied in an amount large enough to raise the pH of the colloid layer to above 8. The alkaline Substance is e.g. an inorganic base such as sodium hydroxide, Ammonium hydroxide or an organic onium hydroxide compound, for example derived from an organic amino compound such as an aliphatic, alicyclic or heterocyclic amine. Preferred amines are sthanolamine, diethanoiamine, triethanolamine, Cyclohexylamine, dicyclohexylamine, dimethylene triamine with dor formula H ^ N-CIIp-NH-GHp-NHp, urotropine and morpholine. the Alkaline substances can consist of a solution in water or a mixture of water and a water-miscible, organic Run out of solvent.

According to a particular embodiment, the hardening of the unexposed parts is carried out by a volatile base or an alkaline compound in the vapor phase, for example "ammonia + water vapor, as is done in the so-called" dry development " ^{11 of} the slide-type process Purpose an ordinary blueprint apparatus can be used to successively carry out the two acts of exposure and development by conveying the original and the phot ο sensitive material in superimposed position, nB with the help of an endless belt conveyor through separate exposure and development departments.

The AnacnialrdaEpfbehandlung preferably followed by a heat treatment by aan example increases the temperature to 60 to 90 ⁰ C to the selective hardening of the undeveloped parts to accelerate the Kolloischiclrfc. .

It is assumed that in the case of the alkaline treatment, di- sonium hydroxide is formed, which when decomposed is hydroxy1— releases radicals that are responsible for hardening (crosslinking) the colloid «

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Fast and good curing results are obtained immediately if one the colloid layer that was exposed to the Ατητηoniakdampf, • Treated with an aqueous liquid "which is a freely distributed Contains metal (a so-called metal sol) which has the property of catalyzing the decomposition of the diazonium hydroxide; this is done in place of the heat application after the ammonia vapor treatment carried out. A suitable metal in this regard is copper. The metal sol treatment technique is illustrated in Example 14-.

With some diazonium compounds, an undesirable background color • (Stains) that can be removed by treatment with a reducing agent. Suitable reducing agents for this purpose are e.g. sodium dithionite, tin (II) Chloride and hypophosphorous acid, 'which preferably consist of a aqueous solution can be applied. The diazonium compounds of Examples 16 and 18 show no staining and will preferred for very neat work and fast processes.

The aqueous liquid that supplies the alkaline substance (here later called the activator liquid), which in connection with the unexposed diazonium compound is the desired Hardening of the unexposed parts of the colloid layer results, can preferably contain a water-miscible solvent, the selective washing away of the uncured parts of the hydrophilic ones Colloid on drawing layer improved. To accelerate the selective hardening by treatment with organic amines, heat is applied to bring the colloid layer to a temperature of, for example, 35 t> is 65 ° C.

The use of an organic, water-miscible solvent in the activator liquid, the swelling of the unexposed parts of the Ko11οidschicht holds back during the washing process.

Organic solvents that are suitable for this purpose are water-miscible alkanols and ketones, e.g. methanol, Ethanol, isopropanol and acetone. The same effect can be achieved through the use of electrolytes, which are known to be are that they remove gelatin from their aqueous solution.

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precipitate (flocculate), e.g. a compound that releases sulfate ions, e.g. ammonium sulfate, sodium sulfate. and other electrolytes, which are known for this purpose.

For "Solvent and Electrolyte Precipitation of Gelatin" we refer to "Photographic Emulsion Chemistry" by G.E.Duff in - The Focal Press, London and New York, (1966), Pages 78-80.

The concentration of the inorganic base, e.g. ammonium hydroxide and / or the organic amines in the accelerator liquid, can vary between 1 and 25% by weight.

After the treatment with the activator liquid, which, depending on the temperature, concentration and type of activator liquid, can last from about 30 seconds to about 8 minutes, the information-wise exposed parts of the hydrophilic colloid on the drawing layer are selectively exposed to a jet of tap water, preferably from 30 to 50 ^° C washed away.

After the wash development, the swollen parts that make up the unexposed areas of the recording layer correspond in an alkanol / water mixture to the shrinkage, preferably in an ethanol / water mixture of about 80:20 contains up to 70:30 volume percent ethanol to water.

Preferably used curable colloids are hydrophilic, water-soluble colloid polymers which contain active hydrogen atoms, such as those present in hydroxyl groups and amino groups are. Both the qualitative detection and the quantitative determination of active hydrogen can be carried out according to the method carried out, which is known as the active hydrogen determination according to Zerewitinoff. Active hydrogen atoms containing curable colloids are e.g. polyvinyl alcohol, polyacrylamide or gelatin or other film- or layer-forming, proteinaceous colloids.

In the context of this invention, the best results with aldehyde-curable, obtained hydrophilic and water-soluble colloids which have the property of sol / gel conversion, such as

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• Gelatin, which also allows easy transfer and good adhesion of the photosensitive layer to the permanent support. has to offer. The sol / gel conversion is explained in the book by RJCroome and FGClegg "Riotographic Gelatin", The Focal Press, London 1965, pages 37-39.

The above-mentioned hydrophilic eblloids can be mixed with suitable latent curing initiators and crosslinking agents Are used that release a hardening substance when heated, e.g. latent polyisocyanates such as those described in British Patents 99i 676 and 1,058,425.

When creating superimposed multicolor colloid samples, the dyes used in the photosensitive co-11 oid layers must be resistant to diffusion and cixemically as inert as possible to processing and washing liquids. If they are used in the production of colored test prints, the ΐΐητ absorption spectrum must correspond as closely as possible to that of the standard printing inks. Details on standard printing inks can be found in HM Cartwright- 'Ilford Graphic Arts Manual (1% 2), Vol. I, pp.502-504.

There are "cold" and "warm" staffiäard colors. Cold shades are e.g. in the U.S.A. by the GATF ~ color cards and in the German forms DU "16508 and 16509. Warm color tones are defined e.g. by the German standard DIN 16538.

W The cold standard colors are characterized by the Verwendund quite pure Purpurpigniente, usually insolubilized Bhodamin- Ehloxin and dyes, which are characterized by a very low sideband absorption in! Blue region of the spectrum.

■ 'The standard warm colors are insoluble due to the use made azo dyes. These dyes are more resistant to solvents, e.g. alcohol, than the ehodamines and phloxins, but are characterized by a much stronger sideband absorption in the blue area, the spectrum off.

Tests have shown that pigments are insoluble or very

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poorly soluble in water and organic liquids Alcohol and polyalcohol types, e.g. glycerol, are also the Required diffusion resistance ". From an aqueous Dispersion-applied pigment dyes are preferred used, although also the use of direct dyes, that are chemically bound to a colloid or polymer cannot be ruled out. For making colored ones The hardenable colloid layer contains pigments as proofs high concentration that the optical density in the wavelength range corresponding to maximum absorption is at least 0.55 amounts to.

Apart from the use of dyes for the production of colored test prints, which determined their absorption spectrum Must meet requirements, all colors are considered, e.g. blue-green, light blue-green, purple, warm purple, black, yellow, Green, brown, orange, red, light blue and metal colors such as pale gold, deep gold, copper and silver. In other words: im In the context of this invention, the term "color" is to be understood to include all pure and mixed colors, as well as blackening and white.

Diffusion-resistant pigments, which are suitable for use in frames suitable for this invention are known under the names "PIGMOSOL" and "COLANYL". These are registered trademarks the Badische Anilin- & Soda-Fabrik AG, Ludwigshafen / Eh., West Germany, for organic pigment dyes which are a dispersant for aqueous media is added. These pigment dyes are characterized by excellent Resistance to light, heat, acids, bases, oxidizing agents and solvents. They are in hydrophilic colloids such as gelatin insoluble.

The black pigment for the black-tinted partial image is preferred Soot.

Even if the pigments compared to the aqueous processing. and washing liquids are completely inert, due to simple adhesive forces they can attach the permanent support to the unexposed Discolour areas to a certain extent. To one

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To prevent direct contact of the pigment with the permanent carrier, the pigment coating on the temporary carrier is covered with a hydrophilic colloid layer (top layer) which does not contain pigments or dyes for the formation of the image. When this composite coating is transferred, the top layer comes into contact with the permanent carrier and comes to lie between this carrier and the pigment-containing coating. The top layer contains the same colloids as the colored layer and preferably also has the same composition as the pigment-containing coating except for the content of visible, image-forming pigment or dye. However, the top layer may contain a small amount of translucent pigments, such as silica particles, which protrude from the layer and are several microns thicker than the top layer. It prevents the rolled up film material from sticking at relatively high (eg 60 %) relative humidity. The top layer contains, for example, 1 to 1.5 g of gelatin per square meter.

In order to obtain images with good resolution, relatively thin, radiation-sensitive, colored colloidal coatings are preferred. Preferably they have a thickness in the range between 1 micron and 15 microns. Good results are obtained with colored colloid layers containing 2 to 10 g of gelatin per square meter. Very good results are obtained with colored layers that have a thickness between 4 and 5 microns and 2.5 to 3 g Contains gelatin per square meter. Contains the colloid layers en. preferably at least 50% by weight GelatiB.

The adhesive force of the transferable coating on its temporary Carrier, which is preferably flexible, must be adjusted so that that an easy one. Peeling from the temporary carrier is possible after the pigment coating with the permanent carrier in Contact has been pressed. Preferably find, therefore use a relatively hydrophobic temporary support - e.g. an unsubbed cellulose triacetate film, a polystyrene film, a polyester film or a film made of vinyl acetate / vinyl chloride mixed polymer and a permanent support with a hydrophilic surface - e.g., a polyethylene terephthalate support suitable for

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Adhesive pelatine coating was subbed such as a hydrophobic carrier that was subbed, it was in the Belgian Patent 721,469 is described. According to a preferred embodiment, the photosensitive coating is composed in such a way that that its adhesive strength on the temporary carrier * is lower in the wet state than in the dry state. That can be achieved by adding hygroscopic agents, such as, for example. a water-soluble, hygroscopic organic compounds such as glycerol, and through the use of wetting agents and plasticizers. After the washout treatment the colloid relief pattern is preferably dehydrated (de-swollen) with a water-attracting alkanol / water mixture, preferably a jtthano l / water mixture so that it is sufficient Retains mechanical strength and is not damaged if another colloid layer is transferred. A a temporary carrier which has a repellent effect on wet gelatin coatings is, for example, one coated with a polyethylene layer Paper base, a paper base impregnated with Vachs, a paper base coated with a cellulose nitrate layer or a paper backing coated with a layer of insolubilized polyvinyl alcohol or with a layer of alginic acid made insoluble with an alkaline earth metal salt.

The permanent support can be rigid or flexible; it only has to be per se or by an adhesive layer or several such Layers for good adhesion of the transferable, hydrophilic colloid coating in both wet and dry Condition.

Depending on the use of the multicolor copy, the one is permanent Transparent or opaque carrier. So it is possible to use metal layers or foils, glass, ceramic or resin substrates, and made impermeable to processing and washing fluids Paper to use.

For purposes such as the production of colored test prints, where several exposures are carried out in a precisely fitting arrangement must be, a resin carrier with high dimensional stability must be used.

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Due to high mechanical strength and minimal water absorption marked resin carrier, which is therefore very dimensionally stable in dry and wet can be produced amis, for example, a linear polyester such as polyalkylene terephthalate. Good results are obtained with regard to dimensional stability with; Aluminum foils sandwiched between two Arranges sheets of paper with high hate resistance; but this material is quite expensive.

Penient resin carriers can be made opaque by covering them with a matt adhesive layer, or by coloring or coloring them. matted in the mass. The matting can be done with the pigments known for this purpose - for example titanium dioxide, zinc oxide and barium sulfate. Matting can also be achieved by producing a "tarnish coating", as described, for example, in Canadian patent specification 65 ² I-438.

As a permanent carrier to be used according to the invention, hydrophobic resin carriers with one or more adhesive layers are used coated with a hydrophilic colloid layer.

Yojp-zuziehende adhesive layers for a permanent hydrophobic resin carrier - for example a carrier made of polyalkylene terephthalate are described in the above-mentioned Belgian patent specification 721,469. In this patent, a Eolienmaterial is claimed, which comprises in the following order: a hydrophobic film support, a layer (A) adhered directly to this ψ hydrophobic film support and containing a copolymer, _ which is wqrden made of 45 to 99 »5 % By weight of at least one of the chlorine-containing monomers vinylidene chloride and vinyl chloride, 0.5 to 10% by weight of an ethylenically unsaturated, hydrophilic monomer and 0 to 54.5% by weight of at least one other, copolymerizable, ethylenic, unsaturated monomers; and a layer (B) which contains a mixture - in a weight ratio between 1: 5 and 1: 0.5 of gelatin and a copolymer composed of 30 to 70% by weight of butadiene and at least one copolymerizable, ethylenically unsaturated Monomers has been obtained.

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Preferably, the subbed permanent film support consists of a hydrophobic film support and the combination of the two Anchoring adhesive layers as described above. The hydrophobic film support can be a film made of cellulose triacetate, Polyethylene terephthalate, polycarbonate, polystyrene, Act polymethacrylic acid esters, etc. The sibstered, hydrophobic film support can be provided with a combination of adhesive layers on one or both sides.

A detailed description of composition now follows and construction of a preferable photosensitive material and its use in making one according to the invention Multicolor image.

A casting composition (coating compound) is prepared which contains gelatin dissolved in water in which one or more selected pigments are dispersed in a concentration, which after application and drying results in a recording layer, the wavelength range corresponding to the maximum absorption has an optical density of at least 0.4. The casting composition preferably contains at least 50% by weight gelatin, based on on the pigment particles and a suitable amount of plasticizer and release agent (a hydrophilic compound such as e.g. glycerol) to give the coating sufficient adhesive strength to its temporary support and to enable that when wet it is easily removed from the temporary wearer, such as an unsubbed one. Cellulose triacetate or Polyethylene terephthalate carrier, can be peeled off. In addition to The casting composition contains one of these ingredients Diazonium compound in an amount sufficient to allow selective curing after exposure. It is however, the amount of this diazonium compound is chosen so that the gelling of the gelatin is not significantly affected and that optimum sensitivity is obtained without reaching the concentration at which the diazonium compound begins to crystallize out of the dry layer. A suitable amount of the diazonium compound is in the range between 15 and 40% by weight based on the dry gelatin.

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The Tiberzug preferably contains 1 to 10 g of gelatin per square meter. Optimal results are obtained with 5 S gelatine per square meter.

To improve the shelf life of the recording layer, its pH value is kept quite low, e.g. below 2 ', 5 Suitable acids for this are citric acid, tartaric acid, trichloro • acetic acid, sulfosalicylic acid, phosphoric acid, boric acid, phytiric acid and naphthalene sulfonic acid.

In order to improve the sharpness of the graphic reproduction, the gelatin layer can contain a filter dye.

A second - the so-called deck- " layer - applied, which is preferably identical to the previous one but does not contain any pigment. The second coat preferably contains 0.5 to 5 g of gelatin per square meter. However, it is not absolutely necessary in this second one to introduce a radiation-sensitive diazonium compound, because it can take off during donning and drying the underlying, pigmented layer diffuse a sufficient amount of this compound into it.

This second coating, together with the pigmented coating underneath, forms a firmly bonded one with the other curable double layer - in other words a "composite

"Layer" - which extends as a whole from the temporary carrier to the permanent .bearer can be transferred.

- For the production of a multi-colored "colored test print image" a set of materials containing such a composite layer is preferably used. Usually contains one Set of yellow, purple, cyan and black pigment coatings, each on a cellulose triacetate carrier. ".

The permanent carrier - e.g. a polyethylene terephthalate carrier is successively coated with a first adhesive layer based on a hydrophobic and hydrophilic building blocks in the correct Ratio containing copolymer, and with a second adhesive layer, which is more hydrophilic than the first and the gelatin,

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and contains a hydrophobic latex polymer, and a white pigment - e.g. titanium dioxide particles "- which gives the support an opaque nature.

The permanent carrier that is preferably used in the production of colored test prints is a hydrophobic one Polyester resin carrier which has been provided with a system of adhesive layers, as is the case in the Belgian patent mentioned above Patent 721,469 is described. The opaque one white carrier has an opacity and a white one that is as close as possible to the white and opacity of the one to be printed Correspond to the printing material.

The production of a multicolored test print proceeds according to a preferred embodiment as follows.

The unexposed pigment coating is transferred to the permanent support subbed as described above * by applying the Surfaces of the adhesive layer and the unexposed coating pressed together in the presence of an aqueous liquid and removed from the temporary cellulose triacetate carrier separates.

The transfer can take place in a device in which the two materials involved are pressed together between rollers. A device suitable for this purpose is described in Belgian patent 740,292.

This device is ¹ check especially for use in transmitting colloid layers in a wet or damp state by a preliminary to a permanent support, and it comprises two cooperating pressure rollers and means for driving said rollers, a first stage for receiving the permanent support before ^ it is captured by the pressure rollers, this stage being arranged to make interrupted or discontinuous contact with the permanent support when it is placed thereon, and a second stage for receiving, above and separate from the first surface at least the front part of the temporary carrier to keep it separated from a permanent carrier when the latter is placed on the first stage, the front ends

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both platforms are so arranged near the nip of the printing rollers are that the carriers "are caught and gradually compressed as they advance by these rollers.

After transferring and drying - e.g. with a stream of hot air - The photosensitive gelatin layer is exposed through a first grid separation slide, which decomposes in light systems is a halftone positive of the original. In the special case of four-color printing, a cyan pigment coating is applied first applied to the permanent support and through the positive cyan printer raster separation of the original exposed.

After exposure, the photosensitive layer is treated with moist ammonia vapor or an aqueous liquid containing an alkaline substance. In order to accelerate the curing, the treatment with an alkaline substance can be carried out at a temperature above room temperature, or a heat treatment, for example between 60 and 90 ^° C., can be carried out. The hardening of the colloid layers which have been treated with ammonia vapor can likewise be accelerated by bringing them into contact with a metal sol, for example a copper sol, which causes the decomposition of a diazonium hydroxide. The uncured exposed parts are selectively änem jet of tap water at 30 - 50 ⁰ C washed away.

The same steps are then repeated with the yellow, magenta and black pigmented Plating in the same order, these coatings already bearing the cyan pigment coating in precisely superposed arrangement thereon, slides are exposed, ö ^{e <hole} respectively through the GSM elbfiltep, purple filter: ^ and black filter grid separation positive through the original. However, the order in which the ear relief images are made can also be chosen differently.

The "exposure" - preferably a contact exposure in one Vacuum frame - is made with a light source that is in the ultraviolet range of the spectrum emits sufficient radiation,

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e.g. with a carbon arc lamp, a xenon arc lamp or a high pressure mercury lamp. The exposure time does not only depend on the photosensitivity of the diazonium compound a "b, but also on the type of pigment, in particular ■ of its characteristic absorption for UV radiation and blue light. In order to obtain a raster relief with optimal point sharpness, the pigment coating is exposed while it is moving with the image-containing layer of the transparent original is in direct contact.

After the treatment in an alkaline activator bath the parts of the Aufzeichmingsschicht will contain the exposed gelatin, preferably washed off without mechanical rubbing by means of running water at a temperature of preferably between 30 "and 50 ⁰ C.

The relief image, which has absorbed a certain amount of water, is then preferably dehydrated, specifically in a dewatering liquid, e.g. an alcoholic liquid containing 70 to vol .-% water and 30 to 70 vol .-% ethanol, excess Liquid is preferably removed by drawing the relief between two smooth and soft rollers - e.g. Rubber rollers - expresses. -

The permanent carrier carrying the first relief image (the blue-green relief image) is pressed into contact with another pigment layer - e.g. the yellow pigment layer between the same rollers, and after a few seconds of contact the temporary carrier is peeled off so that the entire yellow pigment layer is applied the already generated blue-green separation image is transferred. This yellow pigment layer is dried before the contact exposure. Drying takes place, for example, with an air stream of 4-0 ⁰ C.

The entire procedure of exposing in perfectly fitting one on top of the other The arrangement, hardening treatment, washing out and drainage are now one after the other for the yellow layer, the purple filter extract and repeats the blackening filter separation image. ..- ■ -... ■

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According to a special embodiment, hardening treatment takes place and washing out with or in the same liquid.

The colloid pattern or multilayer colloid pattern obtained can ■ protect with a transparent resin top coat and make it shiny, according to a preferred embodiment Spraying is applied. Such a suitable top coat consists of polyisobutyl methacrylate. '

The following examples illustrate the invention. Unless otherwise stated, the percentages are given by weight percent.

example 1

I. Preparation of the photosensitive layers

The following ingredients are mixed together at 5O ⁰ C:

14.6% aqueous gelatin solution 240 g.

10% aqueous solution of a wetting agent of the following formula:.

^^^ - 0 (GE ₂ GE ₂ O) ^ OGE ₂ GE ₂ -OQO ₃ Ha . 4.5 ml

HELIOGENBLAU B COLANTL DOUGH (a blue-green pigmented version, sold by • the Badische Anilin & Sodafabrik AG., Ludwigshafen / Eh., Combined with 2.5 g

10% aqueous solution of

η υ <£ ^ ~ 0 (CH ₀ CH ₀ O), .- OCHoCH ₀ -OSO ^ Na 9 ml

n — OqJtI _x , (- £ - = * & - «r dd H- dd O

Mixture of Gyzerol and water (1: 9) '32.5 ml 20% aqueous citric acid solution 20 ml

5% aqueous solution of the mixture of

CgH ₁₇ - <£ ^> - (OCH ₂ CH ₂ ) ₈ -0H / ■

CoH. _n - <? ^r ~% - (OCH ₀ CH ₀ ) 0-OCH ₀ COOH

(17/83%) ■ 5.25 ml

GV.486 '

109882/1700

^ •? I »- i J ⁵ J ^ ** _

11.7% solution of saponin in one Jutnanol / water mixture (1: 4) 5 ml

p-Diazo-2,5-dimethoxy-1-morpholine-benzene-

chloride, zinc chloride. 10 g

Water '136 ml

Water to make up to 500 ml

The mixture is in a ratio of 45 g / m2 and "at 35 ° C on an unsubstrated cellulose triacetate film 0.10 mm thick, which serves as a temporary support.

The composition and manufacture of the apply "pigment layer" are the same as for the blue-green pigment layer below A., with the difference that instead of blue-green pigment, 4 g of a yellow pigment dispersion, sold by the inking units Hoechst AG, Frankfurt (M), under the trade name IMPERON GELB K-GG., Can be used.

C. Photoemgfindliche ^ purge layer Composition and preparation are the same as indicated under A for the cyan pigment layer, only none is used Cyan pigment dispersion used, but 45 ml of one Purple pigment dispersion containing 10 parts of LITHOLSCHAELACH BBM PIGMOSOL (registered trademark of Badische Anilin- & Soda-Fabrik AG, Ludwigshafen / Ehein, West Germany).

The composition and manufacture of the black pigment layer are the same as for the blue-green pigment layer under A., with the difference that now 0.4 g of the blue-green pigment dispersion described in a mixture can be used with 5.4 g of a carbon black dispersion, which under the trade name Russdispersion P 130 from Degussa, Frankfurt (M), is being sold.

II. Production of the permanent support A biaxially stretched polyethylene terephthalate film with a thickness of 180 microns is subbed on both sides at 25-3O ° C and in a "ratio of 1.6 g / m2 with the following composition:

109882/1700 BAD ORIGINAU

Mixed polymer of vinylidene chloride, N-tert-butyl acrylamide, η-butyl acrylate and ^ -Vinyl pyrrolidone (70: 23: 3: 4) 5.5 S

Methylene chloride 65 ml

1,2-dichloroethane; '·' 35 ml

The layer obtained in this way is produced with one as follows Mixture coated:

1350 g titanium dioxide (mean particle size: 0.11 micron) are dispersed in 5 liters of water, the 25 ml DEQUEST 2006 contains (registered trademark of Monsanto Chemical Company, St. Louis, Mo., USA, for a dispersant that corresponds to the following structural formula:.

0
HO-P-ONa

* 0 century ₂ 0

KaO-P-CH ₀ -K-CH ₀ -P-ONa

ONa ^v

Ip-JN-UtIp-

ΟΝε '

The dispersion is stirred vigorously at 5 to 15 ° C. for 10 minutes and then heated to 35 ° C. At this temperature, 400 ml of a 10% aqueous solution are added with constant vigorous stirring Gelatin solution added. Thereafter, the following composition was added with slow stirring to avoid foaming :

a 10% aqueous gelatin solution 1800 ml water I30 ml

^ 20% latex of the copolymer

ψ Butadiene and methyl methacrylate (50:50) 2500 ml

10% aqueous solution of the sodium salt

of oleyl methyl tauride 37 ₅ 5 ml

/ 5-chloroethanol 5OO ml

The coating is carried out in such a ratio that after drying, a layer of 5 microns remains.

III. processing

The permanent carrier is for 1> έ minutes in an ethanol / Water mixture. 'The volume ratio of ethanol to ■ \ ".". Water is between Ϊ and 6: 1, but preferably 2: 1. - .; ■ -.

GV.486 '

10 9882/17 00

IVi e cyan pigment layer on its temporary support when wet and pressed between soft rollers against the permanent support moistened as described. To a contact time of 30 seconds, the temporary support is peeled off so that the cyan pigment layer is permanent Carrier sticks. The transferred layer is air-dried and placed in a vacuum frame in which it with the blue-green filter grid separation positive one to be printed multicolored template is brought into contact.

The pigment layer is made with a carbon arc light source (1 40 amps) from a distance of 70 cm for 5 minutes exposed.

The exposed pigment layer is 180 seconds in a Dipped bowl containing the following alkaline, activating composition:

Triethanolamine 250 ml

.. water 250 ml

Isopropanol 2000 ml

gaseous ammonia to saturation.

The relief is developed by washing with running water at 35 ^° C. without rubbing. Then the relief image is immersed in a mixture of ethanol and water for 1 minute (70:30 vol.-96).

In the same manner as described for the cyan pigment layer, the yellow, magenta and black pigment layers are also used Transferred to the already formed relief image and each exposure in a precisely superimposed manner Arrangement carried out through the corresponding grid excerpt positive. The exposure times will be the sensitivity of the differently pigmented recording layers customized.

The received multicolor image made up of superimposed Blue-green, yellow, purple and black relief images serves as a proof for the printer who clicks on this Way the quality of the blue-green filter, yellow filter, purple

109882/1700

BATH ORIGINAL,

Assess filter and black filter grid extract positives can. .. "· '."

Example 2 '■

Example 1 is repeated, however, each pigment splint after application on their temporary support covered with a protective layer at a ratio of 33 g / m2 is obtained from the following composition:

• Gelatin 135 g

^ 10% aqueous dispersion of silicon

"dioxide particles (mean particle size 2-3 microns) in 8% aqueous gelatin solution · 30 g

11.7% solution of saponin in one

Mixture of ethanol-water (1: 4) 20 ml

TERGITOL 4 (registered trademark for 7-ethyl-2-methyl-4-undecanol ester of Sodium hydrogen sulfate (Union Carbide and Carbon, New York, USA) ■ 15 ml

Water up to 1000 ml

Example 3

Example 2 is repeated except that it becomes the protective coating coating composition 4-0 ml of 20% aqueous citric acid solution and 100 ml of water added, before increasing to 1000 ml is filled. .

Example 4

Example 2 is repeated, but before the casting composition the protective layer is brought to 1000 g ^ the following mixture is added:

20% aqueous citric acid solution 40 ml

p-Diazo ^^ - dimethoxy-i-morpholine-benzene chloride, zinc chloride '10 g

Water 150 ml

Example 5

The recording materials used are those of example 4 identjah.

The procedure is followed to obtain a multicolor image of Example 1, but with the difference that the alkaline, activating treatment with warm, moist Arampniak-

GV.486 109882/1700

steam is carried out in a diazo apparatus "Actina S" ("Actina S" is the trade name for a diazo copier by Eegma N.V., Brussels, Belgium). The treatment lasts 10 seconds.

The multi-colored image finally obtained in this way has a brownish background color (spots) which removes it by immersing it in a bleach bath with the following composition for 2 minutes:

Sodium dithionite (Ka ₂ S ₂ O ₄ ) "100 g water to make up to 1000 ml

Example 6 ■ "." ...

The procedure of Example '5 is repeated, but with the difference is that after color development, the background stains are removed from every single color image. That monochromatic belief image made lighter in this way is washed in water before it is dipped into the ethanol / water mixture and the next colored one Colloid layer is preserved.

Example 7

Example 5 is repeated, but the bleaching bath is the the following composition is used:

Tin (II) chloride dihydrate. 100 g

Citric acid 50 S

Water to make up to 1000 ml

Example 8

Example 5 is repeated, but the bleaching bath is the the following composition is used: - ■

Hypophosphorous acid (H ₅ PO ₂ ) 200 g

Water to make up to 1000 ml

Example ff ", - '

Example 4- is repeated, but as an activator liquid the following composition is used:

Methanol '100 ml

concentrated, aqueous ammonium hydroxide 100 ml

^{CT 486} 109882/1700

Isopropanol. ■ 800 ml

The activating treatment is carried out in the bath at 35 to 55 ° E carried out and takes 2 / to 5 minutes. ;

The selective washing treatment is done with flowing Water at 35 ° C -

Example 10

Example 9 is repeated, but with the difference that the p-Diazo-2,5- <ä-imethoxy-1-morpholine-'benzolchlorid.Zincchlorid by the same amount of 4- (Dimethylamine) -phenyldiazoniumchlorid.Zinkchlörid is replaced.

Example 11

* Example 9 is repeated, but with the difference that p-Diazo-2,5- <3-imethoxy-1-morpholine-benzene chloride. Zinc chloride by the same amount of p-p-ethyl- (2-hydroxyethyl) -amino [] -benzenediazonium chloride.> £ Zinc chloride has been replaced.

Example 12 "·.

A polyester film that can be written on with ink or pencil, a so-called drawing film ¹ - consisting of a polyethylene terephthalate carrier, which is covered on both sides with a semitransparent coating based on titanium dioxide dispersed in hardened gelatin, which is a latex polymer such as a copolymer of vinyl chloride, vinylidene chloride, η-butyl acrylate and itaconic acid Ψ (63: 30: 5 = 2 mol%) is used as a permanent carrier for applying a black photosensitive layer in a ratio of 45 g / m2 made of the following composition:

14.5% aqueous gelatin solution, 240 g of 10% aqueous solution of the wetting agent

-0 <-OHoCH ₀ O) y _L -0C5H;, - CH _o -bS0, Na 4.5 ml ^v 22 ^y 4 d 2. 3 '^

under the name "Russdispersion P 130" from Degussa, Prankfurt / Main, West Germany, distributed soot dispersion 5.4 g HELIOGENBLAU B COLANYL TEIG (registered Trademarks) in combination with 0.4 g

^GV · ⁴⁸⁶ 109882 / Ί7 00

2131865 ml Is 9 ml 63 ml 20th G 10 ml 136

10% aqueous solution <1 «3 of the above wetting agent

Glycerol / water mixture (1: 9)

20% aqueous citric acid solution

4- (N-Hydroxyethyl-N-ethylamine) -phenyldiazonium chloride, zinc chloride

water
The applied layer is dried “at 20” to 30 ^{° C.}

The dried photosensitive recording layer is in direct contact with a piece of tracing paper on which there is a drawing of a machine part in black ink ", exposed. The exposure time "is 10 seconds, and the exposure takes place with a UV lamp of 1000 watts, which is arranged at a distance ^ of 10 cm from the photosensitive layer.

After exposure, the recording layer becomes with damp. Ammonia vapor "treated. By washing away with running water at 35-37 ° C, a positive, black image on a semi-transparent support.

Instead of using the UV incandescent lamp for exposure, use a flash lamp of 4 kV, which emits in the ultraviolet range. The washing method, that of the treatment with ammonia vapor gives the same result.

Other suitable drawing films that can be used as a support for the photosensitive, hydrophilic applied according to the invention Colloid layers are described in Belgian patent 7 ^ 4 837. These films behave look like tracing paper, i.e. they allow e.g. a drawing or a pattern to be touched up, and they can be used with Describe well with pencil and ink.

Example 13

Example 12 is repeated, except that the following coating composition is used to produce the photosensitive layer used : .

10% aqueous gelatin solution 140 ml

15% aqueous carbon black dispersion with 2% "'. Poly (N-vinylpyrrolidone) 40 ml

GV.486 10988 2/1700

5% aqueous solution of the wetting agent TEEGITOL 4

(registered trademark.) 10 ml

Citric acid '2g

4- (N-diethylamino) -phenyl diazonium chlorine id. Zinc chloride "5 g

Water 105 ml

Example 14

The recording materials used are the same as that of example 4.

The alkaline, activating treatment is now carried out in two steps: first, the "exposed material" is applied Placed in a humid ammonia-saturated atmosphere of 15-25 ° C for 30-90 seconds; after that it will be 30-90 seconds heated to 80-90 ° C in a high-gloss flat plate; the Gelatin is heated in contact with the plate.

Example 15 .

Example 14 is repeated except that after the material moist ammonia vapor has been exposed, it is 60-180 seconds in a 10 ~ * molar Kupfersol at 15-25 ⁰ C submerged, which is prepared as follows;

500 mg of copper (II) sulfate pentahydrate are used in one liter Dissolved in water. From a 25% igo ^ aqueous ammonia solution 10 ml together with 100 ml of a 0.4% aqueous Gum arabic solution added. It comes with water on 2 liters filled up. The solution is heated to 90 ° C. and, with stirring, 30 ml of a 1% strength aqueous hydrazine hydrate solution admitted.

The presence of a small amount (1 g in 2 liters) of sodium nitrite or sodium sulfite increases the stability of the sol.

Example 16

I. Preparation of the photosensitive layers

The following ingredients are mixed together at 50 ° C :

11.7% aqueous gelatin solution - 600 g

^{GV 486} _o 109882/1700

LUCOHYLBLAU LBGO (a blue-green pigment dispersion, .sold by Badische Anilin- & Soda-Fabrik AG, Ludwigshfen / Rh.) 8.2g

combined with water 127.5 ml

12.5%> aqueous solution of the sodium salt of oleyl methyl tauride

water

Mixture of glycerol and water (1: 9) 5% aqueous solution of the mixture of

,-OH/

30th ml 50 ml 21 ml

CqH ^ _n - <f ~ *> - (OCH ₀ CH ₀ ) n-

(17/83%) 12 ml

11.7% saponin solution in one Ethanol / water mixture (1: 4) 20% aqueous citric acid solution

10% aqueous solution of 4-N, N- (dihydroxyethylamino) phenyldiazonium chloride, cadmium chloride

This mixture is applied in a ratio of 45 g / m 2 at 35 ° C. to an unsubstrated cellulose triacetate film 0.10 mm thick, which serves as a temporary support.

11 ml 40 ml 200 , ml

^B · Yellow_gef ^ bte _A _2hotοemgfindliche_Schicht The composition and production of the yellow pigment layer are the same as for the blue-green pigment layer under A., with the difference that now instead of the blue-green pigment, 8.5 g of a yellow pigment dispersion are used, which was developed by the Farbwerke Hoechst AG, Frankfurt (M), is sold under the trade name IMPEEON GELB K-GG.

C. Pur £ ur__gefärbte _i _p_hotoem £-sensitive layer The composition and preparation of the magenta pigment layer are the same as g for the blue-green pigment layer under A., with the difference that instead of blaugrüneh pigment dispersion 14.5 a purple pigment dispersion are used, the 10 Contains parts of the following substance:

109882/1700

PERMAWEWTCARMIW FBB COLAWYL DOUGH (a purple pigment dispersion sold by

of Badische Anilin- & Soda-Fabrik AG, Ludwigshafen / Rh.)

D. Black colored β _α _ £ ΐιο ^ οβΐΕ £ | ίηα.1ίο1ιβ_§ £ ΐιΪ £ ΐιΐ The composition and production of the black pigment layer are the same as for the blue-green pigment layer under A., with the difference that now 1.3 g of the blue-green pigment dispersion described are used as a mixture with 17.6 g of a carbon black dispersion which is sold under the trade name carbon black dispersion P 130 from Degussa, Frankfurt (M).

II. Manufacture of the permanent support

The permanent carrier is produced according to Example 1.

III. Processing -

The processing occurs as described in Example 1, but with the difference that after the three minute exposure of the pigment layer, the latter of 1.5 to 2 minutes in an atmosphere yon 45-50 ⁰ C is brought, which is saturated with wet ammonia vapors.

Example 17

Example 2 is repeated, but before the casting composition brings the protective layer up to 1000 g, the following mixture is added:

20% aqueous citric acid solution 40 ml 4-N, W- (dihydroxyethylamino) -phenyl-diazo-

nium chloride, cadmium chloride 10 ml

Water 150 ml

Examples 18 and 19

Examples 16 and 17 are repeated, but the one mentioned Diazonium compound by an equivalent amount of p-DiazQ-IT-ethyl-R-hydroxyethyl-m-toluidine chloride.} £ zinc chloride replaced. .

^GV · ⁴⁸⁶ 109882/1700

Claims (1)

Claims 1. Process for the production of a colored colloid relief pattern, characterized in that it includes the following steps: (1) Information-wise exposure of a hydrophilic colloid layer containing a photosensitive diazonium salt contains, with electromagnetic radiation capable of decomposing the diazonium salt, which hydrophilic colloid layer contains a hydrophilic colloid which has the property by a aqueous, alkaline treatment in the presence of the unexposed diazonium salt less water-soluble to become, (2) the treatment of the information-wise exposed colloid layer in the presence of water with an alkaline substance, which in conjunction with that in the unexposed Parts of the recording layer left behind Diazonium salt results in selective hardening of the colloid layer in the unexposed parts, (3) washing away the exposed parts of the colloid layer, leaving an EelM pattern that matches the unexposed parts of the colloid layer. - 2. The method according to claim "1, characterized in that the Colloid layer contains one or more dyes or pigments as soon as it is exposed. 3 · Method of making a multicolor pattern, thereby characterized in that hydrophilic, colored colloid layers are used ^ which contain a diazonium compound, the method comprising the following steps: (1) transferring a colored, hydrophilic colloid layer, which contains a diazonium compound and a hydrophilic colloid which has the property less water-soluble due to an aqueous, alkaline treatment in the presence of the unexposed diazonium salt to become, by a temporary carrier, who as to the permanent carrier to which the Layer to be transferred, which is relatively hydrophobic, is applied to this permanent support by making it in a damp or moistened state against the GV.486 109882/1700 Colloid layer presses and removes the temporary support, leaving the layer on top of the permanent Carrier remains, (2) exposing the transferred colloid layer in mainly dry state with information-wise modulated electromagnetic radiation, which decomposes the diazonium salt, ■ (3) treating the "exposed colloid layer in Presence of water with an alkaline substance ' ... those in connection with that in the unexposed parts the diazonium salt remaining on the colloid layer results in selective hardening of the colloid layer in the unexposed parts, (4) washing away the exposed parts of the colloid layer, and '· (5) repeating steps (1), (2), (3) and (4) with the hydrophilic colloid layers, which have an arbitrary color, and their transfer to the same permanent Carrier in superimposed position an already formed colloid relief pattern. 4 .. The method according to any of claims Λ to 3 »characterized in that the alkaline substance increases the pH of the hydrophilic colloid layer to over 8. 5 «Method according to any of the preceding claims, characterized characterized in that the alkaline substance is an inorganic base or an organic onium hydroxide compound is. 6. The method according to claim 4, characterized in that the alkaline substance is ammonia vapor or an organic one Amino compound is. . ■ 7. The method according to claim 6, characterized in that the organic amino compound ethanolamine, diethanolamine, Triethanolamine, cyclohexylamine, dicyclohexylamine, dimethyl is entriamin, urotropine or morpholine. 109882/1700 ■; ■■ "■ - ■. COPY BATH ORIGINAL 8. Method according to each of claims 1 to 7? characterized, that the alkaline substance as a solution 'in water or as a mixture of water and one with Water-miscible solvent is applied. 9. The method according to claim 4, characterized in that a colored pattern of superimposed, colored Colloid layer parts and the hydrophilic colloid layers from a relatively hydrophobic, temporary support can be transferred to a relatively hydrophilic, single, permanent support, namely 1) by pressing on a first, colored colloid layer in the wet state (with an aqueous liquid moistened) against a hydrophilic side of the permanent carrier and peeling off the temporary Carrier, 2) by exposing the transferred colloid layer through a transparent Easter or line template through, 3) by developing a relief pattern by washing away the exposed parts with an aqueous liquid, 4) by transferring a second, colored colloid layer on the first colloid pattern formed and 5) by repeating the steps of exposure, development and transfer of one or more, further, colored colloid layers until the desired multicolored pattern is obtained. 10. The method according to claim 4, characterized in that that the permanent support has an opaque appearance. 11. The method according to claims 1 to 10, characterized in that that the colored, hardenable colloid layer or the layers with active, electromagnetic, means of a slide to be exposed to modulated radiation, while the colloid layer or layers of the Is or are facing the radiation source. 109882/1700 _copy BATH ORIGINAL 12. The method according to claim 11, characterized in that that the slide is a transparent bast or line template is. . 13. The method according to claim 4, characterized in that the colored, hardenable colloid layers on iTrwem temporary support are covered with a non-colored top layer which contains the same colloid (or the same colloids) as the colored colloid layer. 14. The method according to claim 13 »characterized in that that the top layer has the same composition as the colored, hardenable colloid layer with the exception of the has colored substances contained therein. 15 · method according to any of the preceding claims, characterized in that the colored, hardenable colloid layer or the layers have a thickness of 1 u until 15 u has or have. 16. The method according to any of the preceding claims, characterized in that the colored colloid layer or the Schubten pigments have or have which are dispersible in water. 17 · method according to any of the preceding claims, characterized in that the colloid layer or layers are a what s he soluble ^ hydrophilic, hardenable Contains or contain colloid which has the property of sol-gel conversion. 18. The method according to claim I7, characterized in that that the colloid does not contain gelatin. 19 procedure according to each of the preceding claims, characterized in that the Kolloidschichi; one Contains diazonium compound derived from a 4,2- land 2,1-, aminonaphtho, a 1,4 ^ -aminonaphthol or iron aromatic pHDiainin is derived from the benzene series GV.486 109882/1700 20. The method according to any of the preceding claims, characterized in that the colored colloid layer contains a hydrophilic, softening substance » 21. The method according to claim 20, characterized in that that the substance is glycerol. 22. The method according to claim 4, characterized in that the temporary carrier is a flexible carrier. 23. The method according to claim 22, characterized in that that the temporary support is an unsubstrated cellulose triacetate film sheet is. 24. The method according to claim 4, characterized in that the permanent carrier is flexible and very dimensionally stable is. 25. The method according to claim 24, characterized in that the permanent support is a hydrophobic resin support subbed to have a surface layer with hydrophilic properties. 26. The method according to claim 25 »characterized in that that a hydrophobic film carrier is used as the permanent carrier, to which have been applied successively are: a not (A) that is directly on the hydrophobic Film carrier adheres toad contains a copolymer that from 45 to 99 »5% by weight of at least one of the chlorine-containing Monomers vinylidene chloride and vinyl chloride, from 0.5 to 10% by weight of an ethylenically unsaturated, hydrophilic monomers and from 0 to 54.5% by weight of at least one other copolymerizable, ethylenically unsaturated monomer is formed, and a rail (B) in a weight ratio of 1: 3 "to 1: 0.5 a mixture of gelatin and a copolymer of 30 to 79% by weight of butadiene and at least one copolymerizable, ethylenic Contains unsaturated monomers. 10918 82/1 7 0 0 27- The method according to claim 25 or 26, characterized in that that a permanent carrier is used which has a layer that contains white pigment particles contains a binder. 28. The method according to claim 27, characterized in that the permanent carrier is a polyethylene terephthalate carrier. ._ 29- Method according to any preceding claim, characterized in that characterized that after the wash development the colloid relief pattern a dehydration treatment by a mixture of a hydrophilic alkanol and water is subjected. 30. Method according to claim 29? characterized, that the dewatering is carried out with a liquid that contains 70 to 30% by volume of water and JO "to 70% by volume Contains ethanol. 51. The method according to claim 1, characterized in that the colloid layer which contains the diazonium compound is heated ^{between room temperature and 90 ° C. after its treatment with the alkaline substance.} 32. A process according to any of claims 1 to 30, characterized gekennzeichfret ^9, "means that the colloid layer containing the Diazoniumverbiridung näeh a treatment with ammonia in the" treated presence 'of water with an aqueous! Liquid containing ^ finely divided metal, das'die decomposition of the diazonium hydroxide promotes. -V. ^. ., _ "- / ■ ^;: ."
^; ^ - " 33 · The method according to claim 32, characterized in that the aqueous liquid containing the finely divided metal is a copper sol, "'■ 3 ^ · method according o ^e ^ - ^em <ler preceding claims, characterized in that the hardenable colloid layer contains gelatin and the washing treatment is carried out without mechanical friction means of running water having a temperature between JQ and has ^p 50th ffV.486 ' 35 · "Process for the production of a multicolored halftone test print, characterized in that hydrophilic, colored eoIIoid splints are used, which are through a Combination of a diazonium salt and an alkaline one Substance that increases the pH of the colloid layer above 8 can be hardened using the following procedure Steps includes: (1) Transfer of a blue-green, hydrophilic colloid layer, which contains the diazonium compound and a proteinaceous, hydrophilic colloid of a temporary support, which is a permanent support to which the layer is transferred should be, is relatively hydrophobic, on this permanent support by leaving it in the presence an aqueous liquid presses against the colloid layer and removes the temporary support so that the layer remains on the permanent support, (2) Contact exposure of the transferred colloid layer in mainly dry state with active electromagnetic radiation through a transparent Line template through which a black and white blue-green filter grid extract positive is a multicolored original to be reproduced, (3) Treatment of the exposed colloid layer with an alkaline substance which is used in conjunction with the in the undeveloped parts of the remaining diazonium salt the hardening of the proteinaceous colloid in the results in unexposed parts, (4) Development of the exposed colloid layer by removing the irradiated parts of the bluish green hydrophilic Washes away the colloid layer with an aqueous liquid, .-. (5) repeating the steps of transferring, contact exposure, Harden and develop in the same way as for the blue-green colloid layer was described, with a yellow, purple, or black colloid layer, so that on the same permanent carrier a multicolored raster image of the GV.486 '"■'""'■ - ' ^l ' ^: " ■ - · ■■■ "■■■■■■■" ■ 109882 / 17OQ ^ i superimposed, colored colloid relief patterns is made, and taking the various contact exposures in register by the specially chosen black-and-white blue-green filter, yellow filter, purple filter and black filter halftone screening are performed positively through "and in which the order and the number of the superposed colloidal relief patterns is chosen arbitrarily. 36. The method according to claim 35 *, characterized in that that the colloidal gelatine is a hydrophilic, contain hardenable colloid. 37 · Procedure according to claim. 35 or 36, characterized in that that the permanent support is opaque and the exposure is carried out so that the to be exposed Colloid layer facing the radiation source. 38. The method according to claim 1, characterized in that the hydrophilic colloid layer on a transparent Carrier has been applied, 39. The method according to claim 1, characterized in that the hydrophilic colloid layer has been applied to a drawing film which serves as a support. GV.486 109882/1700