DE1571816A1 - Thermal copying process - Google Patents

Description

Heat co pi er process

The present invention "relates to a method of recording or reproduction of information with the help of electromagnetic Radiation and a heat-sensitive material containing at least one heat-sensitive substance in the when exposed to electromagnetic radiation, heat is generated.

In Belgian patent specification 656 713 a heat-sensitive recording material has been described which is used for recording can be used by thermal imaging. The material comprises at least one slatt or layer, dss or the contains thermoplastic polymeric particles with or without a binder, the binder being different from the particles in it Permeability and / or fat-friendliness differentiates. The, material provides permeable and impermeable and /

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or hydrophilic and hydrophobic sites in an image-wise distribution.

For the purpose of image generation, the recording material is according to the above-mentioned Belgian patent specification of the effect exposed to image-wise distributed thermal radiation. The thermoplastic polymer present in the sheet or layer Is hydrophobic and can be embedded in a hydrophilic binder in a weight ratio greater than 1: 1. goal of The present invention is a recording method to propose that on generating differentiated permeability and / or Pett-friendliness and / or solubility and / or meltability is based on the effect of electromagnetic radiation and primarily of visible light

Subject the method according to the invention can be the most varied Types of printing forms, for example for screen printing, planographic printing, letterpress printing, etching printing, magnet printing and the hectographle are produced.

In addition, the material according to the invention is suitable for making legible copies of an original, which can be transparent or opaque reflective

The subject of the invention is methods of recording or reproduction of information by imagewise exposure of a recording material to electromagnetic radiation and is characterized in that at least one recording layer (either attached to a base or can be self-supporting) one or more hydrophobic

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contains thermoplastic polymers in finely divided form and

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that the layer of an aqueous dispersion of the thermo-

made plastic polymeric particles / was, the particles in thermally conductive contact with one or more substances stand that absorb at least part of the wave range of electromagnetic radiation and convert it to heat Umwandeis can. The intensity and the duration of the exposure is so great that on or in the layer a difference in permeability and / or fat-friendliness and / or solubility and / or meltability created image

The process according to the invention does not require that the heat-sensitive layer contain a binder. It will, however the use of a hydrophilic binder in a weight ratio of less than 1: 1 based on the thermoplastic particles is preferred. The best results are obtained with a recording layer made up of one or more hydrophobic thermoplastic polymers, which are dispersed in a hydrophilic binder in a weight ratio of 3: 2.

A preferred embodiment is used for exposure uses electromagnetic radiation, the majority of which (at least 70 # of the radiation energy) in the wavelength range is below 700 nm. The exposure is preferably with visible light performed.

The exposure time should not exceed 10 * "see. You should for one and the same area of the recording material less than 10 see. and preferably 10 "to 10 * sec.

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The method according to the invention is based on selective or different heating of the recording material, its properties, for example its meltability, its water permeability, its solubility in water or organic solvents and / or its hydrophilic character being changed.

The image-wise differentiation of the properties brought about by the action of heat on the electromagnetic radiation-absorbing substances can be achieved both when the thermoplastic polymer particles are in thermally conductive contact with one another within the recording layer and when they are brought into contact by close contact between two different carrier materials.

The principle of the recording method according to the invention can be briefly illustrated as follows: The recording layer consists of a finely divided, hydrophobic thermoplastic polymeric material. It is produced from an aqueous dispersion which optionally contains a hydrophilic binder so that the spaces between the thermoplastic particles are permeable to water. If the layer now contains light-absorbing substances that allow a heat exchange with the polymeric particles and if this system is briefly exposed imagewise to intense electromagnetic radiation, then the temperature in the exposed areas suddenly increases and changes the physical properties of the layer.

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This change in physical properties can be used in various ways to produce images. The. Possible methods for this are described below:

In its preferred embodiment, the recording process according to the invention consists of the following steps: 1. Provision of a recording material which is equipped with at least one essentially dry and water-permeable layer which contains particles which consist entirely or mainly of a hydrophobic thermoplastic polymer, which in a weight ratio greater than 1: 1 is dispersed in a hydrophilic binder. The softening point of the particles is preferably 10 to 20O ⁰ O above room temperature and their size is between 0.01 / u and 50 / u. The particles are in thermally conductive contact with one or more substances that absorb visible light or part of the visible wavelength range and convert it into heat.

2 · Imagewise flash exposure of the recording material with electromagnetic radiation, the main part of which consists of visible light, so that the recording material exposure to light causes a selective or differential decrease in its permeability and / or fat-friendliness and / or experiences solubility and / or meltability.

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The imagewise exposure can be both progressive (e.g. exposure of a tape-shaped recording material) or happen simultaneously. In the second case, for example, by reflex exposure or fluoroscopy of an original such as for example a print template or a halide silver see-through ' image. The image can be exposed both correctly and reversed and as a positive or negative to be developed.

With regard to the change in physical properties, it is not necessary that the recording material be extreme Changes, for example, so that individual points of the material are completely permeable and / or completely fat-friendly and / or become completely soluble and / or completely meltable.

Rather, the degree or nature of these differentiations depends on the intended use of the recording material in other words how the record is to be read or developed. From the further Description shows that the inventive method for the majority of recording and copying techniques photographic and / or mechanical field can be used.

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Thus, the method according to the invention is suitable for producing prints by the reflex copy method or according to the usual fluoroscopic method, for example by contact or direct exposure · When used the reflex method, the exposure intensity and the heat sensitivity of the recording material is advantageously chosen so that the directly from the light source the light-sensitive material directed rays the physical properties of the heat-sensitive material change practically no or only a little.

The image-wise reflected light then gets into the material the practically usable image differences between those struck by the reflected light and those struck by this light are not hit spots.

The coating of the recording material should be sufficiently transparent for the reflective exposure. For the fluoroscopy process, it is advantageous if the recording material, in particular a multi-coated material, is opaque.

The term "transparent" is to be understood in connection with the light source used. If a gas discharge is used for the exposure, the emitted waves will be in the range between 0.3 / U and 1 ai . When using a light source that supplies visible light, greater or lesser proportions of infrared and ultraviolet radiation must be taken into account.

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To achieve a warming effect with visible light, A finely divided black or dark colored figment or a corresponding one can be incorporated into the photosensitive material Dye can be incorporated. These additives can also be contained in another sheet or layer, which is in contact with the recording material, so that a heat transfer between the additives mentioned and the thermoplastic polymer rope is guaranteed.

Without limiting the scope of the invention, it should be said of the mechanism of the recording process that the finely divided hydrophobic thermoplastic polymeric particles covered by a film of moisture or a wetting agent encased in a hydrophilic binding agent and diapered, as a result of the local very intense heating come into contact with each other and thereby an essentially impermeable Form a polymer network in which the hydrophobic particles stick to one another.

Ia should follow the general description of the invention now syetem and structure of the various heat-sensitive Materials as well as the type of light source used and the development techniques used are described.

Figures 1 to 8 show enlarged sections of 7 types of heat-sensitive materials according to the present invention.

Figure 9 is a graph of flash exposure method according to the reflex procedure. --.__

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FIGS. 10, 12 and 13 are echematic representations of recording materials in connection with an attention direction.

Pig. 11 shows the graphical representation of one for the further suitable device described below.

In Fig. 1 a heat-sensitive material is shown, that of a heat-sensitive layer (1) on the Base (2) is attached and the dispersed particles of a hydrophobic thermoplastic polymer (3) and Particle (4) contains one or more substances that absorb electromagnetic radiation and convert it into heat can in a hydrophilic binder (5).

Fig. 2 shows a recording material in the form of a self-supporting Sheet 6, consisting of a dispersion of magnetic radiation absorbing particles (4) and of thermoplastic polymeric particles (3) in a hydrophilic binder (5).

As shown in Fig. 3, a thermosensitive material may also be a thermosensitive, substantially dry one and porous layer 7 attached to the base (2). The layer (7) consists primarily of hydrophobic thermoplastic polymeric particles (3) and particles (4) which absorb electromagnetic radiation and can transform it into warmth. The layer (7) is preferably made of an aqueous latex system in which

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the polymeric particles can be covered with a film of moisture that prevents them from sticking together, but through Heat can be destroyed. The heat-sensitive material can also be like Pig. 4 shows a thermosensitive layer ^ contain a layer carrier (2) and an intermediate layer (8) in which particles (4) of a substance are accommodated which electromagnetic radiation is absorbed and converted into heat.

Another possibility is illustrated in FIG. 5. There is (9) a cover layer which absorbs the radiation Contains particles and (1) the heat sensitive Layer on the base (2).

In Fig. 6 a heat-sensitive layer (1), a layer support (2), a 2w ££ c ⁱ ! Iö: üoeMelrfc (8) with a cover layer (9) is shown. Here the two last-mentioned layers contain the radiation-absorbing particles (4). It will be readily appreciated that in materials such as those shown in Figures 4 to 6 in which the radiation absorbing substance (whether particulate or otherwise) is housed in a layer other than the recording layer, the layer containing the radiation absorbing substance needs to be less heat-insulating in order to prevent the heat given off by the absorbent substances from being distributed over the entire layer. On the other hand, the conduction of heat from the substances to the polymeric particles need not be impeded. These factors and the layer thickness must be considered when selecting suitable layers for radiation-absorbing

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Substances to be considered

Pig. 7 shows a thermosensitive layer (1) on top of a Base (2) · layer (1) contains in a hydrophilic binder (5) hydrophobic thermoplastic polymeric particles (3) and particles (4) of a radiation-absorbing Substance.

As a heat sensitive material it is also a with the heat-sensitive coating material impregnated carrier material suitable, for example one for the production of Usual Japanese paper stencils.

Although only radiation-absorbing substances in finely divided form (in the dispersed state) have so far been described in detail, these substances can also can be used in other ways, for example as a solution or as a uniform phase or layer.

As already mentioned, the thermosensitive layers or self-supporting films according to the invention can have a certain amount Amount of hydrophilic binders included. For example, hydrophilic, natural colloids, modified hydrophilic natural colloids or synthetic colloids are suitable for this hydrophilic polymers. More precisely, the binders are selected from the group of water-soluble natural ones or modified, natural hydrophilic colloids, such as gelatin, glue, casein, zein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose,

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Carboxymetb ^ lhydroxyethylcellulose, hydroxyethylate starch, gum arabic, sucrose octaeaate, ammonium alginate, sodium alginate and hydrophilic derivatives of such colloids. Synthetic, hydrophilic polymers, such as, for example, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylamine, polyethylene oxide, polyethylene sulfonic acid, polyacrylic acid and hydrophilic copolymers and derivatives of such polymers are also suitable.

Some of these polymers, as well as their derivatives, are in the weakly acidic or weakly alkaline range in water solvable.

The hydrophilic binder used in the production of the material according to the invention should be curable with a view to higher mechanical strength. A film-forming material rom gelatin type containing, for example, by reaction such as formaldehyde or glyoxal are cured old an aldehyde. Also suitable for this are alum and other hardening agents which can be processed into a layer together with the colloid or the finished recording material is treated with their solutions.

The use of hardeners in recording materials containing hydrophilic binders generally depends on the desired mechanical strength. The amount of hardening agent used can be between 0.5 to 5 wt .- ^ be. The treatment of the recording layer or the self-supporting film can be carried out with a solution

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whose concentration of hardener is between 2 and 25 wt .- #.

Pure a wet or dry transfer of parts of the A recording layer which has not been imagewise exposed on a receiving material contains the hydrophilic binder preferably a plasticizer. Suitable plasticizers for gelatin are urea and potassium thiocyanate.

Other suitable plasticizers for gelatin are described in J. Phys. Chem. 60 (1956) 1299-1306. In the case of wet transfer the plasticizer should be present in the dampening liquid in order to transfer the unexposed areas to improve the recording layer by pressing it against a receiving material.

The hydrophobic, thermoplastic polymer, which according to the invention represents the most important heat-sensitive substance of the recording material, should form a porous or water-permeable layer after casting from an aqueous dispersion at a temperature which does not significantly exceed room temperature and, after drying. The polymeric particles soften preferably between and 200 ^° C. above room temperature. Examples of suitable polymers are those which have a melting point or a softening temperature between 10 and 200 ^° C. above room temperature. In particular, suitable are, for example, polyethylene and polyvinylidene chloride having a melting point of 110 and 190 ⁰ C, and the following polymers with the softening temperatures: Polystyrene (100 ⁰ O) ₉

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Polymethylmethacrylate (70-109 ° C) _t Polyäthylmethaerylat (5O ⁰ C), polyvinyl chloride (about 70 ⁰ C), polyacrylonitrile (about 100 ⁰ C), poly-N-vinylcarbazole (200 ⁰ C).

As is known, the softening temperature can be lowered by adding so-called plasticizers. Details on suitable plasticizers and the softening temperature of homo- and copolymers are in the work Chimie Macromoleculare - Generalites, by Georges Champetier, Librairie Armand Colin Paris Ve ⁴ IQ, p. 194 - 198, to be found. Then it seems that one can achieve a range of softening temperatures by copolymerization or copolycondensation, which depends on the proportion of the monomer or condensation reagent IBt ₁ , * üae for the copolymerization or the copolycondensation iii. fr-j the Moicirulargewicht for the dae erfinduagsgesSfe <s ^?;;?. ren fal geeigenten polymers may vary within wide limits * polymers having a molecular "weight in the range 5000 van" to 1 million are preferred. Particularly suitable is polyethylene with a molecular weight of 15,000 to 50,000. However, there is a certain relationship between the melting point or the softening temperature and the sensitivity (imaging temperature) of the receiving layer. Other factors also seem to play a role. It was observed that recording layers with the same heat sensitivity are obtained both with polyethylene and with polyvinylidene chloride.

For the production of the recording material according to the invention suitable hydrophobic thermoplastic Ilomo- and

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Copolymers can be used as an aqueous dispersion containing a hydrophilic binder. The aqueous dispersion of the homopolymers or copolymers is preferably prepared by free-radical chain polymerization in emulsion of one or more polymerizable monomers by known processes. These methods are described, for example, in the work by W. Sörenson and TW Campbell, Preparative Methods of Polymer Chemistry, Interscience Publishers, New York (1961). Use is made of dispersion auxiliaries here, as described by K. Laux in "Die Grenzflächenktivstoffe" in Winnaeker-KÜchler * s "Chemische Technologie ¹ * Carl Hansen Verlag, Munich (1960) pages 155-242.

In addition, aqueous dispersions of polymers are to be used take into account that by dispersing a solution of a water-insoluble polymer in a water-immiscible solvent in the aqueous solution of a hydrophilic Binder are produced. Examples of solvents that may be mentioned are chlorinated hydrocarbons, such as methylene chloride and trichlorethylene.

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According to another process, aqueous dispersions of polymers are obtained by dispersing molten thermoplastic polymers in water in the presence of wetting agents. To improve the For dispersing properties, the polymers can contain a certain number of hydrophilic groups, such as in the case of partially oxidized polyethylene.

Suitable dispersions of polymers can also be used obtained by dispersing mechanically finely divided polymeric particles in water. Surface-active substances and / or hydrophilic protective colloids, such as polyvinyl alcohol or gelatin, are preferably used for this purpose. By However, dispersions made by polymerization emulsion are preferred. According to this polymerization process the monomer is dispersed in the form of fine droplets in water, the emulsifying agent (soaps, ammonium oleate * sulfonated fatty alcohols, etc.), protective colloids (carboxymethyl cellulose, polyvinyl alcohol, etc.), a buffer system, surface-active substances and water-soluble catalysts, e.g. Lasseretoffperoxid or a persulfate contains. You get such a stable dispersion of the polymeric particles in water.

The polymer particles in the dispersion should be 0.01 at up to 50 u. The larger the particles, the lower the resolution in the recording. Very good The results are dispersions with one particle size

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in 0.05 to 2 and dispersions whose particle size is between IyU and 1 m / u are called colloidal systems. A colloidal system whose carrier phase consists of water (dispersion medium) and its dispersed Phase formed by particles of particle size l / U - 0.001 / U is called hydrosol. Good results are obtained with those hydrosols whose polymeric particles are not larger than 0.1 / U. Recording layers deliver equally good results, containing from 0.5 g to 10 g of the thermoplastic polymeric particles per square meter. The thickness of the invention The recording layers used preferably vary between 0.5 / U and 10 / U. As mentioned earlier, it isn't necessary for the production of the heat-sensitive according to the invention Layers to use a binder. You can use the support and / or the drying process for the Choose a layer so that natural adhesive forces occur between the binder-free layer and the base. A simple Gluing (e.g. by heating) the polymeric particles to one another and to the base without affecting the porosity of the layer is impaired, increases the mechanical strength. Since a binder is not absolutely necessary, the amount can of the hydrophilic binder in the recording material vary between 0-6 and a relatively high percentage. The amount of the hydrophilic binder is mainly determined by the required hydrophilic-hydrophobic difference determined, which is obtained when the heat-sensitive layer is heated imagewise. In general is

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a weight ratio of 11 liters of the hydrophilic binder and the hydrophobic thermoplastic particles too high. On the other hand, with a ratio of 3 parts by weight of hydrophobic thermoplastic particles to 2 parts by weight of the hydrophilic binder very clear image-wise change from hydrophilic to hydrophobic and from permeable to impermeable, both for making copies as well as for reproduction purposes is useful.

The temperature at which the heat-sensitive material experiences a substantial loss of its permeability is preferably in the range between 40 and 200 ^° C.

Das Wärmeempf: 'iidli? Hp material can of course be used or during the emergence of the visual differentiation are heated in their entirety to a certain temperature »below that necessary for image production Temperature is. Such measures will make the Amount of heat by which the thermoplastic particles at certain points of the layer by conduction or Heat exchange with the light-absorbing substance is to be increased, reduced accordingly.

Pigments suitable for the process according to the invention, that convert visible light into heat are, for example, the following!

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Ruse, graphite, heavy metal oxides or sulfides, in particular heavy metals with an atomic weight between 45 and 210, such as manganese or lead sulfide or Heavy metals even in finely divided form, such as silver, bismuth, lead, iron, cobalt or nickel. Ruba is preferred as the light absorbing material for the present invention.

Further useful radiation-absorbing pigments and information on radiation-absorbing substances are given in Belgian patent specification No. 657 502 included.

In a particular embodiment of the recording material, the hydrophobic thermoplastic polymeric particles themselves contain substances that absorb visible light and convert it into heat. Such polymeric particles can be, for example produced by carrying out the emulsion polymerization in the presence of the absorbent substances dispersed in the reaction medium.

As an example of an intimate mixture of dispersed pigments and polymeric particles, the Preparation of a dispersion of polyethylene and Ruse are described.

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40 g of a partially oxidized polyethylene, prepared according to the British Patent Specification No. 997135 by oxidation of polyethylene having an average molecular Arge wight of 7,000, a melting point of 130 ⁰ C and an acid number of 26 -. 30 are melted between 130 and 15O ⁰ C. 2.2 ecm of a 5.0% potassium hydroxide solution, 18 g of n-hexadecyloxy-decaoxyethylene, and 20 g of carbon black with a particle size of about 0.04 / u are added in portions to the molten polyethylene. This gives a viscous black paste which is allowed to cool to room temperature. The black polymer is then finely ground and passed through a 60-mesh sieve (mesh size 0.25 mm).

60 g of the MaELguts in 300. The dispersion is now heated with stirring to 90 ⁰ C and the autoclave is then closed "While the temperature to 150 ⁰ C increases, to speed up the stirrer to 2,000 rpm. After 30 minutes, the autoclave is allowed to cool to room temperature. In this way, a black dispersion with a pH of 8.3 is obtained.

Another procedure can be used by a certain

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Part or all of the hydrophobic thermoplastic polymeric particles contain a substance in dissolved form, which electromagnetic radiation is transformed into heat, so that the transparency and heat sensitivity of the Recording material can be influenced by the polymer particles themselves.

The heat-sensitive layer should be 0.01 to 1 and preferably 0.1 to 0.5 percent by weight of pigment included on the total weight of the layer. If no colors are to be reproduced, black or deep black colored pigments preferred. Just the case In the reflex copy, the optical density of the light-absorbing layer (gray layer) should preferably be between 0.25 and 0.78.

The reproduction of colored originals should include the colored substances and mixtures of such substances, which only absorb light from a part of the visible spectrum and convert it into heat, preferably light absorb one of the primary colors (red, green, blue) or the subtractive colors (blue-green, purple, yellow).

Substances that absorb visible light of a part of the visible spectrum and the absorbed light energy convert into heat are for example in the groups of

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Azo, the triaryl methane, the xanthene, acridine, methine, azine, phthalocyanine, antraquinone and similar dyes can be found.

These substances can be used in the dispersed and / or dissolved state. PUr the dispersed form a grain size smaller than 0.1µ is preferred.

The amount of substances in a heat sensitive Recording material depends on the desired heat sensitivity of this material, which is available standing radiation intensity and the expected effect of the available heat on the substances.

When the colored substances are incorporated into the heat-sensitive material, they are preferably set in an amount that causes an optical density between 0.3 and 5.

The manufacture of the heat-sensitive layers can be carried out with conventional means such as rollers, brushes, spray devices, doctor blades and air brushes, which allow a control of the thickness and the distribution of the coating material.

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Yes

In the case of a recording material which consists of a heat-sensitive layer on a base »can this base can be rigid or flexible depending on the intended use of the material · JBr can also be used be permeable or impermeable, for example water permeable such as a transparent fabric « If flexibility is not important, sheets made of metal, glass or plastic, fiberboard, cardboard and the like can be used.

Depending on the intended use, the inventive Material can be built up in different ways. For example, you can use the heat-sensitive layer Apply (with or without a hydrophilic binder) on a hydrophilic layer, which in turn acts as a carrier serves. A hydrophilic layer is understood here to mean a layer that is replaced by water or aqueous Solutions is wettable * This layer can be porous or water permeable. You can, for example, to Mainly consist of natural or synthetic hydrophilic colloids. Examples of such layers are a gelatin layer, a light-sensitive silver halide layer, a water-permeable germ-containing colloid layer for the silver salt diffusion process, a colloid layer, which contains pigments or dissolved dyes or a reaction component suitable for a color reaction, a hydrophilic colloid layer, the developer substances for silver

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Contains halides or complex silver salts or a hydrophilic Kollold layer with finely divided metals, such as silver, which can be etched away.

In addition to a hydrophilic binder, the heat-sensitive layer can contain all kinds of additives, such as electrically conductive particles, e.g. carbon black, further dyes that can be bleached, distilled or sublimed, reactant components for dye formation, catalysts for color reactions, development nuclei, light-sensitive substances, developer substances for silver halides or complex silver salts, and finally _f feänverteilte metals which can be etching, reaction components can be preferably below 80 ⁰ C and distilled from other image-forming materials. Furthermore, hardening agents for the hydrophilic binder and optionally drying agents can be contained in the layer, which harden the hydrophobic thermoplastic polymer at elevated temperature.

If reflex exposure is used, the concentration of these additives should not be so high that the heat- sensitive layer becomes too opaque.

The heat-sensitive layer, which optionally contains a hydrophilic binder, can also be applied to a hydrophobic layer which can serve as a base; There is a layer under the hydrophobic layer

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understood that not or only slightly wetted by water will.

Such layers or substrates are made, for example, from cellulose ester derivatives, polyesters, Polystyrene, glass, etc.

Furthermore, the heat-sensitive layer according to FIG Invention between two hydrophilic layers, two hydrophobic layers, one hydrophilic and one hydrophobic Layer, between two permeable layers, two impermeable layers, or between one permeable and an impermeable layer.

In a layer or film that is in contact with the heat-sensitive material or in water-permeable relationship, additives may be included which are of practical interest for the production of visible images in accordance with the recorded thermal image, e.g. pigments, dyes, reaction components for the Färbstoffbildung, developing agents, reaction components or dyes distill preferably below 80 ⁰ C or can sublimate development nuclei for the silver salt diffusion process, catalysts for color reactions, conductive particles, and light-sensitive substances.

The effectiveness of electromagnetic radiation that to be converted into heat depends essentially on

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their intensity. For example, a recording material which, when exposed to a light source, is more specific Energy changes its physical properties inadequately, completely satisfactory results deliver when the Strahluhgsenergie increases accordingly will. As the radiation energy increases, so does the distance between the light source and the recording material grow. From the image areas of an original The radiation energy that is absorbed and converted into heat is dissipated all the more quickly and can produce the adjacent imaging The shorter the irradiation and the more intense it is, the less they affect the element. Lamp systems, which provide these high intensities are generally available and do not form part of the present invention.

Lamps with high radiation intensity and a relatively short exposure time are so-called flash lamps, more precisely Gas discharge flash lamps.

In connection with the present invention get good results with a xenon gas discharge lamp with energies from 300 to 1000 watts. Second in time span

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nen of 10 to 10 seconds.

According to a preferred embodiment of this invention, this gas discharge lamp has the shape of a thin one Tube, which is arranged in a hollow glass cylinder (Fig. 9) »so that a uniform exposure of the recording material ι that of the outer wall of the cylinder, possible will.

Details about gas discharge lamps which are suitable for carrying out the method according to the invention can taken from Belgian patent specification 664 868.

Lower energy gas discharge lamps can also be used if the energy emitted is focused on a relatively small, heat-sensitive area. For example, a gas discharge lamp with an output of 40 saturation is suitable. Seconds for copying 6 6 cm and 6 χ 9 cm originals onto a heat-sensitive material according to the present invention. For recording materials whose optical density is at least 1, a power of 0.3 watts is sufficient. Seconds per square centimeter to obtain the required image differences · It goes without saying that the exposure can be progressive or intermittent. Kit other T / orten, the heat-sensitive material can either be scanned image-wise with a modulated light point of high intensity, for example with a

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Laser beam or it can be progressive through a slot through which, for example, the copying light of a continuously radiating tube lamp is focused.

A great advantage of the thermal copying process according to the present In comparison to the classic thermographic copying process, the invention lies in the high sensitivity, the sharpness of the image and the possibility of visible light to use. This makes it possible to reproduce originals which contain image marks which neither are infrared-absorbing and thermally conductive.

During exposure through an original, the original lies between the radiation source and the recording material. After a first possible combination, the heat-sensitive layer in contact with the original, optionally using a transparent one Intermediate sheet or an intermediate layer. The support of the recording material can be used in this combination be opaque or transparent. According to a further embodiment, the recording material is with its back (layer substrate), which in this case is preferably not thermally conductive, with the original in Brought in contact *

If the radiation is directed onto the support of the recording material, the support must be sufficient be transparent.

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During the reflex exposure it becomes semi-transparent Recording material placed between the radiation source and the original. The original (negative or positive) contains surfaces that reflect the copying light or it is a transparent original that is in contact is provided with or near its rear side with a radiation-reflecting element. Before the examples a brief overview is provided for carrying out the reproducing method of the present invention are given about the various systems that, starting from the heat-sensitive Materials suitable for making copies and artwork.

According to a first system, the image-wise differences in the transmittance caused by the exposure are determined and hydrophilicity is used to create an image-wise diffusion of imaging substances in the recording material to run off, for example by treatment with liquids or the transfer of such substances from the recording material into a receiving material. The image-wise diffusion is caused by the mentioned Differentiation of the physical properties enables. For this purpose, the recording material provided with an image can be immersed in an aqueous dye solution the dye only at the points of the recording material (Layer or film) can diffuse, which have remained permeable and sufficiently hydrophilic.

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Of course, instead of a dye solution, a solution of a catalyst can also be used, which initiates a color reaction between the components and the recording material, or the solution of a colorless reaction component which is capable of a color reaction with a colorless or pale reaction component in the recording material.

A second possibility is to incorporate a bleachable colored substance into the recording material, which is decolorized by a bleaching agent which diffuses into the areas of the recording material that have remained permeable. On the other hand, an etchable metal, such as colloidal silver , for example, can be dispersed in the recording material and thus image-wise etched out by allowing the etching liquid to diffuse into the permeable areas of the recording material. The heat-sensitive layer can moreover be applied to an etchable material, for example a zinc or copper plate. In this way it is possible to produce a letterpress or gravure form.

Another application of the diffusion process is to transfer the image-forming substance into the recording material and by diffusion from the areas that have remained permeable to an image receiving material to transport. For example, it is possible

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the recording material or a liquid-permeable layer associated therewith a soluble dye incorporated which is capable of diffusing into a receiving material when the heat-sensitive material is wetted.

According to an interesting method, the heat-sensitive layer or a layer assigned to it contains liquid or solid substances, for example encapsulated dyes. After the image-wise impermeability of the heat-sensitive layer has been established, a pressure is exerted on the surface of the recording material. As a result of this pressure, the capsules burst and stain the heat-sensitive layer in the areas that have remained permeable.

The contents of the capsules can be transferred through these points, for example to a receiving material (recording method without processing liquid or bath). The production of suitable capsules is among others in Belgian patents 628 650, 634 666, 634 667 and 634,668.

Instead of the dye, a colorless reaction component or a catalyst, optionally encapsulated form, can also be incorporated into the recording material.

A-G 141

30 ^ 609883/0362

which is capable of a color reaction with a reaction component in the receiving material.

It is also possible to incorporate the recording material include silver salts which form complexes and which can diffuse into their soluble form in a receiving material containing Seduktions- or development nuclei, wherein an image-wise in accordance with the locations of the recording material, which have remained permeable Silver precipitation occurs.

In this diffusion process, the imaging needs Substances such as dyes or etchable metals or reaction components must not be contained in the recording material itself. You can just as well be in be accommodated in a layer or a carrier material which is in connection with the recording material.

The recording material, for example a self-supporting film, on the other hand, after exposure, can represent an image-wise water-permeable membrane through which an aqueous dye solution is able to diffuse. In this way, a printing master is obtained with the aid of which several copies of an original can be produced on a transfer material.

The membrane can also be used to produce electrolytic prints, since the membrane is in contact with a

A-G 141

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The receiving material acting as an electrode allows the electrolyte to pass through only at the permeable points; with the result that an image-wise electrolytic deposition of the imaging substances takes place on the electrode material.

According to another system, the permeable and soluble areas of the heat-sensitive material become removed for example by washing out or by degradation of the hydrophilic binder. In this case it can the recording material contains a dye, for example a (colored) pigment or a dissolved dye, so that when the image areas are treated with a liquid, a reproduction of the original is created.

Using this system, a gravure stencil is obtained when the heat- sensitive recording layer is applied to an etchable metal base. After the permeable and hydrophilic parts of the recording material have been removed, for example by washing out, the uncovered metal surface can be etched in an image-wise manner. This process can be used, for example, to produce printed circuits. After the remaining parts of the recording layer have been removed, for example with the aid of an organic solvent, the etched metal plate is ready for use as a gravure printing stencil.

A-G 141

BATH ORIGINAL

^'32 ~ 009883/0362

According to this method, letterpress forms can also be produced by simply washing off the permeable and hydrophilic parts of the heat-sensitive recording layer. In this case, the washing process can, if necessary, be followed by the hardening of the remaining parts of the recording material. A relief image is obtained in this way.

If the recording layer is placed on an electrically conductive base, such as aluminum, is attached, it can be used to make an electrostatic printing plate. By washing out the permeable Where the recording layer is located, the electrically conductive substrate becomes corresponding to the exposed image

exposed. The remaining parts of the recording layer then have a significantly higher electrical level Resistance as the conductive pad. As a result of this, electrostatic charging occurs on the recording material a charge image. This charge image can either by known methods, for example with Using a powder, developed or used for the electrostatic transfer printing on an insulating transfer material will.

In addition, the recording material treated in this way can also be used to produce conductivity images will. Such materials and their application are '

A-G 141

- 33 -

in Belgian patent documents 589996 and 599 628 described.

Another possible application of the system described is the production of stencils or Screen printing stencils. For this technique, one or both sides of the permeable substrate are covered with a recording layer. Japanese paper (Xoshino paper), nylon fabric with a mesh size of 0.2 to 0.08 m * are suitable for all carriers. or bronze fabric (see Example 5).

In screen printing technology, it is well known that the printing ink can only be applied to the open (permeable) areas of the fabric reach the print substrate. These vacancies are obtained by the method of the present invention by washing out or etching away the calibration layer in the places that have remained permeable or hydrophilic.

According to a third system, the permeable and hydrophilic areas are transferred to an image receiving material in a moist and / or heated state by printing and tearing them off.

This transfer procedure is possible if

the cohesion of the receiving material is greater than that of the

A-G 141

ß ORJGJNAL

009883/0362

permeable sites of the recording layer, and if the adhesion between the permeable sites and the receiving material is stronger than the cohesion of the permeable areas of the recording material.

After compressing a moistened and imagewise exposed recording material with a receiving material, which is preferably a hydrophilic and / or has a porous surface and the subsequent separation of the two materials results in a satisfactory transfer printing. In this case, the recording material preferably contains either a recording layer which contains a hydrophilic binder in which the hydrophobic thermoplastic polymeric articles are dispersed Binding or a recording layer which is built up from a porous layer of said polymeric particles on a hydrophilic, preferably a colloid, layer with considerable swelling capacity.

The opposite method to the transfer method is possible if the adhesion of the substance in the contact material - here referred to as a8 transfer material - is less than that of the substance in the permeable areas of the recording layer, and when the adhesion between these permeable sites and the transfer material is stronger than that of the substance of the transfer material. Then, for example, a carbon paper with a little hydropnobic surface, like it for that in the

Belgian patent specification 600 508 is used against the moisturized image-wise exposed Recording layer are pressed. After the carbon paper has been peeled off, they remain on the recording material the parts of the paint layer corresponding to the permeable and hydrophilic. The hydrophilic The binder of the recording material can be swollen before being pressed together, so that a Relief image is created that has closer contact with the Color layer enables.

According to this third system, hectographic transfer originals can be produced if the torn material contains a hectographic dye which is soluble in alcohol or a reaction component which can form a dye with a second component, for example in a liquid or a transfer material.

By modifying the third system, the unexposed areas of the heat-sensitive material can be transferred to a receiving material together with a layer of softened polymer. For this purpose, the layer of a polymer that softens at low temperature, e.g. 3. below the temperature at which the heat-sensitive recording material loses its permeability, placed on the recording layer.

0 0 9 8 8 3 / 0362- - «

"_ BAD ORK31NAL

- 3d -

By pressing the exposed recording layer together with a receiving material such as paper simultaneous heating, for example with the help of two heated rollers, and then separating the two materials one finally achieves the effect mentioned at the beginning (recording method without processing liquid).

A recording material suitable for the process described here is shown in FIG. The material consists of a heat-sensitive layer 1 on a polymeric layer 10 with a softening point which is below the temperature at which the heat sensitive layer becomes impermeable. The polymeric layer adheres to the base 2. The heat-sensitive one Layer contains dispersed particles of a hydrophobic thermoplastic polymer 3 and particles 4 of an or several substances that absorb visible light and can convert i η heat into a hydrophilic binder 5 ·

According to another system, when using a low-melting substance (e.g. a dye) in the recording layer itself, this dye by fusing the recording layer, which is with the transfer material is in contact to transmit.

A-G 141

- 37 - ~, -0JQ9883 / 0362

According to a fifth system, the exposed recording material is used for planographic printing. This happens either in connection with a bold printing ink (in this case using a dampening system) or with a printing ink that consists of a mixture of a colored aqueous phase with a colorless or almost colorless one colorless oleophilic phase. In this context, reference is made to Belgian patent specification 676 898.

Multicolor images can be obtained using a thermosensitive material composed of more than one heat-sensitive element is borrowed. For example, it is possible to reproduce at least two colors of a subtractive mixture. A recording material is used for this type described above, consisting of a transparent support, one side of which is covered with a heat-sensitive layer, for example a red Contains dye and the other side a heat-sensitive layer with a green or blue dye wearing.

Multi-color prints can also be made. For this purpose, three heat-sensitive Materials used. They contain substances that emit light from the red, grin and blue areas of the Absorb the spectrum and convert it into heat, such as substances in the colors blue-green, purple or yellow.

* 00 98 83/0 36

- 58 -

The thermosensitive material containing the blue-green substance, for example, is exposed to the red parts areas assigned to the original are impermeable and hydrophobic.

Accordingly, the layer containing the purple substance reacts to the green one, and the layer containing a yellow substance Layer on the blue parts of the original.

To produce the multicolor prints, the matrices obtained in this way are peeled off one above the other to fit.

This printing system can use both aqueous printing inks (compare e.g. Belgian patent specification 676 898) as well as bold offset printing inks in the colors required for the subtractive process (blue-green, purple, yellow) or in the colors required for the additive process (red, green, blue).

For a reproduction of originals, the separate representations in the pure primary colors blue, green and red wear (e.g. a letterhead in the colors blue, green and red) are three separate heat-sensitive materials used, which sensitizes to yellow, purple and blue-green are, respectively, contain blue, green and red dyes in the heat-sensitive layer.

A-G 141

_ ₃₉ _ 009883/0362

Example 1;

A cellulose triacetate base provided with a gelatin adhesive layer is coated with the following casting solution (12.5 m ² with 1 kg):

650 ml of a 6% aqueous gelatin solution 100 ml of a 105% aqueous pyrogallol solution and 20 ml of an 11% aqueous saponin solution 1000 ml made up with water.

After drying, a heat-sensitive layer is applied. The casting solution for this layer has the following composition (application 10 m per kg casting solution):

400 ml of a 3 # aqueous gelatin solution 160 ml of a 40 # aqueous emulsion of polyethylene (Grain size smaller than 0.1 yu; mol weight approx 15000 to 30000)

140 ml of a 3 # aqueous solution of a condensation product of oleic acid and methyl taurine and 1 ml of a 50 # aqueous carbon black dispersion.

The above copy material has a density of 0.27 after drying.

Processing:

Like in Pig. 9 indicated schematically, the above copy material (19) brought into contact with the heat-sensitive layer (20) with the original to be reproduced (21.), the light-absorbing image parts (22) and a reflective one Background (23) owns. . - - *

BADORiGINAL AG 141 - 40 -

009883/0362

It is exposed in reflex, whereby the base of the copy material described above is placed against a glass cylinder (24) which has a diameter of 8 cm and in the axis of which a xenon lamp (25) is arranged, which has a light energy of 610 watts emitted at a distance of 4 cm. The exposure time is 1/2000 sec. The light is essentially composed of waves from the visible range of the spectrum.

The exposed copy material can be used in a simple manner as a printing form, the copies being obtained thereby be that the processed copy material is immersed in water - treatment time 15 seconds. - and by distance the excess water is pressed against a receiving paper, which by treatment with a 15% aqueous iron (IIl) Chloride solution was prepared.

6 black-blue copies of the original are obtained, which are produced by reaction of the iron (III) chloride with that of the liquid Parts of the copy material leaking lyrogallol arise. It is advisable to use the printing form before each copying process moisten again.

Example 2;

A polyethylene terephthalate pad provided with an adhesive layer 0.1 mm thick is coated with the following casting solution (50 g casting solution per m):

935 g of a 10 year old. aqueous gelatin solution 30 g of a 10% aqueous saponin solution, 30 g of a 3% aqueous solution of

009883/0362

AG 14 "» -41-

BAD ORiQiNAL

Uostapon T (commercial product of Farbwerke Höchst AG) 5 g of a 4% aqueous formaldehyde solution.

After drying it is used to produce the heat-sensitive Layer the following casting solution applied (36 g / m):

100 g of a 10% aqueous gelatin solution 160 g of a 40% aqueous dispersion of polyethylene according to Example 1

8 g of an aqueous carbon black dispersion (100 g of this dispersion contain 53 g of carbon black, 23 g of water, 18 g Glycol and 6 g of nonylphenyl polyethylene oxide) 80 g of a 5 # aqueous solution of sodium tetredecyl sulfate

5 g of a 4 5 ^ strength aqueous solution of formaldehyde and 640 g of water.

Processing; It is exposed as described in Example 1. The exposure

2 energy was 0.8 watts per cm.

The exposed material is stretched on a planographic printing cylinder in the usual way and colored with the following printing ink:

10Og of a carbon black dispersion of the above

Settlement 20 ml of an 80 jCigen aqueous solution of a partially ethereal

th melamine-formaldehyde resins 27 g of a copolymer of vinyl acetate and ammonium crotonate (95: 5)

27 g 1,5-uexanediol BADOEiGJWAL

2 g of a 10 η ammonia solution

009883/0362 AG 141 - 42 -

6f5 g urea

13 * g of a 53 ^ igen aqueous dispersion of a copoly-

mers of butyl acrylate and vinyl acetate (1: 1) 80 g of white spirit (. b.p. 180-200 ⁰ C)

20 g xylene

Only the areas of the processed copy layer corresponding to the image parts of the original are exposed to the aqueous colored phase of the printing ink wetted.

The final prints are obtained in the usual way. Similar results are obtained if the carbon black dispersion in the above-mentioned heat-sensitive layer is replaced by 30 ml of a 10 jSigei aqueous dispersion of finely divided silver replaced will.

Example 3:

The copying material according to Example 2 is exposed to light as described there, then moistened with water and the heat-sensitive layer is pressed against a receiving paper. As indicated in FIG. 11, both materials are guided by two rollers (37 and 38), one roller (38) that comes into contact with the receiving paper (36) being heated ^{to about 35 ° C.} The two materials are moved at a speed of 10 cm / sec. The materials are separated behind the rollers, with a thin layer of the heat-sensitive layer being transferred imagewise onto the receiving paper. A copy of the original is received '

009883/0362

Example 4:

The copy material according to Example 2 is as described there exposed, then moistened and the heat-sensitive layer in good contact with the dye layer of a hectographic Brought colored film, which however does not contain the usual hydrophobic protective layer. After a contact time of about a minute the layers are separated, whereby in the places that correspond to the image parts of the original, the dye layer is transferred. You get a reversed one Image of the original that can be used as a printing form for spirit printing.

Example 5t

Japanese paper (paper weight 14 g / m) is divided into the following Solution immersed:

200 g of a 10 # aqueous gelatin solution 200 g of the polyethylene dispersion according to Example 1 2.5 g of the carbon black dispersion according to Example 2 40 g of a 5% aqueous solution of sodium

tetradecyl sulfate and
400 g of water.

After drying, the coated paper has a weight from 20 g / m. The paper treated in this way is exposed as described in Example 2 by means of an electronic flash. Afterward is in a 5 # aqueous solution of sodium salycylai immersed and the layer parts that correspond to the image parts of the original are washed out,

_. AA _ 0 0 9 8 8 3 / 036-2

After washing and drying, a form suitable as a screen printing form is used Material received.

Example 6:

A "barytaized paper (60 g / m) is made with the following Coated casting solution (36 g / m):

150 g of an aqueous gelatin solution

200 g of an aqueous dispersion of colloid silver 8o g of the polyethylene dispersion according to Example 1 40 g of a 5 # aqueous solution of sodium tetradecyl sulfate

2.5 g of a 4 # aqueous formaldehyde solution.

Processing:

As indicated in FIG. 12, it is exposed in reflex. The original is one on a practically non-thermally conductive Base (44) located gelatin layer (43), which a Contains negative silver halftone image. A xenon lamp (35) with an energy of 1.3 watts per meter serves as the light source The copy material (40) consists of the heat-sensitive layer (41) and the base (42). Then the Material passed through a conventional bleach bath, whereby only the areas corresponding to the image parts of the negative silver image are bleached. You get one positive copy of the original.

AG 141 - 45 -

009883/0362

Example 7:

The cellulose triacetate film provided with an adhesive layer is coated with the following casting solution:

900 ml of a 10% aqueous gelatin solution 30 ml of a 10% saponin solution 3o ecm of a 5% aqueous solution of a condensation product of oleic acid and methyl aurine.

After drying, a second layer is applied using the following casting solution (36 g / m):

50 ml of a 10 lgen aqueous gelatin solution 80 ml of a 40 # dispersion of polyvinyl chloride

4 ml of the aqueous carbon black dispersion according to Example 2 2.5 ml of a 4 ml aqueous formaldehyde solution.

Eb is dried and exposed as described in Example 2. The light energy is 1 watt. Lake. per cm.

The processed material is immersed in a 5 l aqueous solution dipped in methylene blue, so that a reversed image of the original - viewed through the surface - is obtained *.

Example 8;

A cellulose triacetate base, which is provided with an adhesive layer, is coated with the following casting solution (15 g / m ² ):

400 g of a 10% aqueous gelatin solution 30 g of a 5% aqueous saponin solution

009883 / 0L36-2- _x

"* BAD ORIGINAL

g of a 5% aqueous solution of the condensation

product of oleic acid and methyl taurine 10 g of an aqueous solution of formaldehyde 200 g of a 10 # aqueous silver dispersion

After drying, a second layer is applied. The casting solution for this has the following composition (application 36 g / m ² ):

50 g of a 10 # aqueous gelatin solution, 80 g of the polyethylene dispersion according to Example 1 40 g of a 5 # aqueous solution of sodium tetradecyl sulfate.

The material is exposed as in Example 6. The exposure energy is 0.9 watts lake. per cm. After processing like in example 6 a positive copy is obtained.

Example 9t

^{The following casting solution (36 g / m 2} ) is applied to the gelatine adhesive layer of a cellulose tetrlacetate film (7 g gelatine per m 2):

100 g of a 10% aqueous gelatin emulsion 160 g of the polyethylene dispersion according to Example 1, 20 g of a 5 # aqueous solution of sodium tetradecyl sulfate

10 g pigment green B Colanyl dough (CI. 10006) 715 g water Processing:

The material is processed as described in Example 2. The exposure energy is A.G141 · -47- 009883/0362 at a distance of 4 cm

6AD

rom original 1OOO watt sec. The exposure time is 1/2000 sec. The graphic original contains black, "blue, green and roto parts of the image on a white background.

The exposed material is washed with a 5 # aqueous Treated methylene blue solution. The color only penetrates into the parts of the heat-sensitive layer that are exposed to light non-reflective black parts of the image and parts of the original image that absorb blue and red light, i.e. the green parts of the image.

A laterally reversed blue image of the black and green image parts of the original is obtained, which is through the substrate is legible through it.

If the green pigment in the above-described layer is replaced by Heliogen blue B Colanyl paste (0.1. 74160) and used in exposed in the same way, all image parts of the original except the red ones are reproduced When replacing the green pigment with Permanent Violet RL Colanyl Dough (30 $ aqueous dispersion of Sirius light blue FP 2 GL CI. 51300) you get a copy in; the all image parts of the original are reproduced.

When using the planographic printing form, for example, the last-mentioned Copy material as described in Example 2 can be used further.

Example 10:

A polyethylene terephthalate layer provided with an adhesive layer (Thickness 0.1 ma) is made with the following casting solution

AG 141 _ ₄₈ . _009883 / 0362

BATH ORIGINAL

'' coated (50 g / m):

g of a 10% aqueous gelatin solution, 15 g of a 3% aqueous solution of a condensation product of methylitaurine and oleic acid 15g of a 10 # aqueous solution of saponin and 5 g of a 4 # aqueous solution of formaldehyde.

Then the following casting solution is applied to produce a heat-sensitive layer (36 g / m):

50 g of a 10 # aqueous gelatin solution 80 g of the polyethylene dispersion according to Example 1 g of a 7 igen aqueous solution of the following link

24 g of a 5 # aqueous solution of the following compound.

SO ₅₅ K SO «K

is Nm

κο -

Il I -MW

H ₃ OCC = CH-CH = CH-CH = CH-C C-

AG 141 - 49 -

009883/0362 BAD ORiGfNAL

124 g of a 5% aqueous solution of the following compound

SO ₉ Na S0, Na

HO-C

N I It Il

.C C = CH - C C-CH,

10 g of a 5 jSigen aqueous solution of sodium tetradecyl

sulfate and
200 g of water.

The material is exposed to light as described in example 9 and further processed according to example 3.

Example 11:

The following casting solution is applied to a cellulose triacetate film provided with an adhesive layer (30 g / m \\

300 g of a 10 5-1 gene aqueous gelatin solution 170 g of a 9% aqueous urea solution 30 g of a 10% aqueous saponin solution 20 g of a 3% aqueous solution of the sodium salt of the condensation product of oleic acid and methyl taurine.

Before casting, the pH of the casting solution is adjusted to 4 by adding aqueous hydrochloric acid.

BAD QRlQmAL AG 141 * _sn_ 009883/0362

After drying, the following casting solution is applied (Application 30 g / m):

50 g of a 10% aqueous gelatin solution, 350 g v / water
90 g of a 35 # aqueous emulsion of poly

vinylidene chloride, prepared as indicated below
25 g of a 5 fSigen aqueous solution of iosodium

tetradecyl sulfate
4 g of the aqueous carbon black dispersion according to Example 2

Processing*

The above material is exposed as shown schematically in FIG. The copying material (30) consists of the base (31), the gelatin intermediate layer (32) and the heat-sensitive layer (33). The original is marked with (34). By means of the xenon lamp (35), the exposure is performed (light energy 0.9 V / att.sec / cm) The exposed material becomes weak ater moistened with V / 22 ⁰ C and contacted with the heat-sensitive layer is in contact consisting of a flat paper from a baryta paper. The binding agent of the barite layer is hardened gelatine (application 50 g / m 2). As shown in FIG. 11, the two materials are guided through 2 rollers at the same temperature. When the two materials are separated, the heat-sensitive layer is transferred imagewise to the receiving paper.

AG 141 _ 51 -

_{e /; 0} - 009883/0362

The printing form obtained can be subjected again to a flash exposure and all printing form can be used in conventional offset printing machines.

Production of the polyvinylidene chloride latex

In an autoclave (capacity 800 ml) equipped with a stirrer. Thermometers and pressure gauges are the following Reagents inserted:

120 com V / ater

32 ecm of a 10% aqueous solution of the sodium salt of the condensation product of oleic acid and methyl aurine

160 ecm of a 10% aqueous solution of the following link

40 cc of a 2 f-aqueous solution of potassium permanganate

eulfate
- 8 ecm of a 5 $ aqueous solution of acidic

Sodium sulfate
160 g vinylidene chloride.

In the above solutions, water demineralized by means of ion exchangers was used.

It is by means of a warm 6O ⁰ C water wheel at a stirring speed of 1000 rev / min heated. Compartment for 30 minutes at this temperature, a pressure of 1.5 to 2 Attt is obtained, which begins to decrease after about 3 hours. After a further 2 1/2 hours at 60 ^° C., a vacuum has developed in the autoclave. The reaction mixture remains in the autoclave for a further hour, cooling to room temperature. J) he ^ obtained white latex _A , _{g 141} ^ DORIQINAl 009883/0362

has a pH value of 2. It is neutralized by adding 2η sodium hydroxide solution. The yield of solids is 35 ^.

Example 12

A polyethylene terephthalate base (thickness 0.1 mm) provided with an adhesive layer is coated with the following casting solution (application 30 g / m ² ):

55 g of a 10 ^ strength aqueous solution of polyvinyl alcohol

22 g of a 10 # aqueous solution of polyvinylpyrrolidone

120 g of a 20% aqueous dispersion of polyethylene (40 g of partially oxidized polyethylene according to British patent specification 997 135, average molar weight 7000; melting point ^{125-130 0} J acid number 26-30; 12.4 g of n-hexadecyloxy-decaoxyethylene and 150 ml V / water)
70 g of water

40 g of the carbon black dispersion according to Example 2

18 g of a 3-point aqueous solution of hatriurate tetradecyl sulfate.

Processing:

The above material is as in Pig. 12 indicated in contact by a rastered negative exposure and is exposed by means of a xenon lamp, distance A cm, energy of the light source 800 Satt.see, exposure time 3.10 ~ ^ sec.

" ^r CTO 98 8 3/0362

After exposure, the layer becomes heat-sensitive rubbed with a cotton cloth soaked in ethanol, the unexposed parts being removed. The same result is obtained with a benzene-soaked one Rag.

Example 15;

A polyethylene terephthalate film (thickness 0.1 mm) with is provided with an adhesive layer, is coated with the following pouring solution (application 50 g / -m):

955 g of a 10% aqueous gelatin solution 50 g of a 10% aqueous saponin solution 50 g of a 5% aqueous solution of the sodium salt of the condensation product of oleic acid and methyl taurine 5 g of a 4 % aqueous formaldehyde solution

In this layer, the heat-sensitive layer is coated according to Example 2. FIG.

is processed further as in example 2. The light source has an energy of 800 watt.see, the exposure time is 5.10 ~ * see.

Example 14:

The following casting solution is applied to a CeÜuloeetrlacetat film provided with an adhesive layer (application 30g / m ² ): 300 g of a 10% aqueous gelatin solution 170 g of water

30 * g of a 10% aqueous saponin solution M _# -54-

20 g of a 3 # solution of the sodium salt of the condensation product from oleic acid and

Methyl taurine

Then a second layer is applied using the following casting solution (application 30 g / m):

50 g of a 10% aqueous solution of gelatin and 350 g of Yfesser 80 g of the polyethylene dispersion according to Example 1

4 g of the carbon black dispersion according to Example 2, 40 g of a 5% aqueous solution of sodium tetradecysulphate

After exposure according to the Pig schematic. 13 is the material in a 5 # aqueous solution τοπ laliumrhodanid dipped and the heat-sensitive layer pressed against a receiving paper. Processing is carried out as indicated in FIG. The still moist, "image-wise transferred layer, which is sensitive to heat, is now pressed against the dye layer of a spirit printing film that does not contain a hydrophobic surface layer. After a Contact time of one minute is separated, with the parts corresponding to the heat-sensitive layer parts of the The dye layer is torn out and transferred. A reverse relief image of the original is obtained, which can be used as a spirit pressure original.

Example 15: '·

Sine polyethylene terephthalate film (thickness 0.1 mra) is with coated with the following casting solution (application 70 g / m): A-G 141 - 55 -

009883/0362

20 g polyhexamethylene adipate

4 g polyisobutylene (average molar weight 10,000) 200 g methylene chloride

Then the following layer is applied (application 35 g / m):

100 g of the aqueous dispersion of polyethylene after

Example 14
600 g v / ater

5 g of the aqueous carbon black dispersion according to Example 2 25 g of a 5 ^ strength aqueous dispersion of disodium • tetradecyl sulfate

The material is exposed as described in Example 11 and further processed.

In processing in accordance with Example 14, a reversed image of the original is obtained, this original can be heated to 100 ⁰ C and sprinkled with iron powder ferrooagnetischem · The powder sticks, so that a magnetic printing plate is obtained ·

Example 16

The following is applied to a polyethylene-laminated transparent paper which has been exposed to a corona discharge Casting solution applied (application 36g / m):

30 ecm of a 5 # aqueous solution of the condensation product of oleic acid and He thy Itaurin. 900 ecm of a 10 ^ strength aqueous gelatin solution 30 ecm of a 10% aqueous saponin solution

Then the following layer is applied (36g / m):

-G. - ~ 0-Ό 9883/0362 '■. - 5ö - _{BAD 0RK3HNAL}

50 ml of a 10% aqueous solution of gelatin 80 ml of a polyethylene dispersion according to Example 1, 4 ml of the aqueous carbon black dispersion according to Example 2 1000 ml of water

Ss is exposed and processed as described in Example 3.

- 57 -

009883/0362

Claims (12)

Patent claims: 1. A process for the production of photographic images by exposure of a heat-sensitive layer, an image-wise change in the physical properties of the layer taking place at the heated areas, characterized in that a heat-sensitive layer is exposed which contains particles of a hydrophobic thermoplastic polymer, wherein these particles are in close contact with one or more substances which are able to absorb the actinic light used for the imagewise exposure and convert it into heat , the exposure being brief and being carried out at high intensity. 2. The method according to claim 1, characterized in that the polymer particles are arranged in a hydrophilic binder are, where the weight ratio of binder to hydrophobic particles smaller than 1: 1 1st. 3. The method according to claim 1, characterized in that a light is used for the exposure which essentially consists of wavelengths below 700 m / rev and since the exposure time is less than 10 sec . 4. The method according to claim 1, characterized in that is exposed by means of an electronic flash or a Gaeentladunge light and the exposure time is 10 to 10 "^ see. - jo ■ -; ■ «,; ... . _Ä ... (5038837.036 2 5. The method according to claim 2, characterized in that the layer containing the polymer particles by application an aqueous dispersion of the particles of the thermoplastic polymer is prepared, so that the weight ratio of Particle to the hydrophilic binder is larger than 3: 2. 6. The method according to claim 2, characterized in that the hydrophilic binder is water-permeable or v / water-soluble is. 7. The method according to claim 6, characterized in that the hydrophilic binder is gelatin or poly-N-vinylpyrrolidone is used. 8. The method according to claim 1, characterized in that the hydrophobic particles consist of a polymer which ^{softens about 10 to 200 0} C above room temperature. 9. The method according to claim 1, characterized in that the hydrophobic particles have a diameter of 0.1 to 50 Ai . 10. The method according to claim 1, characterized in that organic dyes or as light-absorbing substances inorganic pigments can be used. 11. The method according to claim 10, characterized in that. as light-absorbing substances finely divided metallic silver or carbon is used. - 59 - 009883/0362 12. The method according to claim 1, characterized in that the heat-sensitive layer has an optical density of 0.25 to 0.78 for actinic light and the Exposure is carried out in the Keflex. J.Verfahren according to claims 1 to 10, characterized in that the hydrophobic polymer particles essentially consist of polyethylene. BATH ORIGINAL AG 141 - 60 - 00 9883/03 62 Blank page