DE1920360A1 - Registering and reproducing information - Google Patents

Description

AGPA-GE VA ERT AG ^; LEVERKUSEN

Registering and reproducing information

Priorities: Great Britain, April 24, 1968, 19 457/63

Great Britain, November 12, 1968, No*. 53 674/68, 54 675/68 and 53 676 / 6S Gevaert-Agfa N.V ,, Mortsel-Antwerpen, Belgium

The present invention relates to the photographic Registering and reproducing information, as well as the suitable recording and reproduction materials for this purpose.

In particular, this invention relates to a method for producing an irreversible change in the physical condition ₍ at the points where the photoconductive material has been exposed to sufficiently strong electromagnetic radiation. The photoconductive element, which is described in more detail below, experiences the action of the electromagnetic radiation a reduction in the permeability to and removability by water. This means that in this element an image or a signal in the form of electromagnetic radiation is registered as a pattern of differences in permeability and removability by water «

According to the invention, a recording material, the at least contains a water-permeable registration layer, which consists essentially of one or more photoconductive compounds and dispersed finely divided material containing hydrophobic particles having a hydrophobic Contain or consist of a substance (1) according to the information exposed to effective electromagnetic radiation, the photoconductive compounds and the dispersed hydrophobic particles are present in the registration layer in such an amount that this registration

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layer without substantial införmationsmässlge Temperature ** ^ ^v forfeit the sufficiently irradiated areas a decrease ^ ί of water permeability learn, and (2) he £ eu $ te latent image by penetration of a liquid in the unexposed or insufficiently irradiated areas of the recording layer developed, which causes a visible change in accordance with these points _f or developed by removing the non-irradiated or insufficiently irradiated areas of the registration layer. .

The dispersed hydrophobic particles must for the most part are in a very close relationship (only very little apart), so that neighboring particles are at any one Place of the registration layer, which is sensitive to electromagnetic radiation, to be able to coagulate, if this layer is sufficiently irradiated at this point.

A preferably used material according to the invention contains a water-permeable registration layer that contains a hydrophobic substance finely divided in a hydrophilic binder, preferably in a weight ratio ratio of at least 1/1, whereby

the registration material continues to be in effective relation with the dispersed, hydrophobic substance contains another substance whose specific electrical resistance is Exposure to electromagnetic radiation decreases.

Using an appropriate amount of the hydrophilic binder it even possible to make liquid and semi-solid hydrophobic to use dispersed material, for example non-polar organic liquids or soft substances like paraffin oil, soft hydrophobic compounds more aromatic Nature, e.g. pyrene and hydrophobic waxes.

The finely divided hydrophobic substance is preferably whole or partially made of a hydrophobic thermoplastic material, which is preferably solid at room temperature (the

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a 1320360

preferably between 30 ° and 20O ⁰ C) = The registration layer preferably contains solid hydrophobic particles which are dispersed in a weight ratio of at least 1/1 in a hydrophilic binder, which particles preferably consist entirely or mainly of hydrophobic thermoplastic material, for example hydrophobic thermoplastic polymeric material.

The hydrophobic substance is preferably applied from an aqueous dispersion in which a dispersant is used is used to disperse the finely divided hydrophobic material, and keep it in dispersed state = the hydrophobic material can be chemically treated to make it to be able to disperse more easily in an aqueous medium «This is, among other things, the case with the partial oxidation of Polyethylene.

Substances whose specific electrical resistance on exposure to electromagnetic radiation decreases, for example, inorganic and organic photoconductive semiconductor materials. The photoconductive that can be used according to the invention en substances can be both η-type and p-type semiconductors or be a mixture of both »

It is assumed that a change in conductivity, possibly also of the charging capacity or the property Electrons in: catch or send out, m a = W « a change in the potential level of the photoconductive particles compared to the dispersed material in the surrounding medium, the cause is that it coagulates dispersed hydrophobic particles takes place = This assumption is based on the knowledge that, theoretically, flocculation and coagulation are the same phenomena = In fact, in a suspended solid system, both are Phenomena characterized by surface reactions between particles, which reactions are the repulsive forces - destroy or reduce between individual dispersed particles (IndcEnq.Chem., C = P = Priesing, Volume 54, Tr = C.,

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U 1910360

1962, pp.38-45, A Theory of Coagulation useful for Design) =

The stability of colloidal particles in aqueous dispersions is attributed to hydration and electrostatic charge. The dispersed particles form an electronic or electrostatic capacity with respect to the dispersing medium, so that they are able to lose, catch or have in common with the formation of electrons of bonds such as ionic, covalent, dipolar, or induced dipolar bonds, or hydrogen bonds ,, These bonds can be classified in the form of binding energy (expressed in kilocalories per mol) ₀
Ionic crystal bonds are the strongest, viz
more than 150-200, covalent bonds about 50-100,
Hydrogen bonds 1-10, and dipolar bonds less
als 5 = Similar to the dipolar bonds, the bonds v. -which are the result of an induced polarization in molecules and atoms, which are normally electrically neutral (London-van der Waals forces) «Such
Bindings are also low ^ Janergetic., In the
Most coagulation processes neither create nor split covalent bonds or ordered ionic crystal lattices, although the system is subject to the ionic equilibrium in the solution.

The electrical capacitance formed around a dispersed hydrophobic or lyophobic particle is built up by the electrical double layer which envelops the particle. It envelops the dispersed particle in a solid
Layer of electrostatic charges, for example from
Ions, and this particle originates from the interior of the colloidal mass, or can be formed on it by a
preferred absorption on it of a dispersant "

During flocculation, four forces act on both the
dispersed Fha <e as well as on the coagulant, namely the Brownian motion, the force of gravity, the
Coulorn's charge and the stirring forces.

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• Colloidal stability depends on various parameters, ■ of which the water-absorbing character of the substances that iValence and the concentration of the ions that make up the

• envelop yawed particles with the electrical double layer, are the most special. It is believed that at least

. one of these parameters by the exposure of the photoconductive Compounds »which are in an operative relationship to the dispersed material is changed, and that a neutralization or a reduction of the charge present in the double layer and consequently a Coagulation takes place which is the direct contact of the hydrophobic surfaces of the dispersed hydrophobic particles has the consequence. It should be noted that the dispersed hydrophobic particles can themselves be photoconductive, or a photoconductor, for example an ionoid photoconductor.

The direct joint contact of the hydrophobic polymer Particles reduce the permeability of the registration layer for water, because then hydrophobic surfaces are in direct contact with one another without a separating hydrophilic hydration layer =

The binding forces between the directly touching hydrophobic ones Particles are forces of adhesion. The adhesion of the coagulated hydrophobic particles can be with the forces of attraction existing between polymer chains Compare- It is possible to control this adhesion by speaking of hydrophobic dispersed particles as hydrophobic Polymer particles of the same or a different chemical structure adopts, thereby preserving the possibility remains to create fewer or more firm physical and chemical bonds between the coagulated particles.

So you can use a mixture of polymer particles, at least some of which are polymer chains with certain groups • contains which in polarity and / or polarizability are different, whereby intermolecular forces are quantum

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mechanical structure, for example charge transfer dö f ■ "■> Complexes that can be formed. Polymers with groups ttni # £ · «* different electron donating or electron attracting <learns Fortune are, for example, polyacrylonitrile, polyvinyl! chloride, polyethylene, polymethyl methacrylate, and vinyl polymers that contain a core with an aromatic character, e.g. polystyrene, polyvinyl naphthalene, polyvinyl anthracene, or poly-N-vinylcarbazole, as well as Mitro- | Cyan and halogen derivatives of such aromatic vinyl polymers Core.

Give these general information and the explanation of the Probable mechanism of action of the inventive In the process, a more detailed description of the composition and structure of various photosensitive devices follows Elements that make up a part of the recording and reproducing material, or such Form material for the use according to the invention suitable is.

According to a preferred embodiment, the photoconductive element contains hydrophobic thermoplastic polymer parts · surfaces with a sufficiently high softening point so as not to coalesce when coated at 30 ° C. These hydrophobic thermoplastic polymer particles are dispersed in a hydrophobic binder in an amount vjelche the substantial reduction in water permeability the layer during exposure is not prevented. These hydrophobic thermoplastic polymer particles are effective Contact with at least one photosensitive substance, that upon exposure to effective electromagnetic radiation causes coagulation of the dispersed polymer particles caused.

Whether a photosensitive substance is used for this purpose suitable or not, can easily be determined in a routine experiment with a mixture of thermoplastic hydrophobic materials Resin particles, which together with the photosensitive

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Substance are dispersed in a hydrophilic binder, preferably not the volume of the binder is larger than that of the resin particles "

Among the Ausdruck'Wirksame electromagnetic radiation "refers to such a type and degree of radiation, which effects the desired reduction of the water permeability of the recording layer without any substantial temperature increase · If the dispersed thermoplastic ^ hydrophobic substances used solid at room temperature are, the temperature is to the Do not exceed the softening point of the hydrophobic thermoplastic particles «

The expression "effective contact" means that the photoconductive substance so thoroughly with the dispersed hydrophobic material that in turn be photoconductive can, mixed is that a decrease in water penetration. permeability of the registration layer under the described Exposure conditions in the sensitivity range of the «inserted, not spectrally or spectrally sensitized Photoconductor material can take place.

In Canadian Patent 787 843 is a method cur registration of information, according to which a water-permeable registration layer is used, whose larger parts by weight from a dispersion of hydrophobic,

polymeric material that is solid at room temperature consists of a hydrophilic binder, the weight ratio of these polymeric particles to this binder being greater ε.1ε 1: 1, and this layer has been formed by producing and drying a layer which contains these particles in an aqueous, contains this medium containing binder, and is capable of being made water-permeable or less water-permeable at any point in the layer by the action of heat and / or pressure. at this point, and where such a layer is heated in terms of information i ^ fP ^^ Uf ^ $ § ^ £ 'and / or the

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Pressure is put on that information in the form differentiated water permeability of the different This registration process is registered, and parts of this registration process that are permeable to water have remained, to be removed "

Preferred hydrophobic thermoplastic, solid at room temperature polymers which are used in latex form are, E-olyäthylen and polyvinylidene chloride having a melting point of 110 or = 190 ° C, and the following polymers with their resrektiven glass transition temperatures: Polystyrene (100 ⁰ C), polymethyl methacrylate (between 70 and 1O5 ° C), polyethyl methacrylate (50 ⁰ C), polyvinyl chloride (at 70 ° C), polyacrylonitrile (at 100 ⁰ C), and toly-N-vinylcarbazole (20O ⁰ C), ..

It is well known that the glass transition temperature can be achieved by adding certain substances called plasticizers Reduce interpolymerization.

The molecular weight of those which can be used in the present invention E'polymers can vary within wide limits, but polymers with a molecular weight between 5,000 and ! "000,000 are preferred. With polyethylene with one Molecular weight between 15,000 and 50,000 can be achieve particularly good results ». Mixed dispersions of polymer particles can of course also be used Consideration, and the various polymer particles can Contain ingredients, for example those that color or opaque the polymer particles.

The aqueous dispersion of the polymeric (homopolymers or copolymers) is preferably prepared by emulsion polymerization of one or more polymerizable monomers using known techniques, for example as described by W.Sörenson and TW Campbell, 2reparative Methods of Polymer Chemistry, Interseience Publishers, I lev ". ¹ York (1961). In emulsion polymerization, dispersants such as those described by K.Laux are used,

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The surface-active substances, Winnackers-Küchlers Chemical technology, Carl Hanser-Verlag, Munich (1960) pp.155-242.

Furthermore, polymer dispersions which are suitable for the use of the process according to the invention can be Manufacture by mechanically finely divided polymer particles, preferably with the aid of surface-active substances and / or optionally with hydrophilic protective colloids such as polyvinyl alcohol and gelatin, dispersed in water A preferred latex of this type contains polyethylene particles » Excellent results are achieved with latexes, which were produced by emulsion polymerization. After this polymerization technique, the monomer becomes in finely divided droplets in the presence of water, Emulsifiers (soaps, ammonium oleate, sulfonated fatty alcohols and the like), protective colloids (carboxymethyl cellulose, polyvinyl alcohol and the like), e.g. a buffer system, a surfactant, and a water soluble catalyst e.g. hydrogen peroxide or a persulfate, dispersed by stirring. The polymer is produced as a stable dispersion of polymer particles in Preserving water »In this case, the electrical double layer is formed by the dispersant.

The dispersed polymer particles can be between 0.01 u and be 50 u. However, the larger the particles, the smaller the resolution when registering »Very good results are achieved with dispersions whose polymer particles are 0.05 to 2 μm in size - dispersions in which the dispersed particles have a size between 1 u and 1 nm are considered to be colloidal systems. A colloidal system whose continuous phase is formed by water and whose dispersed phase is through 1 u to 0.001 u large particles are formed, is a hydrosolo. Good results are obtained by using such Hydrosols are used, the polymer particles of which are not larger

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are than 0.1 u. Good results can also be achieved, if an amount of polymer is used in the registration layer which is between 0.5 g and 10 g / m2. The thickness of the registration layers according to the invention preferably varies between 0.5. and 10 u.

The carrier and / or the drying technology of the layer can be chosen such that between the layer and the carrier, optionally with a suitable adhesive layer has been coated, natural adhesion takes place.

When in the photosensitive recording layers according to the invention a hydrophilic continuous phase is present, and it is preferred that these become hydrophilic polymers which act as binders, e.g. hydrophilic natural colloids, modified hydrophilic natural Colloids, or synthetic hydrophilic polymers »In particular, it can be water-soluble, natural or film-forming modified natural hydrophilic colloids such as gelatin, glue, casein, zein, oxyethyl cellulose, carboxymethyl cellulose, Ethyl cellulose, carboxymethyl-oxyethyl- cellulose, gum arabic, sodium alginate and hydropHiIe Derivatives of such colloids. It can also be a synthetic hydrophilic polymer, such as polyvinyl alcohol, polyvinyl-IJ-pyrrolidone, Poly vinylamine, polyethylene oxide, eolystyrenesulfonic acid, Polyacrylic acid and hydrophilic copolymers and derivatives of such polymers. Preferably own the hydrophilic polymers have such a high molecular weight that they are film-forming and to some extent hardened for higher mechanical strength can be. For example, gelatine can be mixed with formaldehyde harden.

Preferred hydrophilic binders are proteinaceous in nature, and in this regard casein and gelatins are preferred.

The weight ratio of dispersed hydrophobic material, to hydrophilic binder is one of the factors

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which determined the photosensitivity of the registration element The thotosensitivity of the registration layer is shown in the Form of a reduction in water permeability or an increase in the toughness of a photographic exposed part of the registration layer against separation from its support by an aqueous treatment (Wegv / asch- • development) measured. It should be noted that when determining the photosensitivity, the temperature of the irradiated Parts of the .Registrierschicht not or not substantially compared to that of the non-irradiated parts.

Experience has shown that one is practical usable sensitivity for the reproduction of information-wise Modulated electromagnetic radiation can be achieved by wash-away development with a weight ratio of dispersed hydrophobic substance, preferably hydrophobic thermoplastic, Γolyrtiereilchen solid at room temperature, to a hydrophilic binder from at least 1: 1, the registration layer preferably contains 35 to 10 <3ew * jfc hydrophilic binder in relation to the finely divided hydrophobic material. Optimal results are achieved with a weight ratio of hydrophobic dispersed Particles of hydrophilic binder of 4: 1.

lie.ch enveloping a preferred embodiment of this invention the photoconductive substances the dispersed hydrophobic ones Particles in the registration layer.

In a particular embodiment, these hydrophobic particles consist of a hydrophobic photoconductive substance, for example i. ^: oly-N-vinylcarbazole, or are. contain hydrophobic particles photoconductive substances dissolved zBin a hydrophobic wax or t'olymeren, or et such substances in particulate form, which are covered by hydrophobic material, or by hydrophobic capsules.

".! In a preferred embodiment, a photolei -

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tender substance, which without heating in an electromagnetically irradiated state dispersed the ..usflockuncj of the hydrophobic Material causes, applied in a dissolved state, and envelops the hydrophobic particles in molecularly distributed Shape = Preferably used photoconductive substances are in view of their compatibility with a hydrophilic polymer sufficient «hydrophilic = if, for example, the hydrophilic Polymers possess the ability of gel-sol transformation, thus the photoconductor material is dissolved in the solution from which the gel is formed and forms with the continuous hydrophilic binder = a solid solution

The thotoconductor materials can be electromagnetic for any type Radiation, Z = B = X-rays, UV light, visible light and, -or infrared light = if the for If you are not sensitive to visible light, you can Sensitize spectrally by means of certain sensitizer dyes =

Ihotoconductive substances, which in themselves are used for visible light are sensitive, one finds in the photoconductive organic Dyes and inorganic colored photoconductor vei bonds, z = B = · cadmium sulfide, cadmium sulfide selenide and lead (II) oxido

Preferred organic photosensitive semiconductor compounds, which their electrical behavior changes when exposed to •, u effective electromagnetic radiation ir ..;. n in the case of organic photoconductive dyes = those which are particularly suitable are

nctoconductive zinc oxide have spectral sensitizing properties = such dyes can be found in the. Xanthene dyes, preferably fluorescein stains, be j. the thiazine and acridine dyes,. preferably the water-soluble acridine dyes. A large number of these dyes are characterized by their fluorescence, and are found in the. American patent 2 L75 OAl described =:

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For the photoconductive properties of fluorescein dyes such as eosin, consider, for example, ^I Semiconductive properties of organic dyes "by A = Τ» Vartanyan, Izvesto Akad »I.'auk, S = ScS = R =, Ser = Fiz"; L6 (1952), pp. 169-185, cf = C "A" _45, 3709 i) referenced "

The dyes are preferably in dissolved form and used in the form of an aqueous solution, which is the .Dispersion of the hydrophobic particles in a hydrophilic Binders are added =

Depending on the type of the organic photoconductive material can be related to the weight ratio of this substance

ι
the total weight of the hydrophobic particles, preferably thermoplastic polymer particles and hydrophilic binder, are only 0.05 % . Very high sensitivity is achieved with fluorescein dyes such as eosin and erythrosin =

According to the invention, organic ones are preferably used photoconductive dyes which are light reducible and incapable of being reduced by a thiol polymer how gelatin was introduced into the sulfhydryl groups (so-called thiolated types of gelatin), to be reduced under protection from light, but which are able to through the sulfhydryl groups of the polymer to be reduced when excited with visible light .. For such a type of dye reference is made to the American patent specification 3,145,104 “These photo-reducible, dyes include photoconductive dyes of the fluorescein class, the thiazine cells, the acridine class, and the porphyrin class = · Suitable photo-reducible dyes are, for example BengalroEa, phloxin, erythrosin, eosin, fluorescein, acriflavin, thionin, riboflavin, chlorophyll, hematoporphyrin, Proflavine and methylene blue »The dyes soluble in aqueous media are preferred, namely Fluorescein dyes, thiazine dyes and water-soluble ones Acridine dyes, which are preferably associated with a protein

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like colloid combined v / earth, which is the hydrophilic • represents the continuous phase of the registration layer =

Preferred inorganic photoconductive substances are inorganic substances such as a photoconductive metal or a photoconductive one Metal compound which is an element of the 6B group of periodic table contains =

Specific inorganic semiconductor materials with photoconductive properties which can be used in the materials according to the invention are Ge, TiOp; ZnO; ZrO ₂ ; ^{GeO 2; In} ₂ ° 3; SnO ₃ ; Bi ₃ O ₃ ; PbO; BeO; Sb ₃ O ₅ , SiO ₂ ; BaTiO ₃ ; Ta ₂ O ₅ ; TeO ₂ ; B ₂ O ₃ ; ZnS; MnO ₃ ; SnS ₂ ; CdS; CdSe; CdS-Se; red lead (Pb_0.), And chromium (III) oxide = These semiconductor materials can be sensitized by many known techniques, such as doping with foreign ions, dye sensitization and heating =

Preferred compounds of this group are photoconductive zinc oxide, titanium (IV) oxide, lead (II) oxide, and preferably the yellow modification (Massicot), red lead (Pb_O ^), chromium (III) oxide and cadmium sulfide =

The preferred type of photoconductive zinc oxide is that in type of photographic recording materials used, and it is best to use photoconductive zinc oxide, which is made by oxidizing zinc vapor »

In the production of a registration layer suitable for the formation of halftone images, Blex (II) oxide gives excellent results Results = There are two types of lead (II) oxxd namely the red lead (II) oxide with a tetragonal crystal structure and the yellow lead (II) oxide with orthorhombic Crystal structure, according to the invention for X-ray photography is preferred =

Further good results can be achieved with photoconductive Titanium (IV) oxide, especially with the type of titanium (IV) oxide that is successful in the registration process such as

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described in British patent specification 1,043,250 will".

Particles of photoconductive titanium (IV) oxide with particularly good properties for the use according to the invention have a grain size of at most 250 nm. Processes manufactured by which titanium (IV) chloride is pyrolyzed (British I ³ V tcntschrift I 101 516) .. Ti tan (IV) oxides with an average grain size between 25 and 100 nm are preferred »

Average grain size means the grain size at the top of the Gaussian distribution curve of a Mixture of particles with a decreasing number of larger and smaller particles

The weight ratios of dispersed non-spectrally sensitized inorganic photoconductor material to the total amount the hydrophobic thermoplastic polymer particles are preferably in the range from 1: 3 to 5.3.

The inorganic type photoconductor materials can be spectral be sensitized or endowed »Sc can for example photoconductive zinc oxide and titanium (IV) oxide are very advantageous by means of fluorescein dyes, for example with eosin and Erythrosine, be spectrally sensitized. photoconductive Bloi (II) oxide can e.g. be grounded with bismuth.

Suitable inorganic colored photoconductor materials with their own c-mpf Indlichkci t for visible .rc-s light are for example photoconductive lead (II) oxide, Cc.dn-.iurr.su If id, cadmium se] enide, and mixed crystals of calcium sulphide - selenide, - .. 'elche' photoconductors possibly in eint.m a white photoconductor, z.3. "Thermoconductive zinc oxide, containing mixture is used './ can earth =

The grain size of the dispersed photoconductor material, uelcho when exposed to active electromagnetic radiation

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a registration layer used according to the invention less Make water permeable is preferably not significantly greater than that of the dispersed hydrophobic Material? = So the grain size is preferably below 10 u, and best still in the range of 0.1 to 0.5 u »

The amount by weight of this photoconductor in the registration layer is preferably sufficient to a practically usable image quality by a wash-away development using exposure times below 10 min = with light sources of conventional copiers, for example U = V = -emissive Mercury vapor lamps such as those used in diazo copiers, tungsten incandescent lamps such as those filled with iodine vapor Tungsten incandescent lamps of the dual spectral copier (trade name) are used. For example, there will be 24 30 V / 39 W lamps in the exposure part of the 76 Dual Spectrum model ;: used =

Sensitive text values are given in the following table as a function of the layer composition «The registration layer contains 20% by weight of glycerol per 100 g Polyethylene =

The registration layers are exposed through a gray wedge with a constant 0.1 using a 1500 W quartz iodine lamp from a distance of 65 cm from the registration layers that are not in thermal contact with the wedge. the latter is carried out in a thermostated (20 ⁰ C) vacuum frame =

Under the same circumstances, all are exposed A wash away development materials in an automatic Developing device as described in Belgian patent 715-932-subject = Die mit of the first not erased: the same level as seen

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Light energy is a measure of sensitivity. Tabel

attempt
No ο

1
2
3
4th
5
6th
7th

Ingredients of the registration layer in g / m2

. existence

1
1

1
1
1
1

Polyethylene latex particles (\ O, 1 y)

3 3 3 3 3 3 3

Photoconductive

Zinc oxide- 0 0 Particle O 0 (0.17 y) 0 5 0 2.5 , 025 1.0 , 025 0 5 1

Eosin

sensitivity

Lux c sec.

10 ⁶

.36

> 90

0.025

1.1 0.7 0.7

Joules / cm-2

575 460 350> 1150 15 9.5 9.5

Practical results are obtained with 0.3 to 1.7 parts by weight of photoconductive material such as photoconductive zinc oxide and 1 part by weight of thermoplastic polymer particles such as polyethylene particles _{or the like}

In addition to the dispersed hydrophobic particles and / or the hydrophilic binder, the photosensitive layer used according to the invention can contain all sorts of ingredients, such as non-photosensitive pigments, plasticizers for the hydrophilic binder and / or for the dispersed polymers that improve their adhesive contact, electrically conductive particles, e.g. carbon black particles , Dyes z ° B = bleachable dyes, water-soluble dyes, reaction components for the production of dyes, catalysts for color reactions, development nuclei, light-sensitive substances, e.g. silver halide. Diazonium salts, developer substances ... for silver halide or complexed silver halide, finely divided metal particles which, for example, can be etched away, reaction components which can preferably be distilled off ^{below SO 0 C,}

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and other image-generating material * Further can this layer contains hardeners for the hydrophilic binder, and optionally hardeners which harden the hydrophobic thermoplastic polymer at higher temperatures

Mach a preferred embodiment contains that according to the invention Photosensitive recording material Substances that increase photosensitivity, but without to expand the range of spectral sensitivity. Such substances are found in hygroscopic compounds = preferred substances are hygroscopic polyols, like glycerolο hygroscopic or weakly hygroscopic Ionic compounds can increase sensitivity, for example lithium chloride and potassium bromide.,

Depending on their determination, the one according to the invention photosensitive element containing materials be composed in different ways = Z = Bo can die containing a photocoagulant composition photosensitive layer can be applied to a hydrophilic layer, which may serve as a support « A hydrophilic layer is understood to be a layer that can be wetted by water or aqueous solutions « Such a layer can be porous or water-permeable. ZoB = this hydrophilic layer can be the main thing from natural or synthetic colloids that are found in Water soluble or dispersible, be composed = Examples of such layers are a gelatin layer, a photosensitive silver halide emulsion layer; a water-permeable keirtide-containing colloid layer for the application of the silver complex diffusion transfer process, a Baryta layer containing gelatin and barium sulfate, a gelatin layer, the pigments or contains dissolved dyes, or contains reaction components, which are able to trigger a color reaction, a gelatin layer which Developer substances for silver halide or complexing

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tes silver halide contains, or a gelatin layer which contains finely divided metal particles that are etched away can be, e.g. silver »

Furthermore, the registration layer according to the invention can be placed between two hydrophilic layers, one hydrophilic and a hydrophobic layer, between two permeable layers, or between one permeable and placed in a non-permeable layer »

A layer or a film which is in contact or water-permeable relationship with the photosensitive layer can contain all sorts of ingredients, ζ.Β »Ingredients which are of practical importance to effect the adhesion to the registration layer» In other words, such a layer can serve as an adhesive layer. Suitable adhesive layers which can be used together with the recording layers according to the invention are described in French patent 1 507 G74. Other ingredients can be advantageous for the development of the registered image, e.g. pigments, dyes, reaction ^{components for the formation of dyes, developer substances, reaction components or dyes, which can preferably be distilled off below CO 0} C, light-sensitive substances, e.g. silver halide or diazonium salts, development nuclei, which are suitable for use in the silver complex diffusion transfer process, catalysts for color reactions and / or conductive particles, e.g. metal particles

Depending on the use of the recording material, the support of the registration layer can be rigid or flexible.

If flexibility is preferred, a leaf-shaped element such as a wallpaper sheet is used. a plastic film, a metal foil or the like »

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If flexibility is not a priority, ϊ slats made of metal, glass, plastic, fiber, cardboard or similar can be used »The carrier can be both permeable and impermeable; it can be water-permeable like a wire grid or a textile fabric

Suitable non-water-permeable carriers are made from hydrophobic resins, e.g. from cellulose ester derivatives, Polyester, polystyrene, hydrophobic metal with a hydrophobic layer coated hydrophilic Metal,. Z = B, with an oxide layer, glass and the like To the adhesion of the registration layer to their To improve the carrier, one or more adhesive layers can be applied ο ■ "

The registration according to the invention can take place in different ways Ways take place, depending on the method by which the registration element is irradiated ο

It should be noted, however, that the present invention not on d ~ js information-based melting or evidence of dispersed hydrophobic thermoplastic particles in the rogistering layer, and that consequently kc-ine information "ssigu heat absorption in the registration layer must take place.

A short, high-intensity electromagnetic exposure, volche a substantial "internal heating of the registration layer does not fall under the scope of the present invention, ..

For this purpose "-.uf die krr." I see patent specification Γ: Ο6 124 referenced. Taking into account the sensitivity of the registration layer produced up to now Exposures longer than 0.1 sec. With continuously acting (no flash light) radiation source !! more common Copier used,

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According to one embodiment, a transparent original which bears light-absorbing symbols is registered by bringing the photosensitive element of a recording material according to the invention into contact with this original, and then exposing this photosensitive element to so strong electromagnetic radiation that an image is registered in the form of differences in water permeability without ₍ the temperature of the parts of this element which correspond to the transparent parts of the original, 'increasing significantly.
According to another embodiment, an opaque or transparent original is projected episcopically or diascopically onto the recording material =

Before the examples, a non-limiting overview of the various systems is given which are suitable for the production of copies and matrices for the reproduction of originals, starting with a recording material according to the invention, image-wise electromagnetically irradiated Feeding image-generating substance to the registration element by image-wise diffusion by means of a liquid treatment, or used to transfer such substances from the registration element to the receiving material Foil) only in the places that remained permeable and sufficiently hydrophilic »Of course , instead of a dye solution, a solution of a catalyst can be used to ■ trigger a color reaction between components in the recording material, or a solution of a colorless reaction component which is capable of entering into a color reaction with a colorless or weakly colored reaction component in the recording material.

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Do another example of the first system possible to incorporate colored substances into the registration element, which by means of a bleaching agent that is permeable to the remaining parts of the registration material diffuse into it, can be bleached »After a An alternative to this system is a conductive substance, r.oBo an etchable metal such as colloidal silver, which is homogeneously distributed in the registration element by a liquid diffusing into the permeable areas image-wise etched away = the photosensitive layer can be placed on an etchable base, e.g. one with aluminum coated resin film can be applied «When using this material, it is possible through image-wise Etching to produce a planographic or intaglio printing form »

Make a second embodiment of the image generation, using diffusion, the image-forming substance incorporated in the registration material is transmitted through Transferring diffusion from the areas that have remained permeable to an image receiving material »This is how it is, for example possible to use a soluble dye in the registration element or to store them in a layer that is more permeable to liquids Relationship is what dye is capable of imagewise to a receiving material diffuse away when the photographically exposed Registration element is wetted «,

Of course, instead of the dye, you can use a colorless reaction component or the registration element incorporate a catalyst to enter into a color reaction with a reaction component in the receiving material »

It is also possible to incorporate the registration material silver salts which can complexed v / ground, and which may in its dissolved form to a receiver About <Uffundi "r" s, the reduction

909847/0863 BATH l

contains germs or developmental germs, upon which in accordance silver is image-wise deposited with the areas of the recording material that have remained permeable »

! lol this diffusion methods, the imaging _n substances need not be present in the registration element itself; they can also be stored in a layer or in a carrier which is in a water-permeable relationship therewith.

According to a second system, the parts of the informationsmärrig electromagnetically irradiated Registriermaterial.:· which wa sufficiently be rc are remained erdurchlässig, ZcBo removed by washing off or by degrading of the hydrophilic binder, and by removing the hydrophobic particles which have not been flocculated by the exposure, By using this technique, a direct, visible copy of the information is obtained if the registration element contained a dye, for example a colored pigment, and / or a dissolved dye before exposure

By using this second system k.nn to make a gravure printing plate by starting from the image-tr cig end en registration layer, which was placed on a "tr.baren metal ^carrier":: oh the removal of the permeable and hydrophilic remaining parts DER Registration layer, r: .B, by washing out, and after the remaining parts of the registration layer have been made sufficiently resistant to the etching solution, the bare mead can be used. 11 bildrriassi α are weigh-etched. In this V / ei se, for example, can produce circuits gedruckte- = K oh the Del crr.ung-, _s Eg by e-inc-s organic solvent, .the icklun after l \ 'eguaschert \.': ; remaining parts of the registration layer can be the etched Ke tfsi.l plate -.je- η, ί-ch .. der. Depth ..and the. ViGiSe _- the session as flat printing form, gravure printing form or letterpress form. ven ^r t ⁵ ndet v; orden *

90984 7/0 8.6 6

Using this second system, it is also possible to produce a stencil or a halftone printing form by one according to the invention in terms of information Electromagnetically irradiated recording material - - goes »To use this technique, at least one Side of a grid material covered with a registration layer, or the grid material represents a part - .. a self-supporting film as described above = Japanese paper (Yoshinö paper) are used as grid material, Nylon fabric with a mesh size of 0.2 bi ~ 0.08 mm and bronze wire mesh are particularly suitable.

As is well known, it is only possible to use the raster printing technique at the open (permeable) areas of the .Gewebes (Screen material) ink pass, and apply to the material to be printed in accordance with this Discard jobs = The vacancies in the image are obtained according to the invention by the registration layer composition in the places where this layer or this film had remained permeable and hydrophilic, washes away or dismantle.

According to a third system, the permeable .and hydros phil remaining parts are transmitted by pinching and pulling out to a receiving material I

This mode of transmission is possible if the cohesion ■. of the construction material of the receiving layer is greater than that of the building material ■: the permeable parts the registration layer, and if the adhesion between these permeable parts and the receiving material is greater than the cohesion of the building material permeable parts »·: - ■ -. .

This transfer is successful if --mr.-n after the compression of an inventive ,. wet, image-wise-electromagnetically irradiated registration elements and eirea.Receiving material ::, preferably a hydro-

909847/0066,. , - .., "Λ. BATH

• has a phile and / or porous surface, e.g. a paper foil, separates both materials from one another = according to this embodiment, the registration layer contains preferred v / egg se a hydrophilic binder in which hydrophobic thermoplastic polymer particles are dispersed.

The mutual type of transfer is possible if the cohesion of the construction material of the receiving material is less than that of the construction material of the permeable parts of the registration layer , and if the adhesion between these permeable parts and the receiving material is greater than that of the construction material of this receiving material. For example, a dye layer of carbon paper with a weakly hydrophobic surface, as used in the method according to French patent 1,466,223, can image-wise on the hydrophilic parts of the after printing onto a moistened material bearing an image produced by exposure Registration material are transferred if it is separated from it = Before the registration layer and the dye layer are printed together, the hydrophilic binding agent of the registration layer can be allowed to swell, so that a relief image is created that allows better contact with the dye layer =

So according to this third system it is possible to have original spirit replicas because the torn material contain a hectographic dye may which is soluble in the transfer liquid, or may contain a reaction component which a dye with the reactant present ^ u are able to form, e.g. in the transmission fluid or in the transmission material =

According to a fourth system, it is possible by using a low-melting dye in the registration element this dye by heating the image-wise washed out registration element in contact with a Transfer material to be transferred to it =

903 8W / Ü8S6

BATH

Ali ί- ¥

The following examples illustrate the invention *
Unless otherwise stated, the denotes the percentages
Weight percent =

At spie 1_ 1 ~~.

A 0.1 mm thick polyethylene terephthalate carrier is im

Ratio of 18 g per m2 coated with the following composition:

20% aqueous dispersion of the copolymer
from vinylidene chloride, N-terto-butyl acrylamide and
Itaconic acid (molar ratio 08/10/2) 1 «.. g

40% aqueous dispersion of polyethylene with

a particle size below 0.1 u and one

Average molecular weight between 15,000

and 30 = 000 12 g

30% aqueous dispersion of silica 12 g

Ethanol 100 g

Water 864 g

This adhesive layer is ^{dried at 30 °} C. on this
Layer, a photosensitive layer with the following composition is applied in a ratio of 50 g / m2:

10% aqueous gelatin solution (Bloom gel strengthening

speed: 260) 200 g

40% aqueous dispersion of colloidal
Polyethylene with a particle size of
less than 0.1 u and an average molecular weight between 15,0OO and 30 = 000 20O g

50% aqueous dispersion of photoconductive

capable zinc oxide (average particle size

0.17 u) '■ 320 g

Glycerol 15 g

Ethanol '90 g

Water 140 g

The photosensitive layer is dried at 25 ° C =

The photosensitive material obtained is 10 in a vacuum
Min = by using a developed silver halide emulsion layer containing a halftone negative copy
a 1500 watt quartz iodine lamp, which is arranged in a reflector, exposed in contact = the exposure occurs

809847/0666: ■

BATHROOM 0FH61NAL

from a distance of 30 cm above the vacuum frame. .

"After exposure, the material is treated with a
abundantly rubbed soft sponge moistened with water.
In this way, the unexposed parts are \ - / egge / ischt, and a relief image is obtained »

Instead of tap water, you can use a 5% potassium thiocyanate or use sodium salicylate solution «

If you look at the composition of the photosensitive
Layer the gelatin replaced by polyvinylpyrrolidone, so
one obtains analogous results, although the differentiation
the solubility between the exposed and the unexposed parts is not as high as when used
of gelatin.

Example 2 ■

A 0.1 mm thick polyethylene terephthalate carrier that comes with
a gelatin adhesive layer is provided in proportion
of 30 g / m2 coated with the following composition "":
10% aqueous gelatin solution 400 g

40% aqueous dispersion of polyethylene
with a particle size below 0.1 u
And an average molecular weight '
. between 15.0Ö0 and 30 * 000 32Og

10% aqueous saponin solution 40 g

3% aqueous solution of the sodium salt
> j OS of the condensation product from oleic acid and
- _; Methyl taurine 40 g

.. _r 4% aqueous formaldehyde solution 20 g

These. Intermediate layer is dried at 30 ⁰ C.

On top of this layer you wear a 50 g / m2
photosensitive layer composed of the following composition. ; ■;:.-.- .. ■.: ■■ ".: -." ■ '.-: "

; : 10% aqueous gelatin solution. . 133 g

40% aqueous dispersion of polyethylene
with a particle size below 0.1 y and
'One' average molecular weight
. 15> 00O and. 3Ο 00Ο. . . ..: 133 g

9O9SA7 / OÖ0S

10% aqueous dispersion of colloidal ■

Silver 250 g

50% aqueous dispersion of photoconductive

capable zinc oxide (average particle size

0.17 γ) 220 g

Ethanol. 90 g

This layer is dried at 25 ° C. ■

The material obtained is exposed in a Buroza 600 diazo copier (marketed by Atlas, DeIf t, Miederlande) set to 3 through a developed silverh: ¹ ogenide emulsion layer containing a negative line copy "

After this exposure, the material turns into a conventional one Dipped bleach bath = ^ Only those parts that match the non-transparent parts of the template, ' are bleached so that a positive copy of the photographic negative is obtained. ·

At s pi e_l__3_

On a polyethylene terephthalate backing that coincides with the same Adhesive layer is provided as described in Example 1,. a photosensitive layer is applied in a ratio of 50 g / m2 on the following composition:

10% aqueous gelatin solution 200 g

40% dispersion of colloidal poly- "'". ethylene as described in example t. 200 g

50% aqueous dispersion of photoconductive Zinc oxide (average particle size 0.17 µ) 320 g

60% aqueous dispersion of a green

Pigment produced by Farbwerke Hoechst, AG,

Frankfurt, under the name Heliogengrün C.K.-

Colanyl batter is put on the market 4Og

Glycerol ... 15 g

Ethanol _: - -. ■. -. ■ -. . 90 g

Water 100 g

The light-sensitive layer is dried ^{at 25 ° C.}

A conventional slide projector is used to apply to this layer a line art projected “This exposure

909SA7 / 0 86 6

BATH

takes place with a 250 watt lamp, from a distance of 1 meter from the photosensitive material. In this way, a tenfold linear enlargement of the original is obtained = IC after an exposure time of 90 min a positive enlargement of the original = the same material is exposed for 3 minutes through a developed silver halide negative knit copy in contact; using a carbon arc that works at 60 A and 3 42 volts (three-phase current) = the diameter of the carbon rods is 20 mm, results in a stable arc of 4 kW power, and is placed at a distance of 1 meter = after exposure, the material is treated as described in example 1, and a positive image of the original is obtained = the same material is exposed to min = in contact using a 900 watt mercury vapor lamp placed at a distance of 25 cm = after exposure, it is exposed like the previous one tet, and obtains the same result latter exposure = v / ill be carried out in a vacuum frame using the photosensitive material is cooled to a hollow metal plate, through which cold water flows (15 ⁰ CK

On a polyethylene-laminated paper backing with a An adhesive layer of the following composition is applied in a ratio of 30 g / m2 with a square meter weight of 120 g cuf:. '.

10% aqueous gelatin solution 200 g

40% aqueous polyethylene dispersion. ■ (example 1). 160 g

10% aqueous saponin solution. 20 g

50% aqueous solution of the sodium salt of the condensation product of oleic acid and methyl taurine 20 g

4% aqueous formaldehyde solution 10 g

Polyethylene glycol with an average molecular weight of 20 = 000 10 g

This layer is dried at 25 ° C =

90 9 847/0866 BADORIGlNAt. ...

On top of this layer you wear a 40 g / m2 1. Photosensitive layer composed of the following composition P-Uf:

10% aqueous gelatin solution 200 g

'' 40% aqueous polyethylene dispersion (Example 1) 200 g

50% aqueous dispersion of photo-

conductive zinc oxide (average particle

large 0.17 u) 300 g

Glycerol 15 g

Ethanol n90 ^

16% aqueous carbon black dispersion

(average particle size O, l u)

with 2% poly-I'-vinylpyrrolidone 50 g

This layer is dried at 25 ° C., exposed to light and treated as described in Example 1 = a positive image of the silver halide template »

Example _5

A 0.1 mm thick polyethylene terephthalate carrier, which is provided with an adhesive layer as described in Example 1, is coated with the following composition in a ratio of 50 q, m2:

10% aqueous gelatin solution _N 200 g

40% aqueous dispersion of polymethyl methacrylate particles with an average of 0.12 u Grosse and Durchschnittsmole- kulargewicht 1.30O ₀ OOO 200 g "

50% aqueous dispersion of photoconductive Zinc oxide (average particle size 0.17 u) 320 g

Glycerol 15 g

Ethanol '90 g

This layer is ^{dried at 30 °} C. The exposure and development are the same as those in Example 1, and analogous results are obtained

The same results are obtained if the 2OO g of polymethyl methacrylate are used by 374 g of a 22% dispersion of polystyrene with an average particle size of 0.13 u and an average molecular weight of 5COOO =

909-84770066 -

Example_l_ _6_

A 0.1 mm thick polyethylene terephthalate carrier that comes with

.a matted layer is provided, which is the main thing

from a urea-formaldehyde resin and crystalline

Silica is in a ratio of 15 q, m2 with

provided with an adhesive layer of the following composition:

aqueous polyethylene dispersion as described in
Example 1 19 g

aqueous dispersion of a copolymer

from butadiene and methyl methacrylate (50/50) 20 g

10% aqueous dispersion of colloidal silica. 50 g

Ethanol 50 g

Water 361 g

This layer is dried at 35 ° C »
On top of this layer is a 50 g / m2
photoconductive layer composed of the following composition
applied:

10% aqueous gelatin solution 200 g

aqueous dispersion mixture of the following
Pigments: 4 parts of L-ermanent Yellow HR Colanyl
Dough (trade name of a water-insoluble
yellow pigment brought on the market by
'Farbwerke Hoechst AG, Frankfurt), 20 parts
Fermanent Carmin FBB Colanyl paste (a water-insoluble purple pigment, marketed by Farbwer.ke Hoechst AG) and 26 parts
Heliogengrün CN Colanyl paste (water-insoluble green figment, applied to the skin
from Farbwerke Hoechst AG) 50 g

50% aqueous dispersion of photoconductive
• Zinc oxide with an average particle size
0.15 u) 300 g

2O% aqueous dispersion of 1olyethylene,
produced as described below 400 g

Ethanol. 90 g

Glycerol. '"- ■ 15 g

The material thus obtained is exposed for 15 minutes through a developed silver halide emulsion layer which
contains a negative silver image by adding a 15ÖÖ
Watt quartz iodine lamp used at a distance of 30 cm
is set up "

909847/0866

1120310

The material is treated for the exposure y \? ie tea greed in Example 1 »A sharp positive copy is obtained» The same results are obtained, internally the photp. Conductive Apply the composition to a thin aluminum sheet

Production of the latex: '. -

In an ⁿ 4QQO ml steel Pomfeenrohr F is a partially oxidized polyethylene .; Il exgeste3.lt

according to British patent specification 997 1.35,. . - ..

(Average molecular weight 7QQQ

crystalline melting point 125-13Q ⁹ C

Acid number 20- ^ 30). - 40 g

n-Hexadecyloxydecaoxyethylene ■ ^: 12.4 g

Water . 15Q g

The bomb tube is closed and rotated at 30-40 rpm and 180-210 ° C. for one hour in order to disperse the mixture. Let 4 ^ § B.Qmbianrqhr cool slowly & \ if temperature = D, ie efh ^a ltens Qi ^ Rsrsiqn is ready for use "

1 "■■ -" ■ -

A 0.1 mm thick, transparent, non-thermally conductive. ■ _; Polyethylene terephthalate carrier is in the ratio of V g _v 'm2 with an adhesive layer of the following. Composition coated:

2Q% aqueous dispersion of the f4isc "hpplympris; .ates of vinylidene chloride, I-tert-butyl acrylic and" itaconic acid (molar ratio 8.5 / 1Q / 2) ^; 12 g

. 40% aqueous dispersion of polyethylene with. an average particle size below OjI u and an average molecular weight '■> · ■■; between 15 »000 and 30 = 000 12 g

30% aqueous dispersion of colloidal Silica '' '12 g

Ethanol '-.''; 100 g ^:

VJasser 'Qß4 g

This adhesive layer is “dried at 30 ° C. = on top of it Adhesive layer is applied at a ratio of 40 g / m2 photosensitive layer composed of the following composition :,

§09847 / 0066

BATH

-.33 -

10% aqueous gelatin solution 100 g

20% aqueous dispersion of polyethylene, prepared as described below. 50 g

50% aqueous dispersion. photoconductive Zinc oxide, produced by the oxidation of zinc vapor and with an average particle size from 0.17 u 13 g

Glycerol 4g

Eosin 0.5 g

Water ■ 233 g

This layer is dried at 45 ° C »

The material thus obtained is for 1 minute through a developed photographic silver halide emulsion layer, which was applied to a transparent cellulose triacetate base and contains a negative silver line image, im Contact exposed = For exposure, a 500 watt incandescent lamp is used from a distance of 30 cm =

After the exposure, the light-sensitive layer is rubbed lightly with a soft sponge which is richly ^{moistened with water at 50 °} C. = a positive line copy of the original is obtained. "

Production of the polyethylene latex

In a 4000ml steel bomb tube you give:

partially oxidized polyethylene, manufactured according to British patent specification 997 135 (Average molecular weight 7000, crystalline melting point 125-130 ° C Acid number 26-30). 40 g

n-hexadecyloxydecaoxyethylene x 12.4 g

Water ■ 150 g

The bomb tube is closed and '1 hour at 30-40 Γ / min. and rotated 190-200 ° C to disperse the mixture. The sealed tube is then allowed to cool slowly to room temperature = the dispersion obtained is ready for use =

ExampleJ.el_Jj_

On a photosensitive material as described in Example 7, is projected using a conventional slide

9Ö98A7 / 0866 BATH

. projectors a negative line art with a 250 watt lamp from a distance of 1 meter. The enlargement is ten times. After 10 minutes of exposure it will be Material treated as described in Example 7. A positive, enlarged copy of the original is obtained.

Example__9

The photosensitive material vd_e described in example 7 is brought into contact with its photosensitive side with the printed side of a graphic template on paper backing o The material is 2 min »through its transparent pad in a flat contact copier, which contains 8 white fluorescent tubes of 20 watts, each are arranged under a glass plate of 45 cm χ 65 cm, and result in a 20 »000 lux light output, exposed»

Mach exposure, the material is rubbed with a cloth moistened with water at 35 ⁰ C soft sponge. The parts of the light-sensitive material that correspond to the image parts of the original are washed. A negative copy of the original is obtained.

At_sp_ie_l JO

A 0.1 mm thick polyethylene terephthalate carrier provided with an adhesive layer as described in Example 7 is coated with the following composition in a ratio of 60 g / m 2 ζ

10% aqueous gelatin solution 100 g

20% aqueous dispersion of polyethylene, prepared as described in Example 7 50 g

Glycerol 5 g

Aqueous carbon black dispersion containing 36 g carbon black (average size: 0.1 lu), 23 g water, 30 g ethylene glycol, and 6 g nonyaphenyl (diethylene oxide) , per 100 ml composition 50 g

contains water 350 g

Lead (II) oxide powder (yellow type) doped with

30 millionths of bismuth (specific surface

1.56 m2 / g) ■ '-. "-. ■ 40 g

909847/0666

Pas Bl ei (II) oxide - «- powder is dis- The layer is at. 30 ^? C dried «

The light-sensitive material obtained in this way is 10 min » duxch e | .ne developed Si4berh.alpgenidemulsionsschicht? the containing a negative line copy, under vacuum means a 1500 watt quartz iodine lamp, which is 30 cm above the Vacuum frame or, exposed in contact »

During the exposure, the material is ^{rubbed with a soft scratch pad 1} which is abundantly moistened with water at 20 ^° C., so that the unexposed parts are wiped away. A sharp, black positive relief image of the template is obtained, analogous results are obtained by mixing the lead (II) oxide powder with an equal amount of cadmium sulfide powder, red lead (Pb-O.), mercury (II) oxide powder, hangan (IV) oxide powder or phrom ί III) pxid-P u 1 replaces <■ The mean pond size of the filler particles is 1 to 3 5y.

A 0.1 mm thick Polyäthylenterephthalatr-Tragar, dpr with an adhesive layer is provided as described in example. 7, becomes in the ratio S / of 45 g / m2 with the following composition coated: _-- «, -

IQ% aqueous gelatin solution 200 g

20% aqueous dispersion of polyethylene, • prepared as described in Example 1 150 g

Eosin "* Q, 25 g

Glycerol. . ■ Cg

5% aqueous solution of isononylplieiiyldecaäthylenoxyäthanol 20 g

Water ■ -.-.- 72 g

The layer v / ill be dried at 30 ⁰ G. The material thus obtained is exposed for 3 minutes through a developed silver halide emulsion layer which is a negative line copy

contains, using a 1500 watt uuartz iodine lamp from a distance of 70 cm. 'oh the Beiich-

909847/0880

1S203S0

Afterwards, the material is treated as described in Example 7 * One positive copy is obtained o Analogous results can be achieved if the eosin is replaced by an equal amount .. Acridine Orange R, known as Basic Orange 14 (CJ, 46 .- »© 05) the following formula is replaced i "■

Cl

Example 1_2

Dispersions with the following respective compositions are poured onto various strips of a subs tarier teia cellulose triacetate carrier ^. :

Composition

en trainer alized ε water ϊ a tr i'umhe3tame taphospha t eosin {C »I. 45 »3wÖ)

15% solution of gelatin in demineralized water

£ 0% aqueous solution of;. οIySthy 1 en with a -particle size-S-JO of O, i u and a D u rch s'chni t tsrno 1 eteu 1 ar of 30 "000

Glycerol _:

12.5% solution of

in "demineralized" water

60 ml

• 2 g

2 g

GO .ml

2 © ml

■ 6 g

1 ml

ml. 2 g
G
ml

** Q rol

SO iml

-G

'40 aril

S.

ml 2 g -2 g

© 0 ml

1 ml I.

These compositions are. "Shed in such a V, that the thickness of erlhaltenen after drying amounts to 40 u ^ ßegistrierschichten-

Bie Eegistriermaterialien be with now.! Your £ laughing a transpareiate Strichvorlag e-placed 3O min * by means of feelichtet eisier r'hilips i © IR 2/25

9098 ^ 7/0866 '

bath

Lamp from a distance of 30 cmο Then the exposed photosensitive layers with water

.35 ° C treated so that the unexposed parts of the Registration layer to be removed «

The sensitivity of the compositions A, B, C bswo D formed registration layers i> -t the highest in composition D, and decreased over C and B after

Example 12 is repeated with the difference, however, that the registration layer is not 2 g of eosin, but 12 g contains yellow lead (II) oxide, and that the sodium hexametaphosphate and the lead (II) oxide are ball milled in demineralized water for 1 hour before the others Ingredients were added »

After 5 minutes of image-wise exposure using a Fhilips HPR 125 lamp and a treatment with water at 35 ° C, '..' only order the non-exposed parts of the different Registration layers removed =

The sensitivity of the registration layers associated with the Compositions A, B, C and »D, respectively, increased from A through B and C to D. .

A 0.1 mm thick, transparent, non-heat conductive one Polyethylene terephthalate carrier is used in the ratio of IG g / m2 with an adhesive layer of the following composition overdrawn :

20% aqueous dispersion of the copolymer from vinylidene chloride, Μ — tert = butyl acrylamide and itaconic acid (molar ratio S8 / 10/2) 12 g

40% aqueous dispersion of polyethylene with a particle size below 0.1 u.

and an average molecular weight; -. between 15,000 and 30,000 -. 12 g

909847/086 6, ''' ^ΊίΆ

30% aqueous dispersion of colloidal silica _; earth 12 g

Ethanol "100 g

Water . ■ ■ '£ 64 g

This adhesive layer is then dried at 30 ° C

The adhesive layer becomes light-sensitive in a ratio of 100 a / m2 Layer applied from the following composition:

10% aqueous gelatin solution. ■ 200 g

20% aqueous dispersion of polyethylene, prepared as described below 100 g

50% aqueous dispersion of photoconductive zinc oxide made by oxidation of zinc vapor; the zinc oxide grains have an average size of 0.17 and 50 g

Glycerol 4g

5% aqueous solution of isooctylphenyl (ethylene oxide) '10 g

Carbon black dispersion, the 35 g carbon black, 23 g water, 30 g ethylene glycol, and 6 g nonylphenyl poly (ethylene oxide) per 100 ml of composition contains 10 g

The layer is dried at 35 ⁰ C »The thus erhal'tene material is 10 minutes" by a developed photographic silver halide emulsion layer containing a negative "Halbtonsilberbild on a transparent cellulose triacetate support, exposed in the contact" In the exposure using a flat contact exposure device , which contains 0 white fluorescent tubes of 20 watts, each arranged behind a glass plate of 45 cm χ 60 cm, and a luminous efficiency of 20 = 000 lux =. During the exposure, the silver image-containing layer is in close contact with the polyethylene terephthalate - Carrier of the light-sensitive layer »■.-..-

After the exposure, the photosensitive layer is carefully rubbed with a soft sponge that contains plenty of Water · · · is moistened at 50 ° C »A positive result is obtained Halftone copy of the original »

909847/0868

1S2036Ö

buckets 4Ö0Ö anl steel Sombenrohr gives roan:

partially oxidized polyethylene., manufactured aaach-the British patent specification

IBS ί average molecular weight - crystalline melting point ϊ 125-13O ^o C

r 26-3Ό) ^: "': 40 g

12.4

'. ISO g

wiwä closed and at 19O-2OO ^Ö C one at 3®-4® t ^ Miw .. 'rotated into the mixture zia disper »- Then the tube is slowly allowed to reach room temperature. The dispersion obtained is ready for use«

Bin I O ₉ mm thick Polyathylenterephthalat-frager, which is provided with Giner Uaftsdiicht in example in a ratio of 40 g / as ^described: m2 with the following

overdrawn : ·

aqueous gel a tine solution 100 g

£ & %%.% * & Aqueous Polyäthylendispersioin, produced: as described in Example 'M 50 g

SO 'Sfciije aqueous dispersion of photoconductive em 2iii | coxiiiä, JjearigäcstiGi 11 duircih. Oxidation of

, with xaerchial particles- of 0.17 y ■. 13 g

- ■ _ ■ 4 g

0.5 g 233 g

ÖIE layer is dried at ^a C 45 * - The -is thus obtained was applying a minute through eiiic developed photo- Silberhalogeiiidetnulsionsschicht that -a negative eimttaitlfc "Wiiad a ^ af ei.nen tr anspar en th gel Iur, lim exposed Kömtakt , you vcscwcaadet a 500 ¹ betting incandescent lamp <from an animal Era;! nu * rag 30 ctn "i'ach exposure ^ is the material

vjie described in Example 1-4 »iflan receives a positive copy "." '■ - "

BAD qßlQlfcjALj

.— 40 -

B oispi e 1_16_

On the photosensitive material described in the example 15, is made using a standard slide projector · »a Line artwork projected with a 250 watt lamp from a distance of 1 meter, which results in a tenfold magnification « After a 10 minute exposure, the material is processed as described in Example 14 positive enlarged copy of the template »

BOi _{- game} JT? :. ": ·.""■■■

The photosensitive material described in Example 15 i.drd brought into contact with its light-sensitive layer with the written side of a graphic template on paper backing

The material is exposed for 2 minutes through its back in a flat contact exposure device that contains 3 glass _tubes: fluorescent tubes of 20 watts each, each containing. are arranged on a glass plate of 45 cm χ 65 cm, and result in a light output of 20,000 lux «

1: After the exposure, the material is ^{rubbed with a soft sponge moistened with water at 35 °} C. "The parts of the original with the images over a". Some parts of the photosensitive material are discarded / ashed = obtained

a negative copy of the submission ,,. -. ■

A 0.1 mm thick Polyäthylehtejrephthalat carrier is im Verholtr * is from 1-R g / m2 with an adhesive layer dor the following composition;

20% aqueous dispersion of the copolymer from vinylidene chloride j li-terto-butyl acrylamide and Itaconic acid (molar ratio 83/10/2) ". 12 g

4O% Ige aqueous dispersion of polyethylene with a particle size below 0.1 u and one Average molecular weight between 15-000 and ..3Q "OpO. ■. ■ 12 g

30% aqueous dispersion of colloidal silica ■. " earth / 12 g

903847/0866 BAD

. Ethanol 100 g

Water - 864 g

This adhesive layer is dried at 30 ° C "Then one carries in a ratio of 40 g / m2, a photosensitive layer of the 'following composition ι

20% aqueous dispersion of polyethylene, prepared as described below 50 g

50% aqueous dispersion of photoconductive zinc oxide made by the oxidation of Zinc vapor (the zinc oxide grains have an average grain size of 0.17 µ) 50 g

Aqueous carbon black dispersion containing 36 g carbon black, 23 g water, 30 g ethylene glycol and 6 g nonylphenyl poly (ethylene oxide) per 100 ml composition 50 g

Glycerol to ^< ? ^contains .4g

Water . 240 g

The layer is dried at 35 ° C. The resulting photosensitive Material is developed for 10 min., Through a silver halide emulsion layer, which has a negative halftone image contains, in vacuum in contact from a distance of 30 cm above the vacuum frame using a 1500 Watt quartz iodine lamp exposed into a reflector is mounted »

After exposure, the material is rubbed with a soft sponge, which is ^{kept moist with water at 20 °} C. This wipes away the unexposed parts, and a black relief image is obtained =

Manufacture of the_polyethylene latex

In a 4000 ml steel bomb tube you give:

partially oxidized polyethylene made according to British Patent 997-135 (Average molecular weight: 7000 crystalline melting point: 125-130 ° C acid number ■: 26-30) 40 g

n-hexadecyloxydecaoxyethylene 12.4 g

Water 150 g

The bomb tube is closed and at 19O-2OO ° C a, Hour at 30-40 rpm "rotates to disperse the mixture" Then let the pipe slowly come to room temperature.

909847/0866
BAD LOCATION ^ iMt ^ ^

cool down temperature ^
done..

The dispersion obtained is usable

Example _1_9

Substrate 0.1 mm thick cellulose acetate strips are coated separately in a ratio of 50 g / m 2 with one of the following compositions. The amounts given here are amounts by weight in grams.

10% aqueous Kase'in-
solution with Na _? CO "
adjusted to pH 9
became ,
340
250
170
100
70
50 l'Olymer dispersion
A. water • 0
7th
42
82
9 7
107 340
250
170
100
70
50 05
125
170
200
215
225 0
7th
42
82
97
107 Polymer dispersion
B. 340
250
170
100
70
50 35
125
170
200
215
225 0
7th
42
82
97
107 J. Polymer dispersion
C. Cl
C3
C4
C5
C6 35
125
170
200
215
225 Al
A2
A3
A4
AS '
A6 Bl
B2
B3
B4
B5
B6

909847/0366 ORIGINAL BATHROOM

The polymer dispersion A is a 20% colloidal dispersion Polyethylene with a particle size below 0.1 u and an average molecular weight between 15,000 and 30 = OOO. The polyethylene was "made by." Emulsion polymerization produced »

The polymer dispersion E-. Is a 20% dispersion coitoid foliate ,. which are made in the following way was * given in a 4000 ml steel bomb tube a mixture consisting of partially oxidized polyethylene, Made according to the British patent specification 997 135, together with a dispersant * This Mixture has the following composition; ;

Polyethylene (Average Molecular Weight 7 "Q00 - More Crystalline Melting point 125-130 "C - acid number 26-30) 40 g

. n-hexadecyldecaoxyethylene 12.4. G

Water 150 g

BQrob & irohr is closed, and at 190-20O ⁰ C one

at 30-4Q rpm, * rotates around the ethylene dispersing sau. Then you let the pipe open slowly Cool room temperature, whereupon the resulting dispersion is ready to use.

Polyraerdispersion C is a 40% strength by weight vc'iEsrige pQlyroethYlmethacrylatclispersiQn, which under the -araen h 400 from Polyvinyl Chenulnc- ₁ Wilmington, Del. vsii. , on "marketed: this dispersion v.-ird" is diluted 20% by weight solids,

Eu each of 21usemmensetzung, s Al, A2, etc .. four to 4 g of glycerol, 4 g of potassium bromide and 100 g of Q _t 25% igo aqueous Erythrosinlosung zugesc-tst "The obtained photosensitive layers are at 25" C dried the so; obtained photosensitive materials are, exposed a developed SilberhalogenidemvUsio.nsschicht with bucket negative pulse in vacuo copy m contact with a 1500 Watt is quarts j odirmpe verv.-oKdet that

BAD ORfGINAU

is mounted at a distance of 65 cm above the vacuum frame, and 24 "000 Lux delivers"

After the exposure of the different registration layers, the latter are ^{rubbed with a soft sponge richly moistened with water at 20 °} C. The non-exposed or underexposed parts are wiped away and a relief image is obtained are necessary to achieve image differentiation in each of the registration layers =

1 2 11th Lux" Sec. 6th 4th 5 , 00 6th , 43: >> 1ΟΟ 29 1 3 , 90 ί . 3 , 36 - / Λ. >> 1ΟΟ 45 11th , 5 2 , 43 , 55 0 B. >> 1ΟΟ )) 1ΟΟ ■ 0 , 60
- 4th 2 C. , 5 3

A subbed cellulose triacetate pad 0.1 mm thick \. is in the ratio of 50 g / m2 with the following composition coated:

10% aqueous casein solution

100 g

20% aqueous dibutylphthalate dispersion

200 g 4 g

4 g € 4 g 100 g

Glycerol

Potassium bromide

water

0.20% aqueous solution of eosin The layer is dried at 20 ⁰ C, exposed in Beispie.l 1 as described and by Wegwaschbehandlüng It developed practically brauchbcre results are obtained. The dispersion of the dibutyl phthalate is prepared by mixing the following ingredients for 10 minutes at a speed of 6000 rpm in an Ultra-Turrax mixer, brought to the market by J ^ nke C. Kunkel K, G., VJ, Germany;

909847/0866

bath

Dibutyl phthalate. . 40 g

Water 160 g

Isooctylphenylpoly (ethylene oxide) _Q ^ _n ^ g

Nonylphenylpoly (ethylene oxide) _Q -i _n 3 9

The same results are obtained by substituting dibutyl phthalate with paraffin oil or carnauba wax replaced,

Japanese paper with a basis weight of 14 g / rn2 is impregnated with the following dispersion:

10% aqueous casein solution 100 g 20% aqueous polymer dispersion B

of example 19 200 g

Glycerol 4 g

Potassium bromide 4 g

0.25% aqueous erythrosine solution IQO g Compartment for the drying of this Japanese paper, there are 12 g of pesticide per m2 Min. In contact through a developed silver halide emulsion layer with a 1500 watt quartz iodine lamp eus a distance of 65 cm after a positive Line image exposed ,,

^{After exposure, the paper is immersed in water at 20 °} C. while gently rubbing with a soft sponge. This treatment rinses the unexposed parts away, and after drying, a positive stencil of the original is obtained.

0 9 8 4 7/0866

Claims (1)

Expectations / lJ Procedure for registering or »reproducing Information characterized in that it is the following Levels includes: ' a) the information-based exposure to be more effective electromagnetic radiation of a recording material, the at least one water-permeable Contains registration layer, which consists essentially of one or more photoconductive compounds and dispersed finely divided material containing hydrophobic particles that are hydrophobic Contain or consist of a substance, the photoconductive compounds and the dispersed hydrophobic particles are present in the registration layer in such an amount that this registration layer without any significant informational increase in temperature on the sufficiently irradiated Make a decrease in water permeability, and b) developing the latent image produced by the penetration of a liquid into the non-irradiated one or insufficiently irradiated areas of the registration layer, resulting in a visible change in Conformity with these sites, or by removing the non-irradiated or inadequate irradiated areas of the registration layer " 2., The method according to / ^ nspruch 1, characterized in that the dispersed hydrophobic particles are for the most part so close to each other ... that neighboring particles can coagulate at any point on the registration layer if the layer is sufficiently exposed to the electromagnetic radiation at this point, to which the photoconductive material is sensitive. 90984 7/0066 Μ » 3. The method according to /.nspruch 1, characterized in that the registration layer contains the hydrophobic particles
a continuous i-hase of a hydrophilic binder contains = '! ·. The method according to claim 3, characterized in that the registration layer these hydrophobic particles in
dispersed form in a hydrophilic binder
contains in a weight ratio of at least
1/1, and that the dispersed hydrophobic particles
are encased in this registration layer by a finely divided photoconductive substance » 5. The method according to claim 1, characterized in that the hydrophobic particles wholly or partially, e auc
consist of hydrophobic thermoplastic substances «. 6. The method according to any one of claims 1-5, characterized in that the hydrophobic particles wholly or for
Mainly consist of a hydrophobic thermoplastic polymeric material., 7. The method according to claim 6, characterized in that the hydrophobic particles by a dispersant
for aqueous media are dispersed = . . "-. The method according to claim 6, characterized in that the film particles are latex particles * 9 * Method according to one of the claims 3 - Z, thereby identified. shows that, the hydrophilic binder consists of at least one proteinaceous binder., 10.Verfahren according to any one of claims 1-9, characterized ^ that the photoconductive substance is a photoconductive one Metal or a photoconductive metal compound that is a Group 6B element of the Deriodic System contains o. 9 0980/0866
BADORfGiNAL 11. The method according to any one of claims 1-9, characterized in that the photoconductive compound'eine organic photoconductive compound. " 12. The method according to claim 11, characterized in that the photoconductive compound is spectrally sensitizing Properties versus photoconductive Has zinc oxide. 13. The method according to claim 11, characterized. that the photoconductive compound is a photoreducible Dye is. 14. The method according to claim 13, characterized in that that the photo-reducible dye is a photo-reducible xanthene, acridine or thiazine dye is. 15. The method according to any one of claims 13-14, characterized in that that the photoreducible dye is a fluorescein dye. 16. The method according to any one of the preceding claims, characterized in that the registration layer and / or an adjacent water-permeable layer a pigment, metal particles, a dye, reaction components to form a dye, a catalyst for a color reaction, a plasticizer, Development nuclei for carrying out the silver complex complex diffusion transfer process, or contains other photosensitive substances than photosensitive semiconductor substances. 17 »Method according to one of the preceding claims, characterized in that the registration layer contains a water-attracting substance. 909847/0 8.6 6. 18ο Method according to claim 17, characterized in that that the registration layer; a hygroscopic polyol or a hygroscopic ionic compound contains » ο The method according to any one of claims 1-18, characterized characterized in that the intensity of the information-wise exposure is such that it does not thermal softening effects of the causes thermoplastic hydrophobic particles present in the registration layer = 2Oo method according to any one of claims 1-19, characterized in that the ± nformation-wise exposed Registration layer with an aqueous solution of a dye, a dye-forming component, a Solution of a catalyst for the production of a dye, or a solution of a bleaching agent is treated » 21ο The method according to any one of claims 1 to 19, characterized marked that the non-irradiated or Inadequately irradiated parts of the registration layer are broken down or removed by means of an aqueous liquid. to be washed away. 22ο Photosensitive recording material, characterized in that it has at least one water-permeable Contains registration layer whose water permeability due to exposure to active electromagnetic. Radiation can be reduced without the temperature increasing significantly, and which layer essentially of one or more finely divided inorganic and / or organic photoconductive Substances and hydrophobic particles in a continuous phase of a hydrophilic binder in one There is a weight ratio of at least 1/1. 909847/0866 SO 23o photosensitive recording material according to claim 22, characterized in that the photosensitive Substance is a photoconductive metal or metal compound that is a Group 6B element of the periodic table contains » 24ο Photosensitive recording material according to claim 23, characterized in that the photoconductive metal compound is photoconductive zinc oxide, titanium (IV) oxide, lead (II) oxide, red lead, chromium (III) oxide or Is cadmium sulfide. ο Photosensitive recording material according to claim 22, characterized in that the hydrophobic thermoplastic particles are hydrophobic thermoplastic polymer textiles = ο Photosensitive registration material according to claim 25, characterized in that the hydrophobic particles by means of a dispersant for aqueous Media are dispersed » 27- Photosensitive recording material according to claim 25, characterized in that the polymer textiles are used as latex particles » 28. Photosensitive registration material according to claim 22, characterized in that the hydrophilic binder is a proteinaceous binder. 29ο Photosensitive recording material according to claim 22, characterized in that the registration layer contains a hydrophilic compound. 30o photosensitive recording material according to claim 29, characterized in that the registration layer is a water-attracting polyol or a contains water-attracting ionic compound. " " 909847/0866 8ADORfGINAL Si 31. Photosensitive recording material according to one of the Claims 22-30, characterized in that the inorganic photoconductive compound in the registration layer in a weight ratio of 1/3 to 5 ^ 3 in terms of the total amount of dispersed hydrophobic Particle is present » 32. Photosensitive recording material according to one of the Claims 22-31, characterized in that the inorganic photoconductive substances with xanthene, Thiazine or acridine dyes are spectrally sensitive are bilized. 33. Photosensitive recording material, characterized in that it has at least one water-permeable Registration layer contains whose water permeability by exposure to active electromagnetic Radiation can be reduced without the temperature increasing significantly, and which Layer consisting essentially of hydrophobic particles in a continuous phase of a hydrophilic binder in a weight ratio of at least 1/1, and at least one, finely divided organic photo-reducible dye, which is unable to protect from light by a thiolated gelatin, but is probably able to be reduced by the sulfhydryl groups of the thio- lated gelatin to be reduced when served through Light is excited. . 34. Photosensitive registration material according to claim 33, characterized in that the photo-reducible Dye a photoreducible fluorescein dye is. 35. A photosensitive Registriermateriai according to claim 34 characterized in j - that _t the photoreduzi ER- bare dye eosin, erythrosine *, acridine orange R, or is methylene blue = 909847/0866