DE2231815A1 - Recording corpuscular radiation - using non-photosensitive supported copying layer - Google Patents

Abstract

Material for recording corpuscular radiation consists of a support a non-photosensitive but corpuscular radiation-sensitive copying layer contg., as main component, a monomeric or polymeric org. material having >150 mol. wt., pref. an epoxy-, maleate- or acetal resin, a polyamide, styrene- or acrylate polymer, a polyester, polyvinyl ester, an HCHO condensate resin, a cellulose ether or - ester, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl phosphonic acid, gelatine, casein, or albumin or a >=10C fatty acid. Recording material is irradiated image-wise with electrons and image formed is developed with water or with an aq. soln. Uses include prodn. of offset printing blocks for lithography, printed circuits and screen printing blocks.

Description

Description of the registration of the material and method of recording of corpuscular rays The invention relates to a material and method for recording of corpuscular beams, especially for the production of offset printing forms.

It is known to apply light-sensitive photoresist layers on workpieces, z. B. semiconductor wafers to be selectively irradiated with electrons (e.g. DOS 1 614 635 and GB 1 121 688). After the irradiation, those hit by the electrons are Parts of the resist removed by developing, and further processing takes place according to the usual procedures in semiconductor technology.

It is also known to produce polymer layers which are insensitive to UV light to irradiate etched images or etch-resistant masks with electrons. But are these are not very suitable for the production of planographic printing forms because they are, for example before and / or after the irradiation, preferably baked in, which is very time-consuming must (DOS 1 696 489, DOS 1 622 285, GB 1 057 947) and / or with organic solvents must be developed in an ecologically disadvantageous manner.

The object of the invention was to provide a recording material and method for electron beams, which is versatile and a development allowed with aqueous solutions.

The invention relates to a recording material made from a carrier and one that is non-photosensitive and sensitive to corpuscular rays Copy layer.

The recording material is characterized in that the copying layer with a monomeric or polymeric organic substance as an essential component a molecular weight above about 150 contains.

The copying layer preferably contains the polymeric organic substance an epoxy resin, maleic resin, acetal resin, polyamide, styrene polymer, acrylic ester polymer, a polyester, polyvinyl ester, a formaldehyde condensation resin, a cellulose ether, Cellulose ester, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylphosphonic acid, Gelatin, casein or albumin.

As monomeric organic substances there are mainly saturated or unsaturated fatty acids with at least 10 carbon atoms are possible according to the invention a method for image recording by means of electron beams is also proposed, in which a recording material of the type described above is imagewise with electrons irradiated and developed with water or an aqueous solution.

The material according to the invention is particularly suitable for manufacture of offset printing plates and is therefore preferably used with a lithographic support Mistake.

A wide variety of materials are used as lithographic printing media such as paper, zinc, magnesium, aluminum, chrome, copper, brass, steel and multi-metal or plastic films are suitable. Preferably mechanically, chemically or with the aid roughened and / or anodized aluminum is used for the electrical current, this is advantageous before sensitization with phosphonic acids or derivatives of phosphonic acids according to the German patent specification 1 160 733, with alkali silicate according to the German Patent 907 147, with zirconium or titanium hexahalides according to the German Auslegeschriften 1 183 919 and 1 192 666 or with monomeric and / or polymeric carboxylic acids has been pretreated.

As mentioned above, the light-insensitive copying layers are those suitable consisting exclusively or predominantly of monomeric or polymeric organic Fabrics exist, e.g. B. saturated and / or unsaturated fatty acids, novolaks, epoxy resins, Maleinate resins, polyvinyl acetals, polyesters, urea or melamine resins, resoles, Polyvinyl phosphonic acid, methozymethyl perlon, polystyrene, polyvinyl alcohol, carboxymethyl cellulose, Polyvinylpyrrolidone or from natural substances such as gelatin, shellac, casein, albumin, Rosin. Mixtures of these can also be used. The layers can be added dyes, plasticizers and wetting agents are added in small amounts.

As a solvent for the fabrikatorisqhe production of the layers water-insoluble substances result in liquids generally known as good solvents in question such as alcohols, amides and ketones; Ethylene glycol monomethyl ethers are preferred Ethylene glycol monoethyl ether, dimethylformamide, diacetone alcohol and butyrolactone.

In order to achieve even layers, organic Solvent these often also ethers and / or esters such as dioxane, tetrahydrofuran, Butyl acetate and ethylene glycol methyl ether acetate were added. For those soluble in water Substances are of course also suitable for water or water-alcohol mixtures.

For the production of the copy material according to the invention for the production of printing plates the substances mentioned above in one or more of the solvents mentioned dissolved, applied to a suitable layer support, and the applied solution is dried.

The coating can be applied by centrifuging, spraying, dipping or applying take place by means of rollers or with the aid of a liquid film and aligns itself also according to the properties of the material to be coated.

The coated print carriers are charged with electrons in a charge density from about 10 8 to 10 2 coul./cm2 at an accelerating voltage of about 5 to 50 kV irradiated. Times are depending on the sensitivity of the layers used from 0.005 to 10 seconds per 2 cm distance at beam currents from 1 / uA to 1000 / um needed. Since the layers are insensitive to light, also to UV light, the irradiation can take place in daylight. The electron beam becomes appropriate controlled by means of a predetermined programmed line and / or grid movement.

Which reactions when the beam hits the layer depending on of the energy of the ray taking place is still unexplained. In the below described For example, the layer is either insoluble at the points struck by the beam or soluble. It can be assumed that in the former case a polymerization or Crosslinking, in the second case a depolymerization or an oxidative introduction by solubilizing groups. Whether a decrease or an increase in solubility occurs depends on the composition of the layer and possibly also on the exposure dose and the developer. The layer behavior can be determined in each individual case easily determined by simple preliminary tests. For the production of planographic printing forms it is preferred to work in such a way that a reduction in solubility or layer hardening occurs because in this case after the development and inking of the lithographic Printing form with bold color a positive image is obtained.

As a developer are surprisingly both initially water-soluble as well as water-insoluble layers water or alkaline or acidic aqueous solutions suitable, which contain inorganic salts, weak acids and possibly wetting agents. Are useful also aqueous solutions, up to about a third their volume lower aliphatic alcohols, e.g. B.

Propanol, or other water-miscible organic solvents contain.

The non-photosensitive copy material has a very good one Can be stored even at higher temperatures and water contents in the air and in the Light. It also shows good developer resistance while the non-image areas the copy layer quickly and cleanly thanks to the aqueous, non-flammable developer have it removed. The printing forms obtained provide a good number of printed copies.

By varying the composition of the layers and the electron beam conditions one can determine the properties of the copy materials for special purposes, as used, for example, for automatic printing form production in so-called copier lines are necessary to control in wide areas.

The process according to the invention is primarily used for printing forms manufactured for planographic printing. The copy materials can also be used after developing by etching in relief or intaglio printing forms or in offset multi-metal printing forms be transferred. The copying compositions according to the invention can also be used for production copied circuits, screen printing forms, tanning images and the like. Can be used.

The following examples illustrate preferred embodiments. Percentages are, unless otherwise specified, percentages by weight. As part by weight (Gt.) put 1 g; if 1 com is selected as the volume part (Vt).

Example 1 An aluminum plate 0.3 mm thick is made by brushing mechanically roughened and 3 minutes at 700 C in 20% trisodium phosphate solution dipped, rinsed with water, treated with 70% nitric acid for 15 seconds and after rinsing again with warm water for 3 minutes in 2% sodium silicate solution Pretreated at 850 C, rinsed with water and dried.

This pretreated Al plate is treated with a solution of 5 pbw. of Novolaks Alnovol PN 429 in 75 Gt.

Ethylene glycol monomethyl ether and 20 pbw, butyl acetate coated and dried.

The non-light-sensitive coated aluminum plate that can be stored for years is now with medium-fast electrons with energies around 10-15 kV in a high vacuum (approx 10 5 Torr) irradiated imagewise. The beam current is 20 µm and the deflection speed 0.5 sec / 2 cm path length. With the same success you can choose 100, uA and 0.05 sec / 2 cm.

The plate irradiated in this way is then described in the German patent specification 1 200 133 type described with an aqueous solution containing 5.0% sodium metasilicate Contains ~ 9 water, 3.0% trisodium phosphate ~ 12 water and 0.4% monosodium phosphate, wiped over. The areas not hit by the electron beam are the Novolak layer peeled off and the hydrophilic aluminum exposed. To the one from the beam The novolak layer is completely insoluble compared to the one used Developer, The following resins or Mixtures of these are applied to aluminum, irradiated and developed: an epoxy resin composed of bisphenol A and epichlorohydrin having an epoxy equivalent weight from 450-500, a styrene Maleic anhydride copolymer with with an acid number of 180 and an average molecular weight of 20,000, a non-plasticized one Melamine resin (Resamin 533 F), an oil-free alkyd resin (melting range 75-850 C, acid number 180-200), polystyrene LG, rosin, shellac and casein.

If instead of the aqueous alkaline developer described above an acidic developer of the composition 5.0 pbw. Magnesium sulfate 0.5 pbw nonionic Wetting agent 20.0 pbw Propanol 75.0 pbw If water is used, one can use the Al carrier with coat and irradiate the following resins: Hardenable phenol-formaldehyde resin (Phenodur 373 U), polyvinyl acetate with an average molecular weight of 110,000, vinyl acetate-crotonic acid copolymer (Mowilith Ct 30), polyester made from 2.5 mol of adipic acid, 0.5 mol of phthalic acid and 4 mol Triol or polyvinyl formal (Formvar 12/85).

Example 2 A bright-rolled Al roll is made mechanically in the strip process roughened by graining and with a 4% solution of polyvinylpyrrolidone in Water coated and dried.

The non-photosensitive material is cut into pieces and, as described in Example 1, irradiated imagewise with medium-fast electrons, but with a deflection speed of 5 sec / 2 cm wavelength. After the irradiation the aluminum foil is wiped over with pure water, which is not exposed to the rays affected parts of the layer are detached.

The affected parts can then be colored with bold paint.

Equally good results are obtained if one uses instead of polyvinylpyrrolidone 0.5% gelatin, 0.5% carboxymethyl cellulose or 5% polyvinyl alcohol with the K value 50 and 12% unsaponified vinyl acetate units dissolved in water as a coating solution used.

Example 3 An anodized Al plate is made with a 5% solution coated by methoxymethyl perlon in ethanol and with that described in Example 1 Apparatus irradiated imagewise, but with a deflection speed of 10 sec / 2 cm path length. When developing with the acidic developer described in Example 1 the layer is peeled off at the irradiated areas, the non-irradiated areas are oleophilic and are colored with bold paint.

Images of the same quality are obtained by using ealresat with the maleinate resin 313 or coated with polybutyl methacrylate in ethylene glycol monomethyl ether and just like developed above, or if one coated with nitrocellulose and with a solution containing 1.5% sodium metasilicate and 0.3% polyglycol.

Example 4 A waterproof paper printing film is made with 0.1% oleic acid coated in ethylene glycol monomethyl ether and imagewise with the electron beam irradiated.

The beam current is 100 µm and the deflection speed 5 sec / 2 cm path length. When developing with pure water, the layer is applied to the detached from irradiated areas, it remains in the non-irradiated areas, is oleophilic and is colored with bold paint.

Example 5 A hydrophilized polyester printing film is made with 0.5% Stearic acid solution coated in ethylene glycol monomethyl ether and with the electron beam with a deflection speed of 10 sec, 12 cm path length at a beam current strength of 20, uA irradiated. When developing with the alkaline mentioned in Example 1 Developer, the layer is removed from the non-irradiated areas. The irradiated Areas are oleophilic and are colored.

Example 6 An anodized Al plate is coated with a 0.01% lauric acid solution coated in ethylene glycol monomethyl ether and with the electron beam with the Deflection speed of 5 sec / 2 cm path length a beam current of 100 / µm irradiated, in the development with the alkaline mentioned in Example 1 Developer, the layer is removed from the non-irradiated areas. When coloring a bold color gives an oleophilic image on a hydrophilic base.

With equal success, stearic acid can be used instead of lauric acid Coating can be used.

Example 7 A mechanically grained Al plate is made by dipping in 800 C hot 0.4% aqueous polyvinylphosphonic acid coated, dried and irradiated imagewise with an electron beam. The beam has a current strength of sec of 41uA and the deflection speed of 5 ehe / 2 cm path length. Then with 2% aqueous orthophosphoric acid developed, with the non-irradiated areas be replaced.

Claims (3)

Claims 1. Recording material consisting of one support and one non-light sensitive copy layer sensitive to corpuscular rays, thereby characterized in that the copying layer is a monomeric component as an essential component or polymeric organic matter having a molecular weight above about 150. 2. Recording material according to claim 1, characterized in that that the copying layer is an epoxy resin, maleinate resin, as a polymeric organic substance, Acetal resin, polyamide, styrene polymer, acrylic ester polymer, a polyester, Polyvinyl ester, a formaldehyde condensation resin, a cellulose ether, cellulose ester, Polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl phosphonic acid, gelatin, casein or contains albumin. 3. Recording material according to claim 1, characterized in that that the copying layer as a monomeric organic substance is a fatty acid with at least Contains 10 carbon atoms. 4, Electron Beam Image Recording Method, at a recording material consisting of a carrier and a non-light-sensitive, to corpuscular radiation sensitive layer irradiated imagewise with electrons and is developed with a liquid, characterized in that a material used, whose copying layer is a monomeric or essential component contains polymeric organic substance with a molecular weight above about 150, and that development is carried out with water or an aqueous solution.