JPS5995533A - Manufacture of photosensitive layer based on polyamide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing photosensitive layers based on polyamides, which are suitable for producing photopolymer printing plates or relief plates. The method comprises at least one polyamide soluble or at least dispersible in a solvent, said polyamide and an optically compatible monomer and/or
or oligomers (both one type, at least one photoN8 initiator and optionally other customary additives) are mixed homogeneously with each other and the resulting homogeneous photopolymerizable mixture is advantageously used. The photosensitive layer is formed by simultaneously applying it to a dimensionally stable support and molding it.

For the production of photopolymer printing plates and relief plates, it is known to imagewise expose a photosensitive layer fixed to a dimensionally stable support and to subsequently remove the non-exposed layer parts (e.g. French Patent No. 1., 520.856
Specification and Federal Republic of Toin Patent Application Publication No. 2202
(Refer to Book No. 357, Mei #I). Polyamides have proven to be particularly advantageous as base materials for the photosensitive layer due to the high abrasion resistance of the printing plates obtained. According to customary known methods, the photosensitive layer is prepared by mixing the polyamide with the other photosensitive layer components (monomers, photonic initiators and optionally customary additives) in a bath liquid in a mutually homogeneous manner. It is produced by mixing and shaping the mixture by casting, centrifugal casting, pressing, extrusion, calendering, etc. to form a photosensitive layer, which is subsequently or simultaneously applied to a dimensionally stable support. The disadvantages of polyamide-based layers produced according to known methods are:
For use in the newspaper printing field, exposure times are too long, which must be partially shortened by additional measures, such as pre-exposure.

The object of the present invention is to provide a photosensitive layer which is suitable for producing photopolymerizable printing plates and relief plates and which, without the use of additional measures, is superior to photosensitive layers of the same type produced on the basis of previously known methods. It was also an object to produce photosensitive layers based on polyamide in a simple and advantageous manner, which can be worked with extremely short exposure times.

Surprisingly, this problem is solved by molding a bath-molten mixture consisting of the components of the MS layer to form a photosensitive layer, under a sufficient mJ block, and at the same time with motion and/or post-mixing. It has been found that the problem can be solved by short-term exposure to temperatures 20-80°C higher than the softening temperature of the mixture.1-.

The subject of the present invention is therefore a DJ bath or at least one dispersible polyamide (with at least one light weight @possible low molecular weight ethylenic olefinic phase) which is compatible with said polyamide. A small amount of additives (all 1 type, at least 1 tub of photopolymerization initiator, and optionally 0 other additives) are mixed to form a homogeneous mixture, and then a homogeneous and photopolymerizable compound is mixed. By molding the mixture to form a photosensitive layer, yt,
A method for producing a photosensitive layer based on polyamide, which is suitable for producing heavy-duty printing plates and relief plates, comprising the steps of: While moving and/or post-mixing under violet cutoff and at the same time in molten liquid form, the softening probability of the mixture is less than 2
The method is characterized by heating at a temperature of 0 DEG to 80 DEG C., preferably 30 DEG to 60 DEG C., for about 5 seconds to about 10 minutes.

In an advantageous implementation of the uninvented process, depending on the method, the mixture is
Subject to inventive heat treatment for 0 seconds to 5 minutes. Another method of this method
In one practical application, the heat-treated mixture is degassed to remove harmful components, such as bath salt residue, during the homogenization and/or heat treatment of the present invention. Alternatively, it can be carried out afterwards or during and/or during degassing.

According to another advantageous modification, the homogeneous, bulkable mixture is immediately formed into a photosensitive layer after the heat treatment according to the invention, and the layer is simultaneously or immediately thereafter fixed to a dimensionally stable support. let In another advantageous embodiment of the method according to the invention,
This will be explained in detail below.

The exposure properties of a photosensitive layer produced by briefly heating a molten liquid photopolymerizable mixture to a temperature significantly higher than the softening temperature of the mixture before being molded into a photosensitive layer are determined by Is the exposure time significantly shorter (e.g. % or %
It could not have been foreseen by a person skilled in the art that the heat treatment of the present invention could improve the photopolymerizable mixture so as to reduce the (On the contrary, the layers produced therefrom exhibit particularly good and even partly improved properties, on the basis of which printing plates or relief plates can be advantageously produced. Relevance is an amazing thing.

Polyamides for producing photosensitive layers or in the molecular backbone which are soluble or at least dispersible in the customary aqueous or organic, even alcoholic solvents known per se for this purpose. Linear synthetic polyamides having repeating amide groups are suitable. Particular preference is given to copolyamides which are soluble in customary solvents or solvent mixtures, such as 1st class aliphatic alcohols (propanol or inglopanol) or mixtures of these alcohols with water. Corresponding suitable polyamides are described in the cited document, Ji
lt is also the number one French national specialty. The details are described in the patent application No. 5, No. 856, German Patent Application Publication No. 2202357, or No. 1,522,469. Suitable for % are mixtures of one or more lactams, especially ε-caglolactam, and at least one dicarboxylic acid/cyamine salt, such as approximately equal amounts of ε-caglolactam, hexamelenezoammonium adipate and 4.4%. It is a copolyamide prepared by co-condensation of a mixture consisting of -diammonium-dicyclohexylmethane adipate.

To produce the photosensitive layer, the polyamide is mixed homogeneously with a photo-M@capable 12-molecular weight ethylenic unfavorable 8W, a photo-N8 initiator and optionally other customary additives.

As photopolymerizable, low-molecular-weight, ethylenically unsaturated compounds, monomers and/or oricomers having a molecule H of less than 5000, preferably less than approximately 2000, which are generally used for photosensitive layers of this type and are known per se, can be used. − is applicable. In this case, it is obvious to those skilled in the art that the photopolymerizable ethylenically unsaturated compound should be compatible with the polyamide and generally have a boiling point of more than 100 DEG C. at atmospheric pressure. A photopolymerizable low molecular weight compound having two or more ethylenically unsaturated double bonds alone or
Preference is given to mixtures with photopolymerizable monomers and/or oligomers having only one ethylenically unsaturated double bond.

Suitable photonable low molecular weight ethylenic amorphous compounds include di- and poly-acrylates and -methacrylates, which can be prepared, for example, by esterifying diols or polyols with acrylic tW or methacrylic acid. be. For this reason (C is particularly ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of about 500 or less, 1,2
-Propanediol, 1,3-propanediol, neopentyl glycol (2,2-methylpropane/ol), J,4-butanediol, 1,1.

Di- and tri(meth)acrylates of 1-trimethylolpropane, glycerin, or hagentaerythrin. Very suitable are monomers and/or oligomers such as 1-methoxymonomers and/or oligomers which, in addition to double bonds, also contain amide groups and/or urethane groups, such as derivatives of (ivy)acrylamide, such as N-hydroquinemethyl. - reaction product of 2 mol of (meth)acrylamide and 1 mol of aliphatic/ol (e.g. ethylene glycol), quinrylene-bis-acrylamide or 1-alkylene with 1 to 8 carbon atoms in the alkylene group It is bis-acrylamide.

Similarly, for example glycol monomethacrylate or glycol monomethacrylate and diincyanate (e.g. hexamethylene diinocyanate, toluylene diiso/
reaction with anate, inphorone diisocyanate-1-),
or hydroxyalkyl-(meth)acrylates (e.g. β-hydroxyethyl-(meth)acrylate, β-
hydroxypropyl-(meth)acrylate), aliphatic diols (e.g. ethylene glycol, 7-ethylene glycol, furopanediol, butane/ol, neope/
Urethane acrylates of monomers or grebolimers, such as those which can be prepared by the combination of tyl glycolla and a compound/yne/anate (such as hexamethylene diinocyanate, -t or isophorone diincyanate). There is C.

The quantity ratio of polyamide and photopolymerizable low molecular weight ethylenically unsaturated compound can be varied within a wide range and can be applied firstly to the photosensitive layer and then to the desired printing plate and relief plate. Depends on characteristics.

This ratio is the amount of the photopolymerizable low molecular weight ethylene unsaturated compound and the amount of the polyamide, respectively.
5M quantity estimate, 25-50 liter volume% and polyamide 45-90 weight 17t%, special weight = 50-75ff
ii Dab.

The fecal dose of Hikari@Kai field opening agent depends, inter alia, on its absorbance and the thickness of the photosensitive layer, and is generally from o, oi to 10 M%, in the sign of approx. It is 0.01 to 5%. As a photopolymerization initiator, all compounds that can initiate polymerization/formation when subjected to chemical action at the edge of fire are suitable. Examples of the photopolymerization initiator include acyloy/and anroin ether, aromatic diketone and its d4 form, polynuclear quinone, an/an derivative, a fena/an derivative, or anruphosphine oxide. Very suitable are benzoin and α-hydroxymethylbenozoin and their alkyl ethers having 1 to 8 carbon atoms, such as benzin-
Isoprobyl ether, α-hydroxymethylbenzoin methyl ether, benzyl molybdenum/
'y-tar N; t benzyl dimethyl ketal,
Benzyl monomethyl-benzyl ketal or benzyl-
Moneopentyl ketal; and also for example German Patent Application No. 2909992, 1. It is an end-type penzoyl-phosphine oxide as listed in IIj.

In addition, in order to produce the photosensitive layer, additives known per se are usually added, such as a low molecular weight saturated compound containing an amide group, a wax, an activator, a thermal polymerization inhibitor, a dye, etc.
The face f'l-, etc. can be shared by N-body known characters.

As softeners, polynuclear II-V molecular weight alcohols and/or N-fitted arylsulfonamides may be used. Examples of heat-reducing adjuvants include hydroquinone, p-quinone, p-toxyphenol, methylene blue, phenol, salts of N-nitronecyclohexylhydroquinolamine, N-nitrone-7 phenylamine, and the like.

The thermal polymerization inhibitor is general VCIJ, O based on the total amount of the photosensitive layer.
J~2. o7 (%), preferably from 0.05 to 1 M% by weight. The total amount of all other IJD substances is generally less than 30% by weight, based on the total weight of the photosensitive layer.

To produce the photosensitive layer, its components namely polyamide,
A photopolymerizable low-molecular-weight ethylenically unsaturated compound, a photopolymerization initiator, and optionally other additives are mixed with each other. This mixing can be carried out in any manner and in any manner, provided that the mixing is carried out homogeneously and without harming the materials, based on all methods known for this purpose.

For example, it is possible to mix several components together in a solution.
It is Noh. In this case, at least the main proportion of the bath agent must be removed again during the heat treatment according to the invention of the mixture in the form of a bath melt (in a form that is milder for the material, for example in a thin-layer evaporator or in a descaling extruder). Similarly, the components of the photosensitive layer can be homogeneously mixed with each other while melting the polyamide in a bath using a mechanical mixer, such as a kneader, a can-closed mixer, an extruder, and the like. I can do it.

The resulting homogeneous photopolymerizable mixture, which generally has a softening temperature of about 80 DEG to 160 DEG C., in particular about 90 DEG to 140 DEG C., is advantageously removed by degassing before shaping into the photosensitive layer. Removes sexual components. Such degassing of volatile components can be carried out, for example, when the components are mixed in a bath liquid as described above, or when mixed using a mechanical mixing device, for example, by adding a liquid auxiliary agent, e.g. Necessary when extrusion aids are used together. Descaling of homogeneous photopolymerizable mixtures is most generally desirable to achieve high quality and good optical clarity and clarity. The degassing of the homogeneous 9M female mixture is advantageously carried out by applying a suitable negative pressure to the bath melt.

The photopolymerizable mixture is shaped into a photosensitive layer and is then subjected to a heat treatment according to the invention, with π being sufficiently excluded from oxygen for a short time and with simultaneous movement and/or post-mixing in the bath melt. 20-8 above the softening temperature of the photopolymerizable mixture
Heating is carried out at 0°C, preferably 30-60°C higher. In order to achieve the desired advantageous properties of the photosensitive layer, it is sufficient to subject the heat treatment to this heat treatment for 5 to 0 minutes, preferably for 10 seconds to 5 minutes. It has been found. Generally, in the heat treatment of the present invention, the photopolymerizable mixture is
Heat to a temperature in the range of 50 to 190°C (material temperature of the WF4 mixture). This heat treatment must be carried out with sufficient exclusion of oxygen in order to avoid material deterioration due to oxidation, framework formation, gel formation, or polymer decomposition. Therefore, the heat treatment is generally carried out under an inert gas atmosphere, for example using a nitrogen protective gas. During IoJ, it was found that during heat treatment it was necessary to heat-treat the bath melt of the photopolymerizable mixture uniformly and completely. For this reason, it is necessary to simultaneously move the bath melt plate mixture or to heat treat it before mixing. This mixing is advantageously carried out in such a way that four layers of melt of the photopolymerizable mixture are formed during this process. Although the heat treatment of the present invention can be carried out in principle with any suitable apparatus, the heat treatment can be carried out with
! It has been proven that it is easy and advantageous to wait for the actual R within the first flight. In this case, it is also possible to use single-screw or multi-screw extruders.

The inventive heat treatment of the bath-melt mixture can be carried out at any arbitrary point during mixing of the components and prior to formation of the photosensitive layer. If the components are mixed in the bath melt, for example in an extruder or other suitable residual mixing device, the mixture can be subjected to a heat treatment already during the homogenization process. In this case, too, the heat treatment can likewise be carried out only after homogenization, during degassing and/or after degassing the bath melt. In this case, the duration of the heat treatment is
related to the point in time. If the bath-melt mixture is heated to a certain high temperature already during homogenization, a relatively long time is required for the heat treatment. In the post-removal heat treatment, the shortest time is sufficient. The bath-molten liquid mixture is already being homogenized and/or degassed (if it is to be subjected to 4C heat treatment, the hot liquid mixture of the bath-melt mixture should be soaked until it is molded into a photosensitive layer). Yes+IJ.

When the components (of the photosensitive layer) are mixed with each other in a bath solution, use the bath 7+! as described above. ! l! Beforehand for the heat treatment according to the invention in liquid form, at least the main part of the bath agent should be removed. Therefore, in this case, the heat treatment must be carried out during homogenization and during and/or immediately after the removal of the solvent. Advantageously, most of the bath agent is first removed under mild conditions, i.e. at relatively low temperatures and optionally in vacuo, and the resulting mixture (which usually still contains about 5 to 10 IO
The content of up to % M (which can also be expressed as '1-filament') is post-treated according to the invention. For this purpose, what has been said above regarding mixtures produced in molten liquid form applies.

After the heat treatment of the present invention, the homogeneous photopolymerizable mixture is molded into the desired photosensitive layer by a conventional method known per se, such as by pressing, calendering or extrusion. In order to avoid additional and unnecessary heat loads on the photosensitive material, it is advantageous to carry out the shaping of the photosensitive layer directly after the non-inventive heat treatment using a photopolymerizable mixture which is still in bath melt form. It is. If the heat treatment is carried out in an extruder, for example, the photosensitive layer can be formed simply by extruding the photopolymerizable mixture through a wide-slit nozzle. According to one advantageous feature of the method of the invention:
It is an OT capability to carry out the homogeneous mixing of the components, the degassing of the nine-M8-capable mixture, the heat treatment and the formation of the photosensitive layer in a slow-fired day process, for example using a suitable extruder.

Photosensitive layers prepared according to the invention are generally solid at room temperature. This layer thickness can vary within wide limits and is generally determined on the basis of the particular intended use.

The thickness of the photosensitive layer is generally from 100 .mu.m to about 7 .mu.m, preferably from 500 to 2000 .mu.m.

Since the photosensitive layer is normally used in solid-layered form with a dimensionally stable support when used for producing printing plates or relief plates, it is possible to prepare the photosensitive layer in the process according to the invention for this purpose. It is advantageous to mold on a dimensionally stable support. This can be done, for example, by applying the extruded material through a wide-slit nozzle directly onto a suitable support, or by applying the photopolymerizable mixture together with the support in the gap between a pair of rolls or in order to form a photosensitive layer. This can be done by penetrating a calendar. Suitable dimensionally stable supports are the materials customary for this purpose, such as steel plates, aluminum plates or copper plates, sheets or films made of polyethylene, polypropylene, polyester or polyamide, coated or impregnated paper, and the like.

The support may be mechanically or chemically pretreated or provided with an additional contact layer in order to improve the contact strength with the 8-layer.

The photosensitive layer produced according to the method of the invention is prepared by exposing the photosensitive layer to actinic radiation one by one, and then removing the unexposed portions of the layer by washing with a suitable white visual bath. It is suitable for producing relief plates and printing plates.

The recording material having the photosensitive layer according to the invention is advantageous because it has smooth exposure characteristics, and is suitable for short-term exposure, such as for example in newspaper printing, without the need for additional means such as pre-exposure. It can also be used in areas where time is preferred. The method according to the invention is simple and economical to carry out and is suitable for producing fine fin 9% as well as other printing plates or relief plates.
Bringing products that are both feminine and advantageous to customization.

Next, the present invention will be explained in detail with reference to Examples. "Parts" and "%" in the examples are based on weight unless otherwise specified.

Example 1 The following ingredients: Polyamide 50 IN-methylol acrylamide and -bisether consisting of ethylene glycol
35-ethylene glycol
10 note b benzoin methyl ether
No. 3 βN-nitrosocyclohexylhydroxylamine 0.5 units and black dye (solvent) Lac 34, C, 1,
1,2195) A photosensitive layer was manufactured from 0-01 Miyako.

The above components were homogeneously mixed with each other in a high-intensity mixing zone heated to 150°C (jacket temperature) with two parts of water in a single-screw extrusion chamber. After homogenization, the mixture can be photopolymerized! 1yl (softening temperature about 100° C.) was held in the extrusion chamber at 150° C. (material temperature) for about 20 seconds and then formed into a 0.5 ran thick layer through a wide slit nozzle. The still hot layer was applied directly to a steel plate coated with a polyurethane adhesive lacquer. Subsequently, the resulting photosensitive layer was imagewise exposed to actinic radiation, and the unexposed areas were exposed to ethanol/
Washed with warm water (8:2). The exposure time required to provide standard specifications was 90 seconds.

Example 2 The procedure was as in Example 1, except that in this case the mixed components were homogenized by adding 5 parts of water and the homogenized photopolymerization: The mixture was degassed under reduced pressure until the residual content was 2%. The degassed photopolymerizable mixture was held on this platform at 150° C. (material temperature) for about 40 seconds, and then, as in Example 1, it was heated to a thickness of 0.05 mm.
It was formed into a 5 mm layer and immediately attached to a steel plate. Again, the exposure time to provide the standard was 90 seconds.

Example 3 Example 2 was repeated, but this time working in a twin screw extruder with screws rotating in the same direction and closely meshing. After degassing, the temperature of the homogenized photopolymerizable mixture was kept at 160° C. (material temperature) for about 20 seconds. A printing plate was produced from the obtained photosensitive layer by exposing the photosensitive layer based on the image and removing the unexposed portions in the same manner as in Example 1.

This required an exposure time of about 80 seconds.

Example 4 The mixed components of Example 1 were bathed in a mixture of 90 parts methanol and 10 parts water, mixed with each other and fed continuously into a twin-screw extruder with rotating and contacting screws in the same direction. . After descaling carried out in two steps at 140°C (jacket temperature) and a pressure of 50 mbar, there is still a residual water layer of 2%.
The bath melt containing was held at 150° C. (material temperature) for about 30 seconds. After extrusion as in Example J through a wide slit nozzle and application to a steel plate provided with an adhesive layer, a uniform, spot-free photosensitive layer with a thickness of 0.5 mm was obtained. For producing printing plates by image-based exposure, an exposure time of approximately 100 seconds was required.

Example 5 Example 3 was repeated, but this time 6 parts of trimethylolpropuff were added to the mixed ingredients.

The softening temperature of the homogenized photopolymerizable mixture was 90° C. after degassing. After heat death q+, degassing was performed at a temperature of 150° C. (material temperature) for about 20 seconds.

Four homogeneous, kel-free photosensitive layers with a thickness of 0.7 mm were formed through a wide slit nozzle, and the layers were then sized between two polyester supports on a 2-Nero unit. . Image-wise exposure of the photosensitive layer and washing off of the unexposed portion resulted in a soft, elastic printing plate. The exposure time was 95 seconds.

Example 6 The procedure was carried out in the same manner as in Example IJ 1, except that instead of ethylene glycol, the reaction product of β-hydroxyethyl methacrylate and toluylene incyanate (2:1) was used. I got it. The softening point of the mixture, which was homogeneous and suitable for one light beam, was 130° C. after degassing.

For the heat treatment, the temperature of the homogenized photopolymerizable mixture was held at 170° C. (material temperature) for about 30 seconds. The shaped 0.7 mm thick photosensitive layer was then applied to a lacquered aluminum support.

Based on the image (exposure of the photosensitive layer and removal of the unexposed layer parts, a hard printing plate was obtained.

The exposure time was 140 seconds.

Comparative Experiment Example 2 was repeated, but in this case the temperature at which the homogenized light was exposed was reduced by 105° C. (material temperature) after degassing. The photosensitive layer produced showed disproportionality in the form of Kel particles. An exposure time of 200 seconds was required to load the printing plate.

Comparative Experiment B The # and @ components of Example 1 were bathed in a mixture of 90 methanol and 1.0 part of water, and the bath liquid was concentrated in a thin layer evaporator to a solids content of about 70%. The bath solution was spread over a polyester support (wet layer thickness s 0.71) and dried at about 70° C. for 2 hours. A homogeneous photosensitive layer with a thickness of 0.5 and a solids content of about 95% was obtained.

This layer is applied to a steel support with a polyurethane adhesive layer. An exposure time of approximately 200 seconds was required to produce the printing plate.

Bisoft Yi, Gyeong C The procedure of Example 2 was repeated, except that 12 parts of a reaction product of hydroxyethyl methacrylate and toluylene diisocyanate (2:2) was used in place of ethylene glycol. The mixture was bathed in a methanol/water mixture (90:10) and the liquor was concentrated in a thin layer evaporator to a solids content of about 63%. The solution was spread onto a polyester support so that after drying at about 70 DEG C. for 4 hours a layer having a layer thickness of 0.7 mm and a solids content of about 95% was obtained. To produce a printing plate using this photosensitive layer, an exposure time of approximately 300 seconds was required.

%W Appearance Basfachchenkesselschaft Patent Attorney Thioji Tashiro Page 1 continuation 0 Inventor Hans-Dieter Zetra Federal Republic of Germany 6718 Grünstadt Bukelhaube 5 @ Inventor Gerhard Pretzkmann Federal Republic of Germany 6840 Lambertheim Giselaerstrasse 9 @l! Lothar Schlemer Federal Republic of Germany 6701 Maxdorf Duesbergstrasse 1 ar 0 Inventor Christoph Taubitz Federal Republic of Germany 6706 Wuachenheim in der Dreinewitz 15 0 Inventor Rudolf Huifial Federal Republic of Germany 6700 Route Wichshaf-en-Alwin-Mitaschplatz 10 ・'77 Inventor Hein-Ulrich Zerta Federal Republic of Germany 6706 Wuhr/＼Inheim Hans ~ Hoffmannstrasse 12 190

Claims (1)

[Scope of Claims] (1) At least one polyamide that is soluble or at least dispersible in a solvent, and a photopolymerizable ethylenically unsaturated adduct of 1-molecular weight that is compatible with the polyamide. , at least one photopolymerization initiator, and optionally other conventional additives to form a homogeneous mixture, and then the homogeneous and photopolymerizable mixture is formed into a photosensitive layer. Photopolymerizable printing plates and relief plates? In a process for producing a photosensitive layer based on polyamide, which is a common material for manufacturing, the mixture of the above-mentioned components is subjected to sufficient acid barrier and at the same time in the form of a molten liquid before being molded into a photosensitive layer. /or while post-mixing,
A method for producing a photosensitive layer based on polyamide, characterized in that heating is performed for 5 seconds to 10 minutes at a temperature 2° to so'c lower than the softening temperature of the mixture. (2) A method according to claim 1, characterized in that, for producing the photosensitive layer, further additives include softeners, activators, thermal polymerization inhibitors, pigments and/or dyes. (3) 30 to 60'C above its softening temperature
3. The method according to claim 1 or 2, wherein the method is heated to a high temperature. (4) The method according to any one of claims 1 to 3, wherein the mixture is heat treated for about 10 seconds to 5 minutes. (5) The method according to any one of claims 1 to 4, wherein the mixture is heat-treated during and/or after homogenization. (6) removing harmful volatile components by degassing the photopolymerizable mixture after homogenization and before forming it into a photosensitive layer;
A method according to claim 6, which processes the chairs according to claims 1 to 5. (8) The method according to any one of claims 1 to 7, wherein the photosensitive layer is formed immediately after the heat treatment of the photopolymerizable mixture. (9) The method according to any one of claims 1 to 8, which is carried out in an extruder that heats the photopolymerizable mixture. The method according to any one of claims 1 to 9, wherein the αO homogeneous photopolymerizable mixture is fixed to a dimensionally stable support during or immediately after the process of forming the photosensitive layer. .