DE1622285B - Process for the production of relief images - Google Patents

Description

are present can be adversely affected.

The heat exposure associated with the use of high energy light sources can increase an undesired thermally induced decomposition of the polymerization initiators with simultaneous formation of the substances initiating the polymerization. This can lead to an effect which, based on silver halide photography, can be referred to as veil blackening, see above that it is not possible to obtain high quality reproductions. The use of longer exposure times to compensate for a reduced light intensity, on the other hand, it increases considerably Measure the time it takes for the photopolymerization process to complete completion, thereby creating in turn, the production costs increase.

In attempts to eliminate or circumvent the difficulties of the previously known methods, The main focus of industry has been on developing more effective vinyl monomers and photopolymerization initiators concentrated. Despite some efforts, the developed Processes and products in the majority of commercial use no more than one slight improvement made.

A method of making relief images that produced a significant industrial advantage, relies on the use of high energy corpuscular rays instead of visible light or UV light for the imagewise exposure of a radiation-crosslinkable layer (cf. USA patent 2,748,288). The advantages that can be achieved with such a method are considerable, with the The main advantage arises from the fact that the exposure values can be reduced to the extent that as it was previously thought impossible; however, the method can be carried out effectively. This advantage arises from the fact that the energy of an electron, which for example has experienced a high voltage acceleration of around 15 kV, several thousand times the energy compared with a photon in the visible range of the spectrum. The required exposure time is therefore only a fraction of the time required to carry out the collotype printing process. The negative forming materials involved in electron beam reproduction do not require the use of special methods of handling and storage as they are not sensitive exhibit against light from the visible range as well as the UV range of the spectrum. The image transfer can therefore be done in daylight. Another benefit of the reproductive processes that are based on the Application of electron beams or other corpuscular beams, results from the fact that the beam of particles of high energy can be precisely regulated and that in this way that is possible reproducing image according to a predetermined pattern, d. H. a programmed grid movement can be scanned. A very special advantage arises from this fact. With the usual Negative methods, the feasibility of which depends on the photolytic effect of the exposure radiation depends, the original to be reproduced (HiId or writing) initially in the form of a drawing or a template. Of the latter one must be A suitable photographic negative can be produced, which is then used for contact printing on the resin-coated surface is used. In contrast, in electron reproduction, there is a need turned off for the production of a negative material because the electron beam itself directly to Formation of the polymer negative is used in accordance with a predetermined, programmed grid movement can be. In addition, the high quality and accuracy of the image reproduction that can be achieved with the

ίο Electron production is possible and that too precise reproduction of the finest details is allowed, with particular advantage for the production of printed documents Circuits are used in which these factors are of particular importance.

In addition to the multiple advantages that reproduction with electron beams offers, this brings in the However, practice also poses considerable difficulties affecting the general commercial application of these Method prevented. One of the main problems arises from the nature of the polymer negative forming material. For the most part, there are the materials used for the stated purposes from monomers or prepolymers that become insoluble when exposed to corpuscular radiation exposed, so that a selective removal of the exposed and unexposed areas becomes possible. The material making up the polymer negative should ideally have a number of properties have a light and effective "deposit in the form of a uniform and continuous film, the use in combination with a large number of etching solutions and - above all - the light one Allow removability with relatively simple means.

The ones proposed so far for the purposes mentioned However, polymer materials suffered from significant disadvantages in one or more directions. One A large number of the known materials had only a limited solubility, so that they can only be used in combination can be used with a relatively limited number of solvents. Since the nature of the Solvent in many cases to a considerable extent the economy of the process in question influenced, this factor is of considerable importance. Other materials, although proportionate easy to remove with a large number of commercially available solvents are not especially useful because they are poor film formers. But it is of the utmost importance that that The material used to form the polymer negative can easily be placed on any type of substrate, regardless of whether these are made of metal, glass or plastic and it does not matter whether they are curved or in some other way are irregularly shaped, as a uniformly continuous layer, i.e. H. essentially free of physical Leaves irregularities. It is essential that the layer in which the polymer negative is formed has a surface for the solutions used in the various stages of the process.

d. H. the solutions, which after exposure to the removal of the areas of the which have not become insoluble Resin layer, like the solutions used to etch the plate surface, are completely impermeable is. Defects in the coating affect the permeability of the formation of the polymer negative layer and make it impossible to make good quality reproductions. Other hard-like materials used for the go-

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The above-mentioned purposes are proposed, despite the fact that the document in the final treatment is good Solubility properties and good film-forming an easy one. Distance, e.g. B. by peeling, not Properties not usable because their resistance is more feasible because the solvency of the ability to withstand the caustic solutions that are used, most of the chemicals used for this purpose is not big enough. The layer in which the poly-5 is no longer sufficient. As a result one had to get up If it arises mernegative, tedious mechanical removal methods such as abutments should be used for treatment and especially for those who resort to etching, scraping, etc. In many If the solution used was completely impermeable, this could damage the surface d. H. represent a total diffusion barrier. Other documents cannot be avoided. This schwiefalls becomes the objective of the entire procedure io rige problem shows itself when using impaired because the etching effect is not affected by some resins, which increase the adhesion Solvent treatment exposed areas strength between resin layer and substrate none remains limited. special treatment is required.

The insufficient resistance and the object of the invention is to provide a method for

The permeability of the known materials to the formation of relief images and / or anti-etching layers of the etching solutions made it necessary to state in the known materials that for image-wise recording it was necessary to apply relatively thick layers to the substrates with electron beams or other corpuscular beams. The disadvantages, which are very much used in such, and which result in a photosensitive thick layer, are obvious; a mixture is to be used, which good layer is necessary, for example, either the activity of the 20 forming properties and after the imagewise developer solution, ie the solution that for removal irradiation of the unexposed layer parts a good voltage of the areas not hit by the rays solubility In conventional solvents and the polymer layer serves to reinforce - which can be achieved through light-colored parts of the layer, a high resistance to heating the solution - or and which gives the solution impermeability to conventional etchants, the developer solution is allowed to stay on the polymer for a longer period of time to let the layer take effect, so that a complete deletion can be removed from the base,
removal of the areas not hit by the rays The maleic acid proposed according to the invention

the layer is reached. In some cases it makes anhydride polymer material not only allows the cooker Thickness of the layer even necessary, a mechanical formation of coating layers of smaller thickness, sunny Treatment such as rubbing, scrubbing or scraping 3 ° which also makes it possible for additional treatments apply to the appropriate areas of the to increase the. Resistance of the coating polymer layer can be completely removed. switch off completely.

It is clear that such treatments inevitably the subject of the present invention is now a

damage the plate. It is also clear for the production of relief images that thicker layers nullify all attempts by radiation crosslinking applied to a layer support to obtain reproductions of good quality, especially barren layers, by irradiation with corpuscular layers of high sharpness. Furthermore, irradiation must be taken into account until the rays struck, that for the reproduction rich in details of the layer have become insoluble, and very thin layers are required on templates, such as those required for microcircuits, which are subsequently removed from the rays. In order to circumvent 40 insoluble areas of the layer caused by the difficulties mentioned, it was necessary, when washing with a suitable solvent, which is necessary for the previously known polymer materials, to resort to radiation-sensitive measures that protect the impermeable-sensitive layer Homopolymer or the layers for the usual etching solutions mixed polymer of maleic anhydride, which is greater. This was particularly necessary if the 45 contained about 10 to about 65 mole percent maleic anhydride (Jj the base of metal units supporting the polymer layer, and a specific viscosity of. The additional treatment consisted, for example, of about 0.05 to about 5.0 has, is used,
wise in a heat treatment following the use according to the invention of the geEntfernung the parts not hit by the rays called homopolymers or copolymers as the material of the image layer with a solvent and before the 50 for the radiation-sensitive layer, etching of the substrate, z. B. the metal base. The layer-forming properties of a good last-mentioned operation became all the more critical, the more the solubility in the unirradiated parts of the layer was reduced and the more the thickness of the image layer was reduced. an exceptional resistance to

The polymer substance, which forms the polymer negative, and impermeability for the etching solutions are achieved in the parts of the layer which are radiated in addition to the properties already listed. The irradiated layer as well as that of the easy removability after the part can easily have etching process from the surface of the base. In most of the known processes, it is necessary to remove the solvent by a simple treatment with an alkaline method in order to achieve sufficient diffusion, which means that the cost resistance to the etching solution is necessary, and the treatment time is reduced and the throughput reduces the polymer negative following the solvent- 60 can be increased significantly,
Treatment of an additional treatment is also to be found in the method according to the invention

throw, through which the resistance of the polymer is possible to arncgativs increased with greatly reduced layer thicknesses. For example, powerful heal because the resistant wedge of Maleinsüurean-Wärmebehandkingen necessary hydridpolymermalerials against Aet / lösungcn far ness / wipe ui to Haftfestig-: r llar / Schiehl and backing to c> 5 greater than the known materials. The multiple reinforce and otherwise the Uiidurchlässigkeit with Maleiiisäureanhydridpolymeren of the type mentioned di: r I liir / scliichl / u increase. Such treatments can in part theoretically not be made more difficult again. will; they consist of an optimal cone

7 8

combination of the desired properties, d. H. the α, / 3-ethylenically unsaturated hydrocarbons,

Film formation, solubility and the impenetrable- z. B. ethylene are also particularly effective. the

speed for the etching solution, which is used to produce the photosensitive layer from a solution of the

Relief images using corpuscular maleic anhydride polymers in a suitable

making radiation ideally suited. 5 Solvent with the desired solids concentration

In the case of the maleic anhydride polymer, tration may be formed. The maleic anhydride polymer is a simple homopolymer which is used in concentrations of about 10 to 65 percent by weight, about 10 to about 65 mole percent anhydride units, percent, preferably about 25 to about 55 percent by weight. H. contains unhydrolyzed units. It can percent, used. The solvent can also be a mixed polymer of maleic io is a commonly used for the preparation of diacid anhydride with at least one monoäthylenisch persen solutions of maleic anhydride polymers unsaturated vinyl monomers, which is a CH ₂ = C <- used, z. B. contains a methyl group, act. ethyl ketone, dimethyl ketone, acetone, methanol, etha-

For the production of the copolymers, nol, chloroform, dimethylformamide or dioxane can be used. In addition to maleic anhydride, any other mono- 15 Further materials that facilitate the deposition of the polymer mers, which are generally in the form of a uniform coherent film with maleic anhydride, can facilitate the solution, where appropriate, monomers of the vinyl type who added one. For example, the polymer solution can have ethylenically unsaturated double bonds. Layering aids, dispersants or stabilizers are a typical example of such monomers. The polymer solution can be applied to the, for example, vinyl alkyl ethers of the general support with the help of the usual formula CH ₂ = CH - OR, in which R is a straight-line method, for example through or branched-chain alkyl groups with 1 to 20 carbon infusions , Brushing on, air-coating represents material atoms, which in turn are caused by inert dropping or dropping. The type of application of the layer of harmful groups such as alkyl, aryl, alkoxy or 25 depends to a considerable extent on the geometric halogen may be substituted. Other monomers, shape of the pad. The thickness of the layer so applied which can be used for this purpose should be between about 0.1 and about e.g. ethylene, propylene, styrene, p-chlorine, 50 microns, preferably between 0.5 and about p-methoxy and p-methylstyrene. In certain cases, 10 microns, lie.

z. B. when the polymer material is produced by means of corpuscular acid anhydride, with the interpolation of the interpolymerization of an alkyl vinyl ether with Ma- desired template with the help of corpuscular acid anhydride Quantities will be. The image generation is best done with not only electrons on a polymer of alkyl vinyl ether, which contains electrons from a conventional cathode ray and maleic anhydride, but also with a tube. Homopolymers of one or both mono-electrons, both lower and higher, can also be used for imaging. Energy more reactants, ie homopolymers of the used, ie acceleration potentials in maleic anhydride and / or the alkyl vinyl ether. Range from about 1 to about 100 kV. In general, the last-mentioned materials have no effect on the desired properties of the 4 ° range, ie those from about 6 to about 30 kV, maleic anhydride-containing polymer mixtures, because they are more effective; The high energy of the electrons, provided that the total amount of maleic acid electrons in the 60 to 80 kV range, means that the anhydride (in mol percent) in the electrons in front penetrate the image layer, so that a flat area located. As a result, there is no mot part of the energy being wasted. The economy, z. B. the alkyl vinyl ether homopolymer 45 speed of a given acceleration potential and by an additional treatment from the polymer to remove its applicability in the given individual case mixture. The presence of additional depends largely on the thickness of the image layer. Polymer substances can even decrease in some cases. In general it can be said that the beneficiary, e.g. B. to gain a greater backlash acceleration potential and thus the penetration space when controlling the polymer viscosity. At 5 ° by virtue of the corpuscular radiation in which the picture eralle cases, it is extremely important that the generating stage within the specified range increases maleic anhydride content in the polymer material with increasing layer thickness of the image layer - regardless of whether it must be a maleic anhydride. The optimal relationship between the mixed polymer and / or maleic anhydride homo-acceleration potential and the layer thickness or layer polymer is - the thickness specified above can easily be within the range given by preliminary tests in the laboratory. The polymer material used can therefore be determined. Generally speaking, determined could be relatively different; Best results are that a sufficient irradiation, leading to a nep, however, are obtained when copolymers used electron density of about 10 ^u electrons per cm ^2, which leads through copolymerization of ma-; one then achieves reproductions of high qualileic anhydride with an alkyl vinyl ether, e.g. B. 60 did and layers that have the necessary resistance methyl vinyl ether, isobutyl vinyl ether, dodecyl vinyl capability against the etching solutions used, ether, hexadecyl vinyl ether and octadecyl vinyl ether. suitable indication of the sensitivity of the

According to one embodiment of the invention, materials resulting in the image layer according to the lirfin-

Material for the radiation-sensitive layer is expressed as the number of electrons

Copolymer of maleic anhydride with Me per cm ² surface of the compounds. This Hnipliiki-

ethyl vinyl ether denotes. ■ Loan wedge measurements are made after a procedure

Mixed polymers of maleic anhydride and carried out, in which the layer of skin is a wall

Dye is incorporated; the dye serves to visualize the extent to which the polymer becomes insoluble as the irradiation progresses. It was found that, in order to achieve an optical density of 0.5, it is necessary to set an irradiation value which is sufficient to achieve an electron density of 10 ¹⁴ electrons per cm ² .

As already mentioned above, the irradiation can be carried out according to a predetermined, programmed raster movement or else using a wide-angle particle beam, so that the entire image to be reproduced is scanned at the same time. The last-mentioned mode of operation can be used, for example, in those cases in which the irradiation takes place through a negative or another medium carrying the image. It has been shown that corpuscular rays, e.g. Require as electron beams, in general, a high-vacuum system in the order of 10 ~ ⁴ mm, so that they function satisfactorily. Despite this requirement, the process according to the invention can be carried out both continuously and batchwise. A continuous mode of operation, in which a large number of layers in which an image is to be produced, are continuously intermittently passed through the irradiation zone, can be carried out in a simple manner with the aid of a vacuum transport sealing device. The latter enables the plates with the image layer to be continuously introduced into and removed from the vacuum chamber with the electron beam gun or any other particle beam source without loss of vacuum. The devices of the type mentioned are known to the person skilled in the art and are commercially available. After the required exposure time has ended, a latent image is present in the image layer, which image is formed from the areas where there is maleic anhydride polymer material which has become insoluble. The parts which have not been irradiated, ie which have not become insoluble, are then removed by treating the layer with a suitable solvent such as methyl ethyl ketone, dimethyl ketone, diethyl ketone, ie one of the solvents listed above which have sufficient solubility for maleic anhydride polymer which has not been made insoluble.

The areas of the plate that have been exposed by the solvent treatment can then be used with a suitable etching solution, the type and efficiency of which depends on the type of plate surface depends, d. H. whether it is made of metal, glass, plastic and the like. Metal surfaces such as copper, aluminum etc. can be treated with common etching solutions; a solution of ammonium persulfate and sulfuric acid containing a small amount of mercuric chloride, for example, is an excellent one suitable etching solution for copper surfaces. Aluminum surfaces can easily be etched with hydrochloric acid solutions. If the surfaces are non-metallic, z. B. on glass or ceramic surfaces, hydrofluoric acid solutions are suitable for etching. Solutions of hydrofluoric acid and nitric acid can be used to etch silicon or germanium will.

Depending on your intended use, the If the object manufactured in the manner described above is to be supplied, it may be desirable to make the etched parts of the surface easily visible, e.g. B. through the use of suitable Colorants, dyes or toners that provide a sufficient contrast between the etched parts and the rest 5 Create the surface of the object. Appropriate treatment can either be done before or during Connection to the etching of the plate can be made. In some cases, etching may not be necessary be so that the colorant, the toners on the

ίο The surface of the plate can be applied directly after the end of the solvent treatment, ie the development stage in which the parts of the image layer that have not become insoluble are removed. The materials used according to the invention for the image layer produce images with excellent opacity in any case, so that any desired and very different post-treatment of the plate is possible, for example with etching solutions, dyes or other agents. The invention is particularly advantageous in those cases in which a treatment with highly active or highly corrosive etching solutions is required in one of the treatment stages because the maleic anhydride polymer materials are extremely resistant to such etching solutions. ^ *

According to a further embodiment of the invention, the sensitivity of the maleic anhydride polymer layer is d. H. the extent to which it responds to the corpuscular radiation by adding a or several suitable crosslinking agents enlarged or strengthened, which consist of a monomeric compound exist that have at least one ethylenically unsaturated, non-aromatic double bond between have neighboring carbon atoms, which are due to the direct vicinity of an electronegative Group, such as halogen, C = O, - Cs N, - Cs C -, - O - or aryl, are activated. Examples of such Materials are Ν, Ν'-methylene-bis-acrylamide, Acrylamide, divinylbenzene, styrene, ethylene glycol, divinyl ether, and the like, usually more satisfactory to achieve Sufficient results, the substances mentioned in amounts of 5 to about 50 parts by weight, preferably from 10 to 20 parts by weight, des To use maleic anhydride polymer material. In some cases it can and is desired optionally possible, the resistance of the insoluble areas of the polymer layer to to enlarge the etching solutions by heat treatment. As explained above, there were such In the case of the older known processes, heat treatments are always necessary in order to achieve the required Resistance to the etching solution has been achieved. Treatment can consist of one the parts of the image layer that have become insoluble after irradiation and after removal of the not from the polymer material struck by the rays for a short time, e.g. B. 30 minutes to an hour, increased Exposed to temperatures between 120 and 140 ° C.

The increased resilience of the maleic anhydride polymer layers according to the invention against

the etching solutions used can easily be proven by the fact that layers with a layer thickness as little as 1 micron already has excellent resistance to highly active acid solutions, which are used to etch aluminum surfaces,

fis z. B. hydrochloric acid. This resilience exists without any heat treatment or any other additional treatment that will increase further of resilience leads. The need

11 12

the application of a heat treatment. The invention will be illustrated more in the case of layers with a thickness of less than 1 micron with the aid of the following examples. further explained.
The main advantage resulting from the invention, B is r> ie 1 1
can be seen without further ado: the optional applicability of a heat treatment in the cases in which 5 A bimetallic plate, consisting of a copper, of which very thin layers are required. layer on a support made of aluminum, is turned into a

After the end of the etching process, a dilute nitric acid solution can be immersed in order to clean the insoluble surface of the plate as well. After rinsing with water and peeling off the areas of the polymer layer, which is drying, the radiation-sensitive layer required for the formation of the relief image can be achieved using suitable solvents; can, without additional mechanical handling, the material used for this purpose consists of a 5 ^O / _O igen development such as scraping, scrubbing or the like. Acetone solution of 1: 1 Mischpolymereri from maleic The replacement can be with solutions anhydride and vinyl methyl ether, the easiest of which spezierreichen which possess the ability to insoluble overall fish viscosity - measured at 25 ⁰ C in L ° / _o sodium Lömachten areas the resin layer has a hydrophilic property in methyl ethyl ketone - 2.0. To lend the material stocks. is flow-coated onto the copper layer

Suitable reagents for this purpose are applied with a layer thickness of 6 microns and

for example, dilute aqueous solutions of Ammo then dried.

The plate coated in this way is then immersed in a water-miscible solvent or mixtures thereof. 20 closed chamber is used, which contains the electrons because the maleic anhydride polymer easily in the jet gun. The pressure inside the can convert a form that is ^{soluble in aqueous alkaline chamber by evacuating to 10 ~ e} mm media, the insoluble can also be reduced. The irradiation takes place in such a way that some areas of the layer can be removed by simple handling of a small part of the methyl vinyl ether-maleic acid anylation with the reagents mentioned. 25 drid mixed polymer layer of the electron gun

The impenetrability of what has become insoluble is posited; to accelerate the electrons, areas of the maleic anhydride polymer layer are applied to a potential of 10 kV. In this way the etching solutions can be further increased if one achieves an irradiation ^{value of 10 14} electrons per cm ^{2 in the layer} immersed in an acetone solution, called substance, effectively accelerates the removal of those parts of the layer that have not been exposed to the electron-insolubility of the polymer as a result of cross-linking, which have not radiated in the same way as those above Portions of the polymer layer can be easily removed by the listed crosslinking agents. Such compounds are easily removed by this solvent treatment, while subject to an alkyl addition reaction with the parts of the layer which were hit by the electrons of the polymer material or the crosslinking agent, completely by the acetone. the molecular weight of the polymer rmaterials remain grasped. The solvent-treated plate is raised in the areas struck by the rays. is then in an oven for about ¹ hour _J2

Heated to a temperature of 130 ^° C. in the manufacture of printed circuits. After finishing

Using one of the usual metal laminates, the plate is converted into a

z. B. one with one. Plastic layer coated etching solution is immersed, which has a temperature of 55 ° C

Metal foil, the laminate is prepared by having and having the following composition:

first a layer of maleic anhydride ammonium persulfate ... 227 g

polymer material 0.1 to 50 microns thick, mercury chloride solution (1.34 g

preferably 0.5 to 10 microns. The loading 45 _{1Q0 m} | \ y _water ) 0 5 ml

Radiation is then either programmed with a sulfuric acid (concentrated) ' ..... 15'ml

th scanning beam or a wide-angle beam. Water "1892 ml

so that those struck by the radiation

Areas of the layer become insoluble. The parts of the copper layer that are not covered by the lische removal of the non-insoluble parts 50 insoluble parts of the polymer layer can then be treated with a, can be removed by the etching solution in about 10 minu-ketone or another Easily remove suitable solvents. The parts of the copper layer that are made of the type mentioned above. Protected by the insolubilized polymer. Etching of the copper foil can be carried out by using an aqueous etching solution, which remains completely unaffected by the etching solution. The insoluble persulfate, mercury chloride, and concentrated sulphurized areas of the polymer layer are made up of oleic acid. The parts of the copper layer that are not closed by the surface of the sheet metal by immersion by the polymer layer are easily removed from the plate by the etching solution in a dilute ammonium hydroxide solution. The remaining im- 60 removed; In this way, the parts of the copper-soluble parts of the polymer layer can be exposed which have not been attacked by the etching dissolving treatment subsequently by a simple treatment with a layer.
Ammonium hydroxide solution can be removed, which

Example 2, which has become insoluble under the influence of the rays

Maleic anhydride polymerize into a water soluble 65

Converts the shape and thus enables the removal. The procedure is as in Example I, with the lighting. In this way one gains a printed image that a copper-clad laminate is in place Circuit made of copper on a plastic carrier. the copper-aluminum metal sheet is used.

B e i s ρ i e 1 3

A copper laminate as described in Example 2 is coated with a material which is a 1 of a 2.5 ° / _o by weight Methyläthylketonlösung: is 1 copolymers of maleic anhydride and isobutyl vinyl ether having a specific viscosity - measured in l ° / _o sodium Methyl ethyl ketone solution - of 2.9. The layer is applied to a thickness of 5 microns. Part of the isobutyl vinyl ether-maleic anhydride mixed polymer layer is then exposed to electron irradiation, so that an electron density of 10 ¹⁴ electrons per cm ^{2 is} achieved (acceleration of the electrons by 14 kV). The parts of the polymer layer which have not been made insoluble are physically removed in the manner described in Example 1. The plate is then treated with the etching solution directly, ie without any intermediate heat treatment; the etching solution had the composition given in Example 1. ' As in the previous examples, the parts of the copper layer which are protected by the insolubilized polymer remain completely unaffected by the etching solution. It couldn't be an unwanted one either. Diffusion of the solution can be discovered. The insolubilized parts of the polymer layer are then removed by treatment with dilute ammonium hydroxide solution.

B e i s ρ i e 1 4

Further reaction is carried out as in Example 3 but using, as the material for the image layer, a 5% Methyläthylketonlösung of a 1: 1 Mischpoly-, mers of isobutyl vinyl ether and maleic anhydride, which has a specific viscosity - measured in l ° / _o sodium Methyläthylketonlösung - by 1.8. The results obtained correspond to those described in the previous examples, ie the maleic anhydride mixed polymer layer was completely resistant to the influence of the etching solution, so that the etching effect only occurred at the points where the copper surface was exposed as a result of the previous solvent treatment.

Example 5

Further reaction is carried out as in Example 3, but now using a 1: 1 copolymer of maleic anhydride and isobutyl vinyl ether having a specific viscosity - comprises of 0.6 - measured in l ° / _o sodium Methyläthylketonlösung. In this case, too, the parts of the layer that have been hit by the electrons are completely resistant to attack by the copper etching solution.

Example 6

The procedure described in Example 1, except that used as the material for the image layer a 5 ° / _o strength Methyläthylketonlösung a 1: -Mischpolymeren of maleic anhydride and Dodecylvinyläther which has a specific viscosity - measured in l ^and / _or strength Methyläthylketonlösung - ■ from 0! , 3 has. The irradiation took place with electrons which had been accelerated with K) kV, so that an electron density of K) "electrons per cm- resulted. Following the removal of the areas which had not become insoluble by the solvent, it was found that the areas were insoluble areas of the layer that had become completely impermeable to the etching solution, but could still be easily removed by immersion in dilute ammonium hydroxide solution after the end of the etching process.

Example 7

The procedure described in Example 1, except that used as the material for the image layer a 5 ° / _o Methyläthylketonlösung strength of a 1: 1 mixed polymer of

ίο hexadecyl vinyl ether and maleic anhydride, which a specific viscosity - measured in 1% methyl ethyl ketone solution - of 0.2. the Areas of the image layer made of the maleic anhydride copolymer that have become insoluble as a result of the irradiation were completely resistant to the copper etching solution.

B e i s ρ i el 8

One operates as in Example 1, but using, as the material for the image layer a 5 ° / _o Methyläthylketonlösung strength of a 1: 1 copolymer of 'Octadecylvinyläther and maleic anhydride. which has a specific viscosity - comprises from 0.5 - measured in l ° / _o sodium Methyläthylketonlösung. The areas of the layer that have become insoluble as a result of the irradiation are completely impermeable to the etching solution and are not attacked by it.

Example 9

The procedure described in Example 3, but used as a material for the image layer a 5 ° / _o strength Methyläthylketonlösung of a 1: 1 copolymer of maleic anhydride and isobutyl vinyl ether having a specific viscosity - measured in l ° / _o sodium Methyläthylketonlösung - from 0, 3 has. After irradiation with electrons - the dosage was made so that a density of 5 · 10 ¹⁴ electrons per cm ² resulted - there were areas in the image layer which had become insoluble and which were completely resistant to the copper etching solution.

B e i s ρ i e 1 10

One works again as in Example 9 specified, but used as a material for the image layer is a 2.5 ° / _o by weight solution of a copolymer of maleic anhydride and styrene, which has a specific viscosity - measured in l ° / _o sodium Methyläthylketonlösung - 1.8 having. Following the irradiation and the further treatment described in Example 9, an insoluble polymer negative is obtained which is completely impermeable to the copper etching solution. The removal of the insoluble parts of the image layer from the laminate after the end of the etching process is again easily possible by immersing it in a dilute ammonium hydroxide solution.

Example 11

A copper-coated laminate of the type described in Example 3 is provided with an image layer, for which a 2.5 ⁿ / _o solution of a copolymer of maleic anhydride and ethylene is used, which has a specific viscosity - measured in 1 ″ methyl ethyl ketone solution - of 2.0 The formation of the insoluble polymer negative

is achieved by exposing the image layer to electron radiation, the density of which ^{corresponds to 10 14} electrons per cm ² (acceleration by 14 kV). The physical removal of the areas that have not become insoluble is achieved by immersion in an acetone solution. The laminate is then subjected to a heat treatment at a temperature of 150 ^{° C. for about 1} _{1/2 hours.} Following the heat treatment, the etching is carried out in the manner described in Example 1. The insoluble areas of the image layer are then removed by immersion in a dilute ammonium hydroxide solution, which is easily possible despite its excellent resistance to the etching solution.

Example 12

In turn, is performed as described in Example 3, but coated the copper-clad laminate with a material which is coated from a 5% solution of a 1: 1 copolymer of maleic anhydride and Hexadecylvinyläther exists which has a specific viscosity - measured in O, l ° / _O iger methyl ethyl ketone solution - of 0.1. Also in this case, the 14η-soluble areas of the image layer that are present after the electron irradiation are extremely resistant to the copper etching solution.

Further embodiments of the invention are described in accordance with Examples 13 to 15 below which crosslinking agents are added to the material forming the image layer, so that the sensitivity of the maleic anhydride copolymer is increased against the electron irradiation.

B e i s ρ i e 1 13

A copper-coated laminate of the type described in Example 3 is coated with a 10% methyl ethyl ketone solution of a 1: 1 copolymer of maleic anhydride and isobutyl vinyl ether, which has a specific viscosity - measured in 1% methyl ethyl ketone solution - of 0.6. Approximately 1% Ν, Ν'-methylene-bis-acrylamide was added as a crosslinking agent. The laminate coated in this way is then exposed to electron irradiation, the density being 1.6 · 10 ¹² electrons per cm ² . The parts of the image layer which have not been irradiated, ie which have not become insoluble, are then removed by treatment with acetone solution. The laminate is then treated directly with the copper etching solution of the composition described in Example 1; intermediate heat treatment was not switched on. The presence of the methylene-bis-acrylamide as a crosslinking agent made it possible to reduce the electron density considerably during irradiation without the impermeability of the layer to the etching solution being reduced. In addition, the remaining portions of the image layer after development were easily removed with a dilute ammonium hydroxide solution.

60 Example 14

The procedure of Example 13 was repeated, but ° / ₀ divinylbenzene was now used as a crosslinking agent l. Electron irradiation with an electron density of 1.6 · H) ¹³ electrons per cm ² resulted in a polymcine negative which was not attacked by the etching solution, but could easily be removed with dilute alkali.

Example 15

The procedure according to Example 13 was repeated, but now 1% acrylamide was used as the crosslinking agent. By electron irradiation with an electron density of 8 · 10 ¹³ electrons per cm ² , a polymer image is obtained which is completely resistant to the etching solution.

The following examples illustrate the beneficial effect of long-chain ethylenically unsaturated Hydrocarbons on the sensitivity of the copolymer to electron irradiation.

Example 16

A .kupferbeschichtetes laminate is coated with a material selected from a 10 ° / ₀ Methyläthylketonlösung strength of a 1: 1-interpolymer. Maleic anhydride and isobutyl vinyl ether; the copolymer has a specific viscosity of 0.6 - measured in l ° / _o sodium Methyläthylketonlösung - on. About 1 percent by weight, based on the weight of the copolymer, 1-hexadecene is added. In the case of electron irradiation with an electron density of 1.6 · IQ ¹⁴ electrons per cm ² , a polymer image that is resistant to the etching solution results, which can nevertheless be easily removed by treatment with dilute alkali. The resistance of the parts of the image layer that have become insoluble to the etching solution is considerably better than when the same procedure is carried out without 1-hexadecene.

Example 17

This example describes the use of aluminum as a base.

An aluminum plate is treated with a 10 ° / ₀ Methyläthylketonlösung strength of a copolymer of maleic anhydride and isobutyl vinyl ether having a specific viscosity - coated comprises of 0.6 - measured in l ° / _o sodium Methyläthylketonlösung. The plate coated in this way is then exposed to electron irradiation at an electron density of 5 · 10 ¹⁴ electrons per cm ² (accelerated at 14 kV). The parts of the image layer that have not become insoluble are then removed with acetone. The polymer image is completely resistant to the hydrochloric acid solution used to etch the aluminum surface. The resistance to the etching solution results from the fact that the etching action of the hydrochloric acid solution is limited exclusively to the areas of the aluminum plate which are not covered by the polymer image layer.

Example 18

This example describes the use of a silicon wafer plate as a base. A chemically polished silicon wafer plate of type N was coated with a 10% strength methyl ethyl ketone solution of a 1: 1 copolymer of maleic anhydride and isobutyl vinyl ether, which had a specific viscosity - measured in Vo'ger methyl ethyl ketone solution - of 0.6. The thus-coated plate was "C and then heated one at a niektronenbestrahlung HlektroneiuliclUe \ on 5 ■ 10" for 15 minutes at HX) electrons per cm'- (accelerated at 14 kV ") exposed. The become not insoluble portions of the layer were subsequently by Treatment with

Acetone removed. The thus formed resistant polymer image was found to be completely resistant to a solution of 4 parts of 70 ° / _o nitric acid, 3 parts of acetic acid and 3 parts of 48 ° / _o hydrofluoric acid, which is used for etching silicon.

Example 19

This example uses a glass pad explained.

A glass plate which had been etched with 6 ° / ₀ hydrofluoric J acid, was treated with a 10 ° / _o by weight Methylketonlösung a 1: l-copolymer of maleic anhydride and isobutyl vinyl ether having a specific viscosity - measured in l ° / _o sodium Methyläthylketonlösung - of 0.6, coated. The image layer was then exposed to electron irradiation at an electron density of 5 × 10 ¹⁴ electrons per cm ² (accelerated at 14 kV). The parts of the layer which had not become insoluble were then removed by treatment with methyl ethyl ketone solution. The become insoluble portions of the image layer were completely resistant ° / _o strength hydrofluoric acid solution, which was used for glass etching against a 25th

In Examples 20 to 23 further embodiments of the invention are described according to which Resistant polymer images can be made from coatings made from mixtures of either polymaleic anhydride and polyalkyl vinyl ethers or one of these two polymers with maleic anhydride copolymers exist.

Example 20

A mixture of 1 part of polymaleic anhydride and 1 part of polyvinyl methyl ether is dissolved in 40 parts of acetone. A copper clad laminate is coated with the above solution. The thickness of the layer is 5 microns. This is then exposed to electron irradiation at an electron density of 5K) ¹¹ electrons per cm ² (accelerated at 14 kV). The non-irradiated parts of the layer are then removed by treatment with methyl ethyl ketone. The polymer image is a short time, about 15 minutes, heated to 15O ⁰ C; thereafter it is resistant to a copper etching solution, while it can be easily removed by dilute alkali.

Example 21

A mixture of 4 parts of polyvinyl methyl ether and 1 part of polymaleic anhydride is dissolved in 100 parts of acetone. A copper-clad laminate is coated with this solution. The thickness of the applied layer is 7.5 microns. This layer is exposed to electron irradiation with an electron density of 5 · 10 ¹⁴ electrons per cm ² (accelerated at 14 kV). The non-irradiated parts of the layer are then removed by treatment with methyl ethyl ketone. The resulting polymer image is resistant to the copper etching solution, but can be easily removed with diluted alkali.

Example 22

A mixture of 1 part of polymaleic anhydride and 3 parts of a 1: 1 copolymer of maleic anhydride and isobutyl ether is dissolved in 40 parts of methyl ethyl ketone. A copper-clad laminate is coated with this solution. The thickness of the applied layer is 5 microns. The irradiation takes place with electrons at an electron density of 10 ¹⁵ electrons per cm ² . The non-irradiated parts of the layer are then removed by treatment with methyl ethyl ketone. The resulting polymer image is resistant to a copper etching solution, but can easily be removed with diluted alkali.

B e i s ρ j e 1 23

A mixture of 1 part of polyvinyl methyl ether and 5 parts of a 1: 1 copolymer of maleic anhydride and isobutyl vinyl ether is dissolved in 300 parts of methyl ethyl ketone. A silicon wafer plate is coated with this solution. The thickness of the applied layer is approximately 0.5 microns. The mixture is then ^{heated to 150 °} C. for 15 minutes; this is followed by irradiation with electrons at an electron density of 10 ¹⁵ electrons per cm ² . The non-irradiated parts of the layer are then removed by treatment with methyl ethyl ketone. The resulting polymer image is resistant to an etching solution of 4 parts of 70% nitric acid, 3 parts of acetic acid and 3 parts / _o hydrofluoric acid 48 °.

Example 24

One works again as indicated in Example 23, but uses an oxidized silicon base as it is Usually used for the production of microcircuits, instead of the silicon wafer plate. Following the removal of the non-irradiated areas of the layer with methyl ethyl ketone, the oxidized surface, the silicon base etched with the following solution:

Ammonium bifluoride 1400 g

Hydrofluoric acid 420 ml

Water 2100 ml

Claims (5)

1 2 with the inclusion of a master copy and a selective patent claims: tive removal of the exposed and unexposed areas of the layer by treatment with suitable 1. Process for the production of relief images solvents. The by the solvent treatment A part of the substrate that is exposed on a layer carrier can then be crosslinked by radiation Layer to be treated by irradiation rectly in a suitable manner, being treated with corpuscular radiation until the rays apply the type of treatment according to the type of application Areas of the layer become insoluble which is aimed at the reproductive process. The above and then removing the sequence of process steps that is not described in Areas of the io made insoluble by the rays are particularly evident in such reproduction processes Layer proved to be favorable by washing with a suitable solvent, which are the reprosides, characterized by the production of very detailed and complicated patterns that a radiation-sensitive layer that acts and in which the image with large Ge homopolymer or mixed polymer of the accuracy and precision must take place, z. B. at the linic anhydride, which takes about 10 to about 15 printed circuit board manufacture. Repro-65 Molar percent maleic anhydride production processes of the latter type are always used holds, and a specific viscosity of about 0.05 associated with an etching process in which the Oberbis about 5.0 is used. surface of the documents physically modified or in 2. The method according to claim 1, characterized in that it is treated in a different manner so that a stable draws that the maleic anhydride polymer 20 is a relief-like image of the template. If one Maleic anhydride homopolymer is. Required or desired, the illustration can go through 3. The method according to claim 1, characterized by using suitable coloring agents made visible draws that the maleic anhydride interpoly become. merisat a copolymer of maleic acid and the previously known processes for hydride with at least one monoethylene 25 management of the processes described above unsaturated vinyl monomers. mainly photolytic and require in- 4. The method according to claim 3, characterized thereby the use of negative-forming distinguishes that the copolymer is a mixed poly materials, which are an essential component merisate from maleic anhydride with methylvinyl substance, which is under the influence of light ether is. 30 energy, d. H. under the influence of visible rays 5. The method according to claim 1, characterized or by UV light, becomes insoluble. In the case of typical records that the radiation-crosslinkable layer of the last-mentioned type, for example, additionally contains a crosslinking agent, which consists of a monomeric compound that is polymerizable under the action of light, materials are used that contain at least one ethylenically unsaturated, non-35 monomer - or more such monomers - aromatic double bond between adjacent vinyl type, which or which has a CH ₂ = C oGruppe bared carbon atoms that have, in connection with a photopoly-direct neighborhood, contain an electronegative merization initiator. When the Photopoly group is activated. merization initiator is a substance 40 the polymerization of the vinyl monomer component upon exposure can initiate. The negative formation occurs in the above-mentioned products Reason for the fact that the photolytically induced photopolymerization to the formation of insoluble The invention relates to a method of producing 45 parts in the places of the image that occurs during the of relief images in an exposure on a layer support exposed to the action of light rays brought radiation-crosslinkable layer through loading. This procedure comes with many modifications Radiation with corpuscular radiation until the and deviations currently on the broadest base summer rays affected areas of the layer are insoluble and specifically used. Thus, according to the USA. Patent and then removing the non-50 2 816 091 and British Patent 825 948 Areas of the copolymers of maleic anhydride made insoluble by the rays as a light layer by washing with a suitable solution-crosslinkable compound for the image-forming layer medium. used. In order to carry out such processes, it is known that in the production of but in each case the use of visible Relief images required for printing forms or by printed 55 light or by UV light. This Erfor-Circuits However, use of photographic methods means a significant disadvantage. can e.g. B. those in which the radiation has a lot of photopolymerization initiators are difficult Polymer image (polymer negative; polymeric resit image) accessible and consequently extremely expensive which acts as a cover, so that playful. The formation of a polymer negative from within different treatment of the structural stability reaching from image 60, solvent-covered Document is made possible. This process stability, reproduction quality, etc. requires it Production of printing forms or of printed forms, in addition, the application is extraordinarily high Circuits are generally based on the following exposure values and thus the use of the light principle: A source of high energy and / or the application is longer on the surface to be treated highly light-sensitive layer applied, d. H. a 65 exposure times to allow the required exposure Layer that is chemically and / or physically achieved. Of course, it does not change if they exclude high-energy radiation that one or more of the components, is set; then the layer in the photopolymerizable layer material is exposed