NO780340L - PROCEDURE FOR COATING A SURFACE WITH A PLASTIC MATERIAL - Google Patents

Description

' The invention relates to a method for coating a surface with one layer of material during heating, as stated.."

in the preamble of the main claim.

It used to be common for surfaces to be coated for protection or for decorative purposes with a •• plastic material that was exposed to elevated temperatures at some stage of the manufacturing process. The invention relates to such methods and in particular methods which are designed for coating a material which expands in connection with said heating with a preferably transparent, thin protective film. By this is meant primarily the coating of material which is produced in web form and which is heat-treated in a through-pass oven. This particular process occurs, especially with floor and wall covering material, in the production of which a web of a strong dimensionally stable material, e.g. a non-woven material of glass fibre, is coated with a polyvinyl chloride paste containing an emulsifier, which after solidification to; • suitable hardness is provided with a decorative pattern of colours,

by means of a pressure process, which partly contains blowing agent inhibitors or accelerators. The web prepared in this way is then fed into a through furnace where the selectively distributed inhibitors, respective accelerators, according to the pattern, provide a selectively distributed, different kind of etching of the PVC material, whereby a relief pattern appears in register with a color pattern. However, the patterned PVC covering does not show sufficient wear resistance and must therefore be supplied with eh film with good wear resistance, good resistance to stain formation and dirt accumulation as well as high transparency, so that the underlying pattern is not obscured.

There are known processes for providing the aforementioned protective coating. According to a'generally applied

■procedure the material is coated- before it enters the oven, \ ..;.' . with polyvinyl chloride added solvent, which evaporates in the gyn, so that a relatively hard coating is obtained. The procedure can be easily carried out and has some significance for e.g. wall^1' articles, but the evaporating solvents entail disadvantages and costs due to health and environmental risks that require special measures such as explosion-proof ovens, gj en recovery facilities etc.. '. ;•:•« •; ''•''V'',W\- '-'' J

This can, according to other known methods, be avoided by adding so much plasticizer to the protective layer's PVC preparation that a suitable coating consistency is achieved. As a result of the increased plasticizer content, the disadvantage arises that the resulting end product has a wear layer that is more susceptible to abrasion, stains and dirt. ■■

In accordance with another method, an attempt has therefore been made to replace this thermoplastic with the thermoset polyurethane. -• ■ However, it has not been successful in providing a functionally, aesthetically and economically satisfactory coating of the exterior/enclosure of this plastic by previously known methods* A hybrid process has therefore been resorted to according to which a known method produced first coating of PVC is supplied with a very thin, often only approx. 0.05 mm thick, varnish film made of polyurethane. ;' A floor material produced in this way does, in factory-new condition, exhibit the good properties that polyurethane has as a coating, but due to wear and tear of the very thin polyurethane layer, these properties soon disappear.

Especially for the production of coating material, there has been a tendency to separate the product functions and choose different material compositions for different layers, so that these are maximally suitable for their individual task. The end product's properties can thereby be controlled and improved economically within a wide range. An important prerequisite is that the raw material mixture by simple methods ("pre-gelation") can be transferred to/, an admittedly solid, but easily moldable state, after which intermediate storage or further coloring and shaping operations can be carried out in addition to those carried out in the last step of the heat treatment ("out-gelation").

The purpose of the present invention is to provide a method for coating a surface with a covering layer of a, when heated, low-viscosity material> in a thickness sufficient for the anticipated wear, to a high degree uniform, if this layer -thickness is practically independent of the occurrence of a relief.

The purpose of the invention is therefore to adapt the curing process of reactive plasters to one of PVC technology's more significant methods, namely the production of relief-patterned .'. ; •' •-.T"i articles. > . '-'V: -"T ■ ''

A further beneficial technical effect has been established

in connection with the method according to the invention. With the cover layer according to the invention, the end result is obtained

a surface coating with some wrinkling. Such a not completely smooth surface is advantageous, especially when it concerns floor material, . while the rapid dulling of the surface as otherwise. 4th;' occurs when smooth, glossy floor covering materials are worn, ■[ appears only after a long time, while the shine of the wrinkled surface is not affected by wear until the tops of the surface are worn down and the lowest parts begin to be affected- • Namely, it is the latter which mainly.reflects the light and gives .the surface its shine. A further object of the invention is thus to provide a surface coating with a certain wrinkle formation.

In the following description of three embodiments of the invention, reference is made to accompanying drawings which contain five principle curves, of which curves I - III relate to the state of the art and curves IV and V to the invention. The drawings show a temperature curve I, a dimensional stability curve II for polyvinyl chloride and a dimensional stability curve III for polyurethane, as well as two dimensional stability curves IV and V which apply to a coating layer made according to the first and second variant of the present method. The description also includes tables, 1-6.

In the following, the invention will be described in connection with a method for producing a floor covering material of the type mentioned at the outset. The production of such a material includes the following steps: ■v ■ 1. Production of a highly dimensionally stable carrier, preferably of an inorganic material, e.g. glass fiber or asbestos fiber, in the form of a fiber pile- '- ' fabric (non-woven material) in web form. " 2. Coating of the carrier with polyvinyl chloride paste to which a defoaming agent has been added. 3. Printing of the solidified.pre-gelled/non-defoaming polyvinyl chloride coating with a color pattern formed from color mixtures to which certain defoaming inhibitors or accelerators have been added. Alternatively, PVC -paste of different color and different blowing agent content in a stencil printing process is applied in a figure pattern 4. Application of a low-viscosity, transparent coating material'in a thin layer (usually 0.2 - 0.4 mm)' on the printed material . '•''/ ':,'"' 5. Introduction of the material web into an oven in which, under elevated temperature, an etching of the PVC material occurs, whereby the degree of etching and thus the final thickness of the material is determined by the amount of esemiddél and-'', inhibitors and accelerators respectively in the individual surface parts. By the fact that the carrier does not: allow itself<;> to be influenced during the esing, it arises.because of this on the PVC material's free surface a relief pattern in register with the coloring the material has received. During the passage of the material in the oven, there is even a hardening gelation of said coating film. 6. The exit of the material from the oven and cooling to room temperature, whereby a floor covering material with a color and relief pattern that includes the carrier,

as well as having a surface that is coated with a transparent wear coating, is achieved.

Curve I illustrates how the material's temperature rises after entering the oven and later falls when exiting it; same. The stay in the oven is thus symbolized by the area A.: The elevated temperature means that the etching in the PVC material is initiated, and it is thereby assumed that the main part of the etching process, and hence the material's thickness increase, takes place within the area B in the figure.

Before entering the oven, coat as mentioned above

(point 4), and according to a known process, the material with a polyvinyl chloride dispersion (plastisol) which by choosing suitable v. v.' plasticizers are given a ytgaji#/?y,erdi >-;X suitable for the coating process for the dimensional stability or viscosity, the latter expression can be used when the material is in liquid phase; It

relative dimensional stability is deposited in the direction of the y-axis on curves II - V. The above-mentioned output value is represented by the connection points for curve II to the left line in the figure. 1 In connection with the heating in the oven, by which the coating is going to be heated, usually by blowing hot air against the material surface, the viscosity first rises due to the initial . gelation and possible evaporation of volatile substances (e.g. solvent) to a maximum value, because with further heating it will decrease somewhat due to the influence of the increasingly higher temperature, but a mainly unchanged shape stability is obtained during the main part of the stay in the oven, thus during the time period in which etch of the polyvinyl chloride material takes place. Upon exit from the oven and the material's cooling, it obtains a higher,..-suitable shape resistance for the application, see the right part of. '...'•■ curve II. ''• '•■/■;£'',- •■•'./..

By choosing the type and quantity of plasticizer as well as the type and quantity • of solvent in the PVC coating as well as the selection of: heating data ' ;" in the oven, the coating material can be adapted so that it has the correct

viscosity for application to the material, a.proper viscosity to form and maintain a film of the desired thickness during the oven run and to maintain a well-adjusted f mold resistance during the .-etching run. The dimensional stability of the coating material during the etching process must not be so great that the etching, which develops only low pressure, is affected in such a way that the desired relief pattern is not obtained, and the dimensional stability must not be so small either that the coating thins out on the raised relief parts.;. It is thus possible with PVC to achieve a coating for runs that functions well, with a sufficiently hard coating with suitable . adjusted thickness as the end result. As mentioned, however, PVC is not an ideal material for the protective film. For example, there are

there is a relatively large tendency for absorption and retention of ■ ink particles, for the migration of certain colors and for damage

by exposure to household chemicals and cigarette embers.

It would therefore be desirable if the coating could take place with another material, and it is thus proposed poly-:,;»._:.. ' urethane, which is formed by the reaction between polyisocyanates and -''" hydrogen donors of, among other things, the polyol type. Even this plastic material can be given a viscosity suitable for the coating process by the correct choice of components as indicated by the left line of the figure part with respect to curve III.

The reaction, which is admittedly accelerated by temperature f or-. the rise, however, needs a certain amount of time before it becomes so extensive that the dimensional stability of the reaction mixture is noticeably increased. However, the physical reduction in viscosity upon heating sets in immediately, so that the increase in temperature at the beginning results in the viscosity of the urethane components dropping strongly, which is indicated in the left part of curve III. Hardening only sets in somewhat later. is then difficult to control and continues rapidly to the final state, which prevails at the exit from the furnace.

The aforementioned conditions lead to two obvious disadvantages.

In the first stage, the viscosity is so low that the urethane component mixture "flows" around on the material surface at the slightest unevenness,..;'.' in addition to this, air drafts - as mentioned, the heating takes place "for- .:'"-steps by air blowing - produces "ripples" on the coating, which gives an uneven coating on the finished material. The other disadvantage is that when hardening is started, the dimensional stability quickly becomes so great that the esing (see area B between the dashed lines in the figure) is affected in an undesirable way, which in extreme cases can lead to nothing being achieved; actually relief patterning, meaning that the expanding material only equalizes the level differences by raising the entire already hardened wear layer. If one tries to avoid this by speeding up the hardening, on the other hand, the period of time in '..»;•< > which the viscosity is very low and thus increases the aforementioned difficulties. If you change the recipe so that the wear layer becomes

more thermoplastic, then the end product's f leak-,. dirt and \\ ;' heat resistance is so much worse that the extra costs compared to PVC seem pointless. As mentioned in the introduction, they have since refrained from using a thick, uniform coating of polyurethane.

The method according to the invention exhibits the same main steps as indicated above. However, the manufacturing step is plated and modified in such a way that the difficulties mentioned are eliminated, whereby a significantly freer choice of coating material is available. Thus, polyurethane can be applied in the form of a thick, uniform coating in such cases where this has not previously been possible.

In principle, this is achieved according to the invention by giving the coating material two main components, namely a first component which determines the properties of the coating in the finished material and which is selected mainly because of these properties, and partly another main component which has the ability to react and form a molecular network. by the influence of a factor which does not appreciably affect other constituent materials, that \ -. • be the coating's first main component or the underlying material. ■ .. • '"" ;

More specifically, one provides in a first step

a cross-linking of the coating layer's other main component, so that this is stabilized, however without adversely affecting the dimensional changes of the coated material during production or the final properties of the coating layer after . the pre- •• position.

By the fact that the second main component stabilizes the first main component in this way to an appropriate degree, this can be selected according to its desired end properties without regard to its physical properties under the aforementioned delicate parts of the forward-.-. the course of the position. The other main component is included on its side

only in the amount necessary for the formation of the network structure and does not need to significantly affect the final quality of the coating. The second main component can therefore be chosen according to its reaction properties, so that it is influenced by the aforementioned/,-■ ;•;

factor in and for the formation of a suitable adjusted molecular network....As '"previously mentioned, polyurethane is of greatest interest as the first main component, and as the second main component acrylic acid esters and/or their prepolymers can be used.

As the aforementioned factor which provides the cross-linking, the use of polyurethane and/or the coating of a foaming agent-added polyvinyl chloride heating to over 180°C must be ruled out,:,.' . while at this temperature one provides hardening of... the polyurethane or initiates the ese process. A factor of a completely different kind is, on the other hand, irradiation with high-energy radiation, e.g. light with wavelengths mainly below approx. 40Cyum or.- i-'.1'* beta rays.. Another alternative is ppp heating t. å.% e.n a temperature that is below 180°C, whereby the other main component. of course must react at this lower temperature. According to the first variant, a smaller proportion of radiation-reactive material is chosen, e.g. acrylic acid esters and/or their olipolymers which are miscible with and possibly react with a mixture of the', —v.;.'-urethane components polyisocyanate and hydrogen donors, e.g. in ! : ) PDI and polyols, coating the substrate with the mixture and irradiating it with high-energy radiation, e.g. light with wavelengths mainly below approx. 40Cyum or beta rays.. Thereby the aforementioned molecular network is formed, which reduces the excessively easy mobility of the unreacted or insufficiently reacted urethane components during the subsequent heat treatment, where the urethane reaction only in the last step leads to a coating layer with desirable application properties. (Coating material that is only based on polyesters or acrylate, on the other hand, due to its mechanical properties, is not as good as a surface coating of polyurethane, in particular not as a high-class surface layer on softened PVC). This method variant is specified in more detail in examples I and II.

According to another variant of the method, one can proceed so that the radiation-reactive material constitutes a larger proportion of the coating mixture and thus forms the first main component. The urethane components are selected so that they react quickly under moderate heat exposure from for example infrared radiators and is then responsible for the viscosity-stabilizing molecular network - during the subsequent main heat treatment which ensures. that of e.g. Impact of PVC-based substrates, e.g. ■. gelation or gelation and etching, after which the substrate with the coating material passes through a zone of energy-rich radiation, which in transfers the coating material to the final state with. the after-/; sought-after performance characteristics. This method variant specifically i-v. can be seen in more detail in example III.

In what follows, the invention will be illustrated by a

example of embodiments, however without thereby limiting the invention beyond what is stated in the main claim. In example III reference is made to the following tables 1 - 6.

Example I

A substrate consisting of paper treated with a release agent,

.coated with a foaming agent-containing, pre-gelled plastisol j ikt on which a color pattern is placed so that at least* one. of; print 7.'fr the colors contain an agent that affects the melting temperature of the ese agent, are produced according to a known method, are coated with a coating material consisting of: v

in a layer thickness of 200 µm, is made to pass a mercury high-pressure lamp with a nominal power of not less than 80 W/cm as well. a hot air oven where the material's temperature is increased. shut up approx. 200°C ■ in less than 5 minutes. ■ ' •

The article treated in this way shows a surface layer with a relief pattern and where the colors are reporting,, with good

chemical and mechanical resistance.

' Example II

On a substrate according to the preceding example, V is applied a 700 μm thick layer consisting of the mixture according to the aforementioned

Example. The web passes through a UV field as in the aforementioned example, to provide a substantially increased dimensional stability mainly in the surface of the coating. The reactions in the coating layer, like in the substrate, are later finished in a heating oven, similar to what is described in example I.

Example III

A substrate consisting of pre-gelled, filler- and pigment-containing plastisol is coated with a coating material consisting of:

is made to pass an infrared radiation field during approx.

In a minute, whereby 150°C must not be exceeded, to be later fed into a hot air oven where the material temperature is increased to / ,;;.V-.:;'ca. 200°C and finally hardened by irradiation with short-wave light=s..gm in the preceding example..'

The above-mentioned polyisocyanate can be replaced by "linkers selected from the group illustrated in Table 1, and the same applies to the hydrogen donors, Table 2, as well as the radiation-reactive component(s) exemplified in Tables'..'3 and 4. '!>>•. -'^.\ i<iif::' ; .," Nevertheless, it is absolutely free to choose other metal catalysts, table 5, and where UV light is used instead of beta radiation, it is possible to use other' photoinitiators, Table 6.

The ethylenically unsaturated double bonds can be activated

by means of organic peroxides provided that they collapse under the influence of heat, and the desired collapse temperature7/ is achieved by suitable choice of peroxide. It is thus possible to utilize a thermal and a radiation-induced reaction course, while the heating of the material in the UV field can be kept low and the efficiency of the photo-initiators is correlated to the type of ethylenic • double bond. : .?'"- It•''_'

In the curves IV. and V are illustrated in the same way as the i - curves ,-;

'■■ ■ II and III the change in shape retention in coating-' " ' ;' the material during the execution of the manufacturing process. Fig. 4 thereby shows the first manufacturing variant according to examples I and IT. First, the material is thus exposed to irradiation, area C, before entering the oven, whereby the stay in the ... oven, which was previously denoted by area A, causes etching of the substrate, which takes place in area B. As can be seen, the radiation causes a rapid increase in the viscosity of the coating material at the aforementioned cross-linking. Thereafter, no significant change in viscosity occurs until the etching process r!. is almost complete, whereby the first main component hardens to -r therein final high form resistance.'.'•'' y- U,-'^^ ' ,-'

j Curve V relates to example III; In curve V denotes. D '•'■, the radiation, with infrared light after which the oven pass is done

(area A). After exiting the furnace and final annealing (area B) during which only an insignificant increase in viscosity occurs, the final hardening is provided by the aforementioned short-;. '' wavy radiation, designated area E in curve V...•

As appears from the description and examples, and as also appears from the following patent claims, the basic idea of the invention is to allow an auxiliary component to be included in the starting material,?:]'/. , for the coating layer. This auxiliary component is chosen so that it can be brought to form a molecular network before the heating, which is necessary for the final treatment of the product, is carried out. In this way, when choosing the main component for the coating material, one will not be limited by its properties during the heating process, but the material can be chosen freely according to the own; creates what you want it to exhibit in the final state. Man". ; ' can thus choose a material which, at least in part of the heating process, normally exhibits far too low a viscosity to

give an acceptable end result. By cross-linking the auxiliary component, a stabilizing effect is achieved, as mentioned

of the coating layer which enables the process to be carried out.-, Within the framework of this inventive concept, the invention can to-' ; is relaxed by the use of different materials and different '■

product types. An important modification, which does not, however, limit the invention, is thus the production of articles made of PVC with a relief pattern and coated with a polyurethane adhesive. , <

Tables

Table 1

The polyisocyanates can be aromatic, hydroaromatic or aliphatic and contain two or more isocyanate groups per : molecule, e.g. tolylene diisocyanate, diphenylmethane diiocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate and prepolymers of . these. V' The hydroaromatic and aliphatic, two- to four- • functional polyisocyanates are preferred.

Table 2 Compounds with active hydrogen according to Zerewitinoff

(so-called hydrogen donors) can be polyols, e.g. ethylene- -' ';■ glycol, butanediol, trimethylolpropane, pentaerythritol, sorbitol;' polyamines such as ethylenediamine, polyethylenepolyamine; sulfur-containing compounds or compounds with different reactive groups, ■ e.g. thioglycol, thiourea, diethanolamine, hydroxyethyl acrylate;

as well. even compounds with a higher molecular weight, e.g. polyester polyols or polyether polyols, preferably, with molecular weight , below 3000. and equivalent weight above 150. V».■-■ ■.

Table 3 -V ,';■'"-Compounds which polymerize under the influence of UV light,' i.e." V radiation with wavelengths 200-400/um, is most often made up of acrylic acid esters and their derivatives, e.g. hexyl acrylate, butanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol monohydroxy triacrylate and their by molecular enlargement, for example, by esterification, derived prepolymers sold under different trade names ("Uvimer" from Polychrome Corp. /■/" ' ' vK

•"Pl ex" from Rohm GmbH, "Ebecryl" from VCB) . ■ ■ >- ,-;<r;>\!

Table 4 Compounds which polymerize under the influence of electron radiation are characterized by the presence of ethylenic unsaturation in the molecules, e.g. acrylic acid esters, methacrylic acid esters, allyl derivatives. and sold under trade names such as "Sartomer" (Ancomer Ltd.).

; Table 5 ■"' ■'■ Metal catalysts consist, for example, of cobalt, tin, magnesium, lead, zinc octoate, -naphthenate, -oleate, -linoresinate or of organometallic compounds such as dibutyltin dilaurate etc.

Table 6 :.'.'.'>.■ The photoinitiators belong to different chemical types, e.g. ■ ,\. acetophenone, benzophenone, anthraquinone, benzaldehyde, ethylphenyl- ' V glyoxalate, carbazole, benzyldimethyl ketal; tioxanthone.. , !^;';: i • ■ " ■

Claims (7)

1. Procedure for coating a surface with a plastic '. material during heating, comprising the following steps? • ■■{■■'■■'■ r1-■•. :>,' -■ preparation of a substrate to be coated; ,'"^> ■;,,.»•,. - coating the substrate with a layer of a material which, due to the properties of a main component, exhibits low viscosity when heated; heating the material to a predetermined tempera-, ^ , turn for a change of state of the substrate </v>': -7 • ■■^1:'' 'ir- <v> V' .'' : <f> f characterized by "'■ . '"";' .•- - that another component of a reactive material is added to the coating material with the property of forming a molecular network under the influence of a physical factor that deviates from the physical one. f prosecutor. which up- . (the heating to the predetermined temperature■ constitutes, '•!''.'•.■' >Ki:' so that through the molecular network is achieved' a first I; ' r,.1:..! stabilization of the coating layer to a firm, but _ • ' yielding state of shape retention,' at least during the said viscosity-lowering heating; .and that the material before the said heating is exposed .to "'.l; <;.> the physical factor which provides a fornething', •. of the other component of the coating material'f or •:■! ,-"'v stabilization of this..' 2. Procedure as stated in claim 1, 'character i" see .t by that a thermosetting plastic is chosen as the main component; - that as the second component a material \ like ', contains at least one ethylenic double bond per molecule and which polymerizes under the influence of high-energy radiation, e.g. ultraviolet or party neutral trawling; - that the material is exposed to one energy before heating. rich radiation, e.g. ultraviolet or particle-;' radiation, so that the other component polymerizes','and-,\ ;": forms the molecular network; and that the heater is at such a high temperature that it hardening of the main component takes place. 3. Procedure as stated in claim 2, characterized by that polyisocyanates are used as the main component, together with polyfunctional hydrogen endona£pjfts.r Æ.o/ner1 •■' prone to reaction with these, e.g. polyols, polythiols, polyamines, for forming a polyurethane adhesive; and - that a compound containing at least one group with an active hydrogen atom and an ethylenically unsaturated bond is used as the second component, e.g. esters 7*7.. of acrylic acid with polyfunctional alcohols or 7-''" esters of allyl alcohol with polybasic acids. 4. Method as stated in claim 3, characterized by the following steps in combination: preparation of the substrate, preferably by coating •■ .< :' ning of a mainly dimensionally stable:,carrier with a 7 : plastic material; $»'': "»-^>- £ \ coating the substrate with said main component' . which.' contains a mixture of polyisocyanates and with these reaction j ons. available polyfunctional hydrogen-.'' ' 7: -f, donors, e.g. polyols, polythiols, polyamines / - .'.;.'•' 7 with more in an equivalent ratio of between 1:5 and'5:1, j-'7:7.; preferably between 1:2 and 2:1> as well as with the aforementioned "other" component containing a majority of ethylenically unsaturated compounds, for example compounds containing at least one group with an active hydrogen atom and an ethylenically unsaturated bond, e.g. esters' of acrylic acid with polyfunctional alcohols or esters of 7' allyl alcohol with polybasic acids, which amount to 1-85 weight percent of the mixture; introduction of the material into a facility for irradiation and heating, whereby it in turn achieves • ,,737 hardening of the acrylate,• change of state of under- ..' !'' the layer's plastic material and curing of the urethane plastic, "' whereby the curing time for the latter ' is'; adapted.in;slik77r that it is essentially thermoplastic under the main '7 part of the change of condition for the substrate:' 5 i Process as specified in claim 1, characterized in that compounds such as ':'.'.•-';!'.\ are used as the main component. contains at least one group with an active hydrogen atom'* and .{^V. ; ■;> an ethylenically unsaturated bond, f ■. e.g. esters of acrylic-7 acid with polyfunctional alcohols or esters of ay.7..,J-allyl alcohol with polybasic acids; that a mixture of is used as the second component polyisocyanates together with polyfunctional hydrogen- . donors that are prone to reaction with these that the second component is hardened to form molecular; v' the web before said heating by means of a pre-heating to a predetermined temperature which is lower than that predetermined for the first-mentioned heating; and w . - that the main component is polymerized at the end of.'. the former heating by means of exposure ^ay/^^V!'^;" the material to energy-rich radiation, e.g.Y ultra- ..' , violet or particle radiation. ' \ 6. Method as stated in claim 5, '•'" .■' *'.',•.' ; characterized by the following steps in combination:,.; <1-> , ; - preparation of the substrate, preferably by coating an essentially dimensionally stable carrier with a plastic material; . coating the substrate with said main component - . ;. containing a mixture of polyisocyanates.• and• with ■ r - ..,,-polyf unks j onel hydrogen donors which are inclined,/V.v' to react with these, e.g. polyols, polythiols, polyamines-with more, in an equivalent ratio of between ■1:5 and 5:1, preferably between .1:2 and 2:1,. as well as with said second component containing a plurality of ethylenically unsaturated compounds, e.g. f compounds containing at least one group with active hydrogen-; :,*;,; atom and an ethylenically unsaturated bond,, e.g. esters of ■ acrylic acid with polyfunctional alcohols or esters' of allyl alcohol with polybasic acids, which constitute 1 -. ;~'"' 1-85 percent by weight of the mixture; introducing the material into a furnace for heating and irradiation, whereby a is obtained in turn hardening of the polyurethane components, condition pre- .:. ring/n of the substrate's plastic material and a polymer---\ ?. -V isation of the ethylenically unsaturated double bonds,' whereby the urethane components are chosen so that they provide an essentially still thermoplastic coating material during the main part of the change of state for the substrate and acquire their final properties only during that ;: 'radiation-induced polymerization. • Trrvvrk; 7. Method as specified in any of the preceding claims, used in connection with a substrate which, during the heating period, receives a significant increase in dimensions during etching, characterized by the following steps in combination: preparation of the substrate by coating a in all substantially dimensionally stable carrier with a plastic material -' : which by selective surface distribution in a well-known manner of easing agent and inhibitors/accelerators imparts different easing propensities by pre- different surface sections; coating the substrate with said main component .'samt-7 with said second component whereby a reactive material is used as the main : ' :' component whose - heat- ■>'•;.''•■' reactivity is so low that the material is still in an essentially plastic state in i at least the main part of the subsequent expansion and gelation or hardening process for the substrate; ''" introducing the material into a facility for irradiation and heating, whereby a cross-linking of the second component, esing and gelation of . ,. the substrate's plastic material and curing of the main component, whereby the curing time for the latter is adjusted so that it is essentially thermoplastic, : during the main part of the setting and gelation process. ? - ; ■■ ' ■ : ■■ :--;r J!v;.;v,;: ■ • r - ~ :tv i''Tr-"l;Vi.:':r