MXPA97006505A - Curable coating composition, procedure to cover a material with the same and article coated obten - Google Patents

Abstract

A radiation curable coating composition comprising a PVC resin, an acrylic or methacrylic compound and a reaction reactive urethane oligomer, a method for coating a material, comprising the steps of applying a coating composition to the material, is also described. according to the invention, heating to heat cure the coating composition and irradiating the composition for radiation curing the coating composition, an article comprising a material coated with the composition according to the invention is also provided, the invention is useful in particular for coating elastic vinyl flooring materials

Description

COMPOSITION OF CURABLE COATING, PROCEDURE FOR COATING A MATERIAL WITH THE SAME AND ARTICLE COATED OBTAINED FIELD OF THE INVENTION This invention relates to a radiation curable and heat-curable composition for reusing sheet materials, more in articulates but not exclusively. for top coating of materials for vimlo floors the sticos, and for sheet materials reversed + i two with the cured composition. The invention also extends to a process for preparing materials of ho a.

BACKGROUND OF THE INVENTION "They usually prepare spent coatings of vimlo flooring products from plastisols, which are dispersions of the fine particles of reams in a plas-i fi er." Most plastisols for vmilo flooring products are formulated using mixed PVC emulsion reams with primary and secondary plas + i fi tters, extensions, abilizers and other additives, after being applied to a substratum, for example a subs + ra + o of fiel + ro or a glass fleece, By means of scattered coating, the plasti-ol layer is melted by heating at an elevated temperature.The spent coating surfaces of vmilo-use materials can also be prepared with a dry powder or color mixture as described in US Pat. French Patent FR?, 54?,? 60 published on April 14, 1984. These dry mix powders are prepared to par + ir PVC suspension reams, [• > plasti f "? cadores, is + abí 1 izadores, extensions and other additives. l, e prepare in a mixer of the Henschel type. The dry mix powder is applied to a felt or vimlo substrate and melted heated to an elevated temperature. Clear spent coatings can also be prepared by mixing PVC suspension resins, plasticizers, stabilizers, extensions and other additives in a Banbury mixer and calendering or extending the product to various calibers. This calendered sheet is then laminated to any of the different substrates, for example a PVC-based film, a felt, a glass fleece, or a non-woven sheet. Worn-out layers of vinyl or plastics made of PVC plastisols or dry powder mixes or a shear mixer (for example, Banbury mixer) show several imitations and disadvantages, such as retention of brightness and insufficient, resistance to wear and insufficient abrasiveness, stain resistance, scratch resistance, resistance to aggradability, resistance to caliber and resistance to various agents uirruos. Some of these problems are further aggravated by the migration of plasticizers to the surface of the worn layer.

In order to improve "the use properties of the thermoplastic layers, several modifications for the plast isol compositions, dry mix and shear mixer * have been opposed, principally by changing the quantity and type The change in the amount and type of external plasti fi ers has not produced any substantial improvement.External plasti fi ers conventionally used in PVC compositions include dialkyl-f-thalates, for example f + alato of dioc + ilo It has been proven that these conventional plas- ticators are insanti sfac + epos for several reasons, one of which is that they have a tendency to regrow to the surface and leave the surface.This leads to undesirable characteristics, It is also known to laminate PVO internally. This is done, for example, by copying a small amount of ethylene or propylene with the vinyl chloride, so that PVC containing a a small amount of full e or polypropylene incorporated in the base structure of the polymer. The small amount of full e + or propylene can be up to about 10% of the total weight of the PVC polymer. It has been proven that internal plastification is unsatisfactory in view of many limitations in terms of applications, formulations and operation. Plastics have also been proposed which have a resin component other than PVC (for example, see U.S. Patent 3,935,330, U.S. Patent 4,100,318, U.S. Pat. 4,216,107, Patent of F.U.A. 4,217,396, Patent of F.U.fi. 4,393,187 and Patent of E.U.A. 4,598,009). These coatings, or superiors, although they show mechanical resistance, usually sati factory, by themselves are not free of problems. The additional top coating and the process by which it is applied may adversely affect the properties of an underlying foamable plast layer and damage the foam cells and causing reduction in the level of dent. Also, since the expensive polyurethane layer is also thin. In some cases, they can be too thin to prevent the migration of plastifers from the base layer to the surface of the backing. Such migration can be prevented by increasing the thickness of the polyurethane top layer, but this makes the flooring materials more expensive. Most of the top layers of polyuret-t are not prepared by covering the polymer base layer that can be formed, for example, from a PVC plastisol, a polyolefin, a polyester, a polyamide, a polyepoxy or a polyacrylate , with a liquid composition of monomers (UV curable) or polymers (based on solvent or water) which composition is subsequently cured at an elevated temperature or is cured with UV to produce an entangled, mechanically resistant, entangled polyurethane coating. The liquid composition of monomers or polymers has a low viscosity which decreases with increasing temperature, before the upper layer becomes solid by interlacing. As a result, the polyurethane top coating is usually of unequal thickness, to the monomer or low viscosity polymer composition flowing in any dented valley .. Another disadvantage, with a foamable material, is that the hot melt viscosity of the polynucleotide composition is very low for pi-eve to go Exhausting gases from the underlying foamed layer or foaming pLastisol »In order to prevent this from happening, in the past a layer of a composition having a melt viscosity has been placed between the foamed or foaming plastisol layer and the composition of polyure + anus. A suitable composition having a high melt viscosity which has been used for this purpose is a PVC resin of high temperature melt viscosity plastifi ed .. FR 2,379,323, published on September 1, 1978, describes a composition of top coating which contains, in addition to the usual polyurethane polymers, an e + i ionically saturated compound. After being applied to a spiral substrate but before being thermally cured, the composition is irradiated with U.V. or an ionization radiation or is heated to a low temperature by infrared radiation. This causes the polymerization of the ethylenically saturated compound, which increases the hot melt viscosity of the composition and changes it to a solid state. The partially entangled composition creates a high temperature melt flow barrier film which prevents the escape of gases from the foamed bottom layer when the latter melts at a high temperature. The cainent and unsaturated compounds used for this purpose are very expensive monomers. A two-step reversing procedure is described in the U.S. Patent. 3,935,330. A coating composition, comprising thermally curable and radiation curable components, is first partially cured by exposing it to ionization or non-ionization radiation and the cure is then completed by a heat treatment. The ionization radiation is a radiation produced by an electron beam or electron that generates sources. Non-ionizing radiation is a radiation produced by carbon-ARC, Tungsten filament lamps, solar lamps, Mercury's arc, Xenon arcs or any other source of radiation of violet or visible light. Including thermally curable components in the coating composition and adding the thermal cure step improves the properties of the coating as compared to the radiation curved coatings only. The Patent of E.U.A. No. 3,935,330 clearly refers to the coatings to be applied to wood and metal, and this method of processing is not practical for foaming products.

BRIEF DESCRIPTION OF THE INVENTION It is an object of the invention to provide a new composition that can be used, for example, to coat a wall covering or a ready-made canvas, more preferably, to prepare a flooring for flooring materials or other flooring materials, which The flooring is substantially free from the disadvantages of the worn layers known in the prior art and does not require an additional top coating * protector. Another object of the invention is to provide a method for coating a substrate with the new coating composition, to prepare materials for elastic floors substantially free of the disadvantages of the materials known in the prior art and which do not require a Additional reversal additional protector. Thus, in accordance with one aspect, the invention provides a radiation curable coating composition comprising a PVC resin, an acrylic or methacrylic compound and a urethane reactive oligomer with radionuclide. According to another aspect, the invention provides a heat curable or cur'able coating composition with radiation comprising a PVC resin that is substantially or completely free of internal or external plasticizers, and an acrylic or methacrylic compound.

According to still another aspect, the invention provides a transparent, radiation curable flexible sheet composed of a PVC resin that is substantially or completely free of internal or external plasticizers and is dissolved with an acrylic or methacrylic compound. According to another aspect, the invention provides an article comprising a material coated with a heat cured composition and cured with radiation comprising a PVC resin, an acrylic or methacrylic compound and a urethane oligomer reactive with radiation. According to yet another aspect, the invention provides an article comprising a material coated with a heat cured composition and cured with radiation comprising a PVC resin that is substantially or completely free of internal or external plastics, and a acrylic or methacrylic compound. According to yet another aspect, the invention provides an article comprising a material coated with a flexible, radiation-curable flexible composition composed of a PVC resin that is substantially or completely free of internal or external plastifiers dissolved with an acrylic or rnet acp 1 ico. According to yet another aspect, the invention provides a flooring material comprising a substrate and a topcoat, said topcoat prepared by thermal fusion and radiation curing a coating composition comprising from 35 to 140 parts by weight of a PVC emulsion resin, from 30 to 80 parts by weight of an acrylic or e + acrylic component, and from 4 to 65 parts by weight of an odor or urethane curable with radiation. According to yet another aspect, the invention provides a material for floors comprising a substrate and an upper coating, said top coating prepared by thermal fusion and radiation curing of a coating composition comprising from 75 to 140. parts by weight of a PVC emulsion resin, from 35 to 80 parts by weight of an acrylic or metacrylic compound and from 4 to 65 parts by weight of a urethane oligomer reactive with radiation. According to another aspect, the invention provides a method for coating a material, which method comprises applying to the material a coating composition comprising a PVC resin, an aepic or metacrylic compound and a urethane oligomer reactive with radiation, heating to heat-cure the coating composition and irradiate the composition to radiation cure the coating composition. The composition can be applied to the material before or after heating. In accordance with yet another aspect, the invention provides a method for coating a material, which method comprises applying to the material a heat curable and radiation curable coating composition comprising a PVC resin that is substantially or completely free of internal or extemal plastifiers, and an acrylic or metacrylic compound, heating to heat cure the coating composition and irradiating the composition to radiation cure the coating composition. The composition can be applied to the material before or after heating.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES OF THE INVENTION In one embodiment, the composition according to the invention is prepared and applied to a substra + or co or a low viscosity mixture, in the manner known to those skilled in the art. After being applied to the substrate, the coating composition is heated to a temperature and for a period sufficient to melt the composition, for example approximately 2 minutes at 200 ° C alcohol. The time and temperature required to gel and melt the composition will depend on the particular composition but can be determined promptly by ru n test. If the substrate is a foamable substrate, for example, a plastisol containing a heat-activated blowing agent, the molten coating composition and the expanded substrate may be enhanced or otherwise formed chemically and / or mechanically. Thereafter, the coated composition is immediately exposed to ionization radiation or non-ionization, for a period necessary to interlock the intertwinable components of the composition. The entanglement freezes any dent and transforms the thermoplastic, flexible layer of the gelled composition into a high-gloss, clear, high-modulus film that is resistant to stain and abrasion. In another embodiment, the composition is prepared as a dry mixture. The dry mix composition is formed into a sheet in suitable calender rolls at an appropriate thickness and laminated to a substrate. The substrate can be, for example, a felt, glass fleece or a layer of a suitable polymer material such as PVC, polyolefin, polyester, polyester, polyepoxy, polyacrylate and the like. Infrared heating is usually used in the rolling step. The hot laminated film is then embossed and immediately exposed to ionization or non-ionization radiation, for a period necessary to interlock the reactive components. This freezes the design obtained by enhancing and converting the thermoplastic, flexible film into a clear, tenacious, high modulus film, resistant to stain and abrasion. Another way to produce a sheet in hot calender rolls is to use a shear force mixer such as a two-roll mill, a Banbury mixer or an extruder. These articles are used to transform the starting materials into a composition ready for application in hot calender rolls. The Banbury mixer, the two-roll mill or extruder dissolves the resin with the acrylic or metacrylic compound and the reactive oligonucleotide with radiation and forms a hot high-viscosity paste. This paste is then fed to the calender rolls (Encyclopedia of PVC by NASS, second edition, vol.3). The composition according to the invention does not require any solvent or diluent that can be released into the atmosphere during gelation and curing. The composition also requires no external or internal plasticizer, so that some degradation of the backing can not occur due to the migration of the plastivers to the surface of the layer. Therefore, the compositions of the invention are normally completely or substantially free of any internal or external plastifyer. Coatings prepared from the composition of the invention have superior tensile strength, creep resistance, chemical resistance and stains as well as excellent gloss retention .. The composition may contain a heat stabilizer, suitably in a cant i ( Jad of about 0.5 to 10 parts by weight Due to its exceptional mechanical strength, use and staining, the prepared spent layer of the composition of the invention does not require a top protective layer.This makes the flooring materials less costly than vinyl flooring materials comprising a polyurethane protective layer The composition of the invention can be applied to thermoplastic vinyl layers, to provide a superior protective layer. Said layer possesses excellent wear properties and is less expensive than the additional polyurethane protective layers. The composition of the invention can also be applied as a spent layer to materials other than the thermoplastic material. The composition according to the invention can be prepared in the form of a low viscosity paste, a dry mix or a PVC and a rnon mix using a high shear mixer, such as a mixer.Banbury. In one embodiment of the invention, a low viscosity paste is purchased from 35 to HO, preferably 55 to 120, approximately 100 parts by weight of a PVC emulsion resin is preferred, from 30 to 80, preferably from 50 to 60, most preferred approximately 65 parts by weight of an acrylic or methacrylic resin, from 0.5 to 65, preferably from 4 to 20, most preferred about 7.5 parts by weight of a reactive reactor with urethane radiation, if 0.5 to 10, preferably from 7, most preferred about 6.0 parts by weight of a heat stabilizer * is required and , if required, from 0.1 to 10, preferably from 0.75 to 4, and preferably 1.0 parts by weight of a photomer. The preferred low viscosity paste may contain other additives, such as an air-releasing agent, a U.V. light stabilizer. and an anti-oxidant. The amount of the air releasing agent is usually in the range of 0.5 to 5.0, preferably 0.5 to 3.0, most preferred about 0.5 parts by weight .. The amount of the antioxidant is from 25 to 1,000, preferably from 100 to 700, most preferred about 500 pprn. The low viscosity paste should have a viscosity of 200c? S to 4000c? S, preferably from 600cps to 2000c? S, most preferred approximately ROOcps, as measured by Brool? 'S HBT viscometer on 20 r *? m and 26 ° C. In another embodiment of the invention, a dry blend of from 75 to 140, preferably from 85 to 130, preferably about 100 parts by weight, or from a PVC suspension resin, from 35 to 80, preferably from 0 to 7 most preferred is about 50 parts by weight of an acrylic or meta-plastic mono-active, from 0.5 to 65, preferably from 5 to 30, most preferably about 15 parts by weight of a reactive monomer with urethane radiation, if required. 0. 5 to 10, preferably 6, most preferred of about 4. 0 parts by weight of a heat stabilizer and, if required, 0.25 to 15, preferably 4, most preferably about 2.0 parts by weight of a photoiner. The dry mix may contain other additives, such as a lubricant and a drying agent. The amount of lubricant is usually 0.5 to 3.5, possibly 0.75 to 3.0, most preferred about 1.0 part by weight. the amount of the drying agent is usually from 1.0 to 10.0, preferably from 2.5 to 6.5, most preferably from 3.5 parts by weight. The dry mix can be prepared by mixing the different ingredients under high shear force and subjecting them to mild heat. As the mixture is heated, the PVC particles absorb the liquid materials present, so that a dry powder composed of PVC particles is formed where the liquid materials are absorbed. The particles tend in some way to be sticky, due to the residual amounts of liquid material on the surfaces of the particles. To combat this tackiness, a drying agent may be added to the mixture, for example an additional small amount of PVC or Cab-0-S? Powder. The dry mix is then a stable powder, somehow free of sand in appearance, which can be stored until it is required to be used. In another embodiment of the invention, a PVC suspension resin is mixed with the acrylic or methacrylic monomer, the urethane reactant with radiation, a heat stabilizer, if required, in a high shear mixer, such as a Banbury mixer, and then calendered on hot rollers to form a sheet that can be quickly laminated. Apart from the presence of a lubricant, for example zinc stearate, the components and amounts present in the high shear mixing mixture may be the same as the dry mixture. However, the effect of the high shear force on these components is to cause the formation of a hot viscous mass that must be used immediately. Thus, the high shear force mixture is fed directly from the high shear force mixer to the calender rolls to form the sheet. The PVC emulsion resins that can be used * in the compositions of the invention are those that are normally used for clear coat applications. They should have a relative viscosity of 2.05 to 3.40, referenced from 2.30 to 2.65. Examples of resins which are suitable for use in the compositions of the invention and which are commercially available include Oxy 605, Oxy 75HC, Oxy 1755, Oxy 1757 and Oxy 80HC, all produced by Occiden + al Chemical Ltd. Similar products are available from other manufacturers, such as BF Goodrich, Borden Chemicals, Nors Hydro (Pevil-on resins), Solvic, A + ochern, Huís and Goodyear. Oxi resins produced by Occidental Chemical I + d are preferred. The PVC suspension resins that can be used in the compositions of the invention are polymers having a relative viscosity of 1.56 to 2.52, preferably about 1.6. Examples of such resins are Oxy 160 from Occidental Chemical Ltd. or VC 47B, VC 58, VC 95 PM, VC 100 PM and VC 100 T, products of Borden Chemicals. Similar resins are available from other manufacturers, such as B.F. Goodrich, Borden Chemicals, Norsk Hydro (Pevikon resins), Solvió, Ato he, Huís and Goodyear. The product Oxy 160 of Occidental Chemical I td is referred to as acrylic compounds (including me + acp 11 eos) suitable for use in the compositions of the invention include mono-, di- and multifunctional acrylic monomers.

Examples of suitable acrylic monomers available commercially include such esters as acpla + or 2-phenoxy + yl (SR-339), acrylate + etrah? rofurfuril (SR-285), isode ilo acrylate (SR-395), isoborrholate acrylate (SR-506), acr * iaia + or 2- (2-ethoxy? -ethoxy) e + 1 lo (SR- 256), diacline + or polyethylene glycol 400 (SR-344), diacrylate of tp propi lengl i col (SR-306), polyethylene glycol diaclet 200 (SR-259), dipen + pentacyl pentacline i + ol rnonohydroxy (SR-399), rnetacpla + o of isodecyl (SR-242), dirnet acrylate + or ethylene glycol (SR-206), C14-C15 of oligo gum finished in etacplato (SR-2100) , tpme + ilol propane ethoxylated triac plate (SR-454), dimethyl acp + + bisphenol A rnetox liado (SR-340), polyethylene glycol dimethacrylate 600 (SR-252), dunetacp lat o of 1, 6 -hexaned? ol (SR-239), isobornyl metacrylate (SR-423), tene + tere + telanganic (SR-- 209), trime + acpla + or de + pme +? lol propane (SR-350) , triethylene glycol di-ethacrylate (SR-205), di-acrylate lat. polyethylene glycol (SR-210) and diethylene glycol dialysis (SR-231), all products of Sarto er. Of these, SR-209, SR-210, SR-423, SR-231, SR-205 and SR-206 are preferred. Particular preference is given to SR-209, SR-205, SR-210 and SR-231. Acylated high viscosity onomorphs and oleic monomers and acryl monomers having lower viscosity can be diluted to maintain the viscosity of the paste composition within the acceptable range. The radiation component of reactive reagent radiation is primarily responsible for imparting toughness and gloss retention to the cured layer of the composition of the invention. It is an essential component for applications where superior surface tenacity is required, + as flooring materials. For applications for floors, the urethane reactive radiation reactant should normally be included in the composition, in an amount of at least 4 parts by weight. For less demanding applications in terms of the surface properties of the coating, such as wall coverings, the amount of this relatively expensive component can be reduced or eliminated. The radiation-reactive urethane ointment component has ethylenically terminal, saturated double bonds and can be prepared in the following manner. A polyisocyanate or t-isocyanate is reacted with a polyol, suitably a diol or triol. The hydroxy groups of the polyolefin react with isocyanate groups of the dusocyan + or to form a polyurethane repellant. The molar ratio of isocyanate to polyol is chosen so that the polyurethane prepolymer has isocyanate + o terminal groups. This prepolymer is then reacted with a hydroxyalkyl acrylate or ester of rnetaepl ato. the hydroxy groups of the acter or rnetacr * oster? They react with the terminal isocyanate groups of the polyurethane prepolymer, so that a urethane oligomer having terminal portions of acrylate or etaclate is formed. When the composition of the invention is subjected to radiation, a polymerization reaction occurs in the double liquors of the acrylate or acrylate portions, creating bonds between the molecules of the urethane oligomer. Of course, it is possible to use * mixtures of d soci anates and tp i socianates and of diols and triols. The use of functional reagents will lead to entanglement and will result in higher viscosity urethane oligomers, which may limit the amounts of functional tp reagents that can be used. Suitable diisocyanates for use in the preparation of the "repolymer *" or polyurethane include 2,4- and 2,6-dusocyanate, toluene, 1,4-phenethylene diisocyanate, naphthylene dusocyanate, di-phenylalanine dusocyanate, d socianates of a, w -al qui le or such as dusocyanate of hexa ethylene and isophorone diisocyanate. Suitable polyols can be any oligonucleotides which can be prepared * with hydroxy end groups, for example, polycarbonates, poly esters, silicone materials, polyhydroxyalkis lacptates, polyhydroxyalkines, elastomeric materials such as silicone diaccolate. poiibuf adieno and polyepoxi materials.

Of the possible polyols to be used in the preparation of the urethane oiler, the silicone materials are very expensive. The polyesters give as a result olí gummers of viscosity a + a. The polyols of acpla + o and methacrylate of polyhydroxyalkyl give as a result urethane oligomers which, when used in the compositions of the invention, do not always show the degree of tenacity desired for the floor. Polyopoxy materials show a tendency to become yellow, and are also undesirably stiff for floor applications. For use on the floor, where a degree of toughness is desired in the final product, it is preferred that the polyol be an aliphatic polycarbonate polyol, a triol most preferred and a diol most preferred. Polycarbonate + or aroune + polyols are not widely available, are generally very viscous and have a tendency to become yellow. Suitable polycarbonate polyols can be based on alkylenglichols, ether glycols and alicyclic glycols or a mixture thereof. Preferred alkaline alcohols include a, straight chain glycols having between 5 and 10, most preferred 6 carbon atoms. An example of a preferred alkyl glycol is 1, 6-hexaned? Ol. In the alkylene glycol, one or more carbon atoms of the alkylene chain can be replaced by an oxygen atom, to form one or more ether linkages. An example of a preferred ether glycol is diethylene glycol. Preferred alicyclic glycols include those which do not have the following structure; 0H (C 0H ( where: x = L, 2 or 3 w = 0 10 z = 0 to 1 Preferably, x has the value 2, ie *, the alicyclic glycol is based on cyclohexane. It is also preferred that the substi uent is in the alicyclic ring is + in located in positions 1,3 or 1,4 with respect to each other. In the cyclic glycol ali, one or more carbon atoms of the alkylene chain may be replaced by an oxygen atom to form one or more ether linkages. Also, one or more of the hydrogen atoms attached to a carbon atom of the alkylene chain may be replaced by a substiuent which does not interfere with the course of the desired reaction, for example an alkyl group having between 1 and 4 carbon atoms. An example of a highly preferred alicyclic glycol is 1,4-di e + anolcyclohexa or. Suitable polycarbonate polyols that are commercially available include KM10-1122, KdlO-1733, KM10-1667 (all S + ahl products) and DESMOPHEN 2020E (Bayer * product). 00 The .AC? Latos and metacp Latos of hydroxyl which are suitable for the reaction with the polyurethane prepolymer for the polyurethane olymer include acp lates and rnetacptes of hydroxyl, and hydroxy propyl and hydroxybutyl, which are preferred the hydroxyl esters. the oligoes of ur * efano may have a viscosity that is too high for convenient handling. If this is the case, the urethane ointment may be mixed with an acrylic or inetacrylic compound which can be used as a component of the composition. For example, a preferred urethane oligomer based on a polycarbonate polyol of molecular weight in the scale of about * 500 to 2000, forms with hydroxyethyl acrylate a urethane ointment whose viscosity is greater than the optimum for handling convenience. This oligomer has been used successfully in a 3: 1 by weight mixture with ethoxylated tpmet i lolpropane tpacrylate. This version is available from the Stahl, E.U.A. of Peabody, Massachusetts, under the designation U26253. It has a viscosity of approximately 100,000 cps at 60 ° C when in midi with a Broo field viscometer using a number 3 spindle at 10 rpm, it is slightly yellow in color and has a slightly sweet odor *. The product may contain a small amount of hydroxyethyl acrylate, since this compound may be used in a molar excess when reacted with the urethane propylene to ensure complete propylene reaction. Any small excess of hydroxyethyl acrylate present in U26253 is incorporated into the composition of the invention and is crosslinked with the other components during the irradiation step and has no significant effect on the properties of the cured composition. Desirably, the urethane igomero has a fairly high weight, say approximately 100,000 or more. At lower molecular weights, the product obtained may be undesirably frigid. Other examples of suitable urethane warmers include urethane aelasts CN-966 and CN-953, CN-966 E75 (urethane acrylate with tprne triacplate + i lol propane ethoxylate) and ON-964 H75 (urethane acrylate with acrylate 2- (2-ethoxyethoxy) et i lo), all Sartorner products. Of the urethane olí gummers, U26253 is preferred. Although the presence of a urethane oiler is necessary to produce a material that has sufficient tenacity to serve as a flooring for applications where such toughness is not required, it is possible to dispense with the urethane olympus. If the PVC resin and the acrylic or methacrylic compound are mixed and then heated, the acrylic or methacrylic compound dissolves the PVC. It is possible to extrude the dissolved PVC, for example, in a transparent, flexible hose. According to another aspect of the invention, therefore, a cur'able composition is provided with radiation comprising a PVC resin that is free of external and internal plasticizers, and is dissolved by an acrylic or acrylic compound. The known heat stabilizers for those skilled in the art include metals compounds to the lime and transition metals. Examples of suitable heat stabilizers for the compositions of the invention are BZ 512 (product of Cib-Geigy) and Synpron 0144 ( product of Synthetic Products Co.). The barium zinc sterilizer 1) 2 512 is preferred. Are photoinitiators and photoinitiators required for compositions cured by r * ad? U.V. of non-ionization. It may not be necessary in this case when the acrylic or metaclic monomer and the oligopoly reactive polyamide network with radiation shows sufficient reactivity + or has a fo + oi in it, so that it does not have to be added. an additional photographer. When present, the photographers or donors must ensure the rapid and complete entanglement of the composition that has been partially cured by a heat treatment. Preferred photoinigenates are phenyl ketone derivatives. Examples of suitable photometers are Trgac re 184, Trgac e 907, Trgac re 2959, Irgacure 500, Irgacure 651 and Irgacure 369 (products of Ciba-Geigy) and Darocur 4265, Darocur 1173, and Mi cure HP-8 (products of Mere! -). Of these, Trgacure 184 is preferred. Of the auxiliary components of the compositions of the invention, phenols hindered, for example, Trganox 1010 (product of Ciba-Geigy), are preferred as nitric oxides. Organically modified siloxanes, such as BYK 3105 (product of BYK Chernie), are preferred as air-containing agents. Fatty acids, for example stearic acid, and their salts, for example z nc stearate and magnesium stearate, are preferred as lubricants. Preferred as drying agents is the molten silicon or a fine particle emulsion PVC resin having a relative viscosity of 2.05 to 2.75. Examples of suitable drying agents are Cab-0-S? L (product of Cabot Corporation) and Oxy 625 (product of Occidental Chemical L + d.) "To prepare a paste of low viscosity, both compounds + are combined , mixed completely to form a paste and the mixture is placed under vacuum, to eliminate trapped air. After the vacuum treatment, the paste is applied as a layer of a predetermined thickness to a substrate by conventional means, such as reversed backing roller, a knife on a roller, a screen coating, a spray gun. or other applicable means. The substrate covered with the paste is then heated, for example in a circulation oven, at a temperature of about 160 ° C to about 220 ° C, preferably about 200 ° C. At the time of heatingThe Intuitive ingredients dissolve the PVC resin particles initially and then form a solid homogenous loop. As a result, the opaque layer of the paste is transformed into a clear tormoplasti ca film. When a composition of the invention is applied to a plastisol layer of vi or the foamable thermoplastic, the composition has a sufficiently high melt viscosity which serves as a barrier preventing the escape of gases from the bottom-foamed layer. when both movies merge. Accordingly, and in contrast to the prior art, it is not necessary to provide an additional layer of a high melt viscosity composition simply to avoid splinters and pin holes * in the surface layer. The clear film, which makes any underlying design visible, can be enhanced or formed in any specific way. The dent can be made chemically or mechanically, in the known manner. Once the configuration is complete, if it exists, the film is cured by exposing it to ionization radiation or non-ionization, to intertwine the compose + es entiazables and to freeze any design obtained by the dent. The entanglement converts the tepnoplasti ca, flexible film into a tough layer resistant to stains and abrasion. Since the film becomes transparent after the initial heat treatment, even a thick film (10 m or more) can be quickly and completely entangled by U.V. irradiation. or E.B. For U.V. radiation an inert gas, such as nitrogen, is used to displace oxygen that causes the inhibition of entanglement on the surface. It is important that the film is completely interlaced, since 2? any remaining monomer or free standing oligomer will tend to the surface of the coating, adversely affecting your Pro ?? ages of use. Dry mixes formulated with PVC suspension resins are suitably prepared by heating the PVC suspension resin at about 50 ° C ± 15 ° C at the same time by stirring in a high shear mixer, for example a Henschel mixer. The liquid portion of the composition, composed of the acrylic or ethacrylic monomer and urethane oligomer reactive with radiation, is then gradually added while the temperature is raised to approximately 80 ° C ± 15 ° C. At this temperature the resin absorbs all the liquid. The dried mixture is then cooled to approximately 50 ° C ± 15 ° C, at which temperature drying agents can be added to ensure that the mixture will remain soak when it is cooled and stored. The dry mix can be processed in several ways before irradiation. The mixture can be calendered on hot rolls (at a temperature of about 160 ° C to 220 ° C, preferably approximately 200 ° C) to a suitable thickness (usually 2 to 30 ml), to form a sheet that is separates from the last roller, it is cooled and stored. This rolled film can subsequently be laminated, for example, on a printed sheet, heated, enhanced if required, cured with radiation and cooled. Alternatively, a layer of the dry mixture in the form of a powder can be applied to a substrate, for example a felt, using any known technique (rubber roll for watering, sifting, etc.). the layer is then melted by heating at an elevated temperature by means of a suitable heating medium, for example an air circulation oven or preferably by infrared. When heated to a temperature of 160 ° C to 220 ° C, preferably of about 200 ° C, which facilitates the cure with final radiation when a non-ionizing radiation is used, such as U.V. Another aspect of the invention consists of adding the suspension ream and the acrylic or ethacrylic monomer, reactive ur-ethane oligomer with radiation, stabilizer, photo-stabilizer and other additives such as lubricants, in a Banbury mixer of high shear strength or a Intensive two-roll mixer and forming a sheet in calender rolls. By way of example, when an upper protective layer of a dry mixture is formed, the dry mixture (20 ml) can be applied by knife coating on a felt substrate that has been coated with a film of vi or gelled print. or not printed (10 rnl). The coated felt substrate covered with the dry mix then passes through an oven (for example 2 minutes at 200 ° C) to melt dry mix. If required, the product is cooled to room temperature. A dent step, if present, is carried out on a texture cooling roller that reduces the temperature of the film. The next step of healing with radiation does not require any specific temperature. ca., The thermal gel step can be carried out * in a furnace using any * medium suitable for the generation of heat. For a low viscosity paste, this step is preferably carried out in a hot air circulation oven. For a dry mix or a mixture in a Banbury high-formula mixer, thermal gelling is preferably carried out on heated calender rolls, although an infrared heater or hot air oven can be used to melt the dry mix, if The mixture is applied as a powder to a substrate. A suitable residence time for thermal gelation is about 2 ± to minutes per minute to layers of approximately 10 rnl in thickness and at a temperature of approximately 200 ° C ± 20 ° C. This time will depend, in general, on the temperature, the thickness * of the layer and the relative viscosity of the PVC resin. The radiation curing of the thermally gelled film can be carried out with ionization or non-ionization radiation. Any source that provides non-ionizing radiation of wavelength between about 180 nm and about 400 nm, preferably between about 250 n and about 400 n, * can be used. Examples of suitable sources are medium pressure mercury lamps, non-mercury lamps that have a different spectrum than mercury lamps (xenon arc, cripton arc, carton >)ono, solar lamps) and sources of U..V. of μ? lso. Of these, the medium pressure mercury lamp is preferred. Most of the pre-ion mercury vapor arc lamps (1 to 2 t) can operate consistently at 100 or 200 watts per linear centimeter. Irradiation U.V. it is preferably carried out under a blanket of nitrogen to eliminate the oxygen inhibition on the upper surface of the cured coating. The intensity of the radiation is typically between 100 and 700 watts / square meter, preferably about 150 watts / square meter. An electron beam can be used as a source of ionization radiation. When an electron beam is used to intertwine the radioactive components, no photoinitiator is required. Also, when cured with the electronic beam, the cured film may be colored or opaque. Said films may be preferred for some applications, such as floor coverings, wall coverings and the like. Although originally developed for flooring applications, the invention compositions can be used for many other applications that require a tough coating, laminate or not to a substrate, such as wall coverings, tablecloths, canvases for boats and decks, and Similar. Felt substrates, woven or non-woven glass fiber, woven or non-woven polyester, nylon, fine cotton, cotton fabrics and the like can be used. Calendered PVC sheets or felts are preferred for floor applications. The compositions of the invention can also be used in unsupported PVC flooring products, for example, floor cover sheet elastic sheet as described in ASTM Standard F1303, classes B or C (vol.15.04). They can be used in foamable PVC and ethylene vinyl acetate (EVA) compositions. The PVC or FVA composition contains a heat activated blowing agent. The composition of the invention is applied to the foamable composition of PVC or EVA and the heat used to cure the composition of the invention also serves to activate the blowing agent, causing the PVC or EVA composition to be foamed. The thickness * of the cured layer depends on its desired application. For individual worn layers for flooring materials, this thickness will typically be in the range of from 1 ml to 50 ml, preferably from 7 ml to 15 ml, most preferably from 10 ml. The same or thickness can be used for the protective layers applied on the top * of the conventional thermoplastic plastisol layers. In this case, the preferred thickness is 5 ± 2 rnl. The following examples are illustrative of the invention and best contemplated to carry out the same, but should not limit * it.

EXAMPLE 1 A paste that contains i. - PVC emulsion resin (Oxy 751-IC) lOO.üpbw 2.- Tetraot ileglycol stellate (SR 209) 55.5pbw 3. - Urethane and triathlon canner of t r i me 111 o 1 ro pa no e t o x i 1 do, mix of: 1 in weight (U26253) 7.5 bp? 4. - Stabilizer of heat (BZ 512) 6.0pbw 5.- Photoi ni ciador (Irgacure 184) l.Opbw 6. - Siloxane air release agent (BYK3105) O.Spbw 7.- Hindered phenol antioxidant (Trganox 1010) SOOppm was prepared by mixing components 2 to 7 and adding the PVC emulsion ream. The components were completely mixed to form a paste of low viscosity and placed in vacuum for 5 minutes to remove any enclosed air. The low viscosity paste was applied on a foamable PVC film printed on felt, using an inverted roller coater or knife reverse. These coatings were cured terribly in an air circulation oven for 2 minutes at 200 ° C, foamed, chemically and / or mechanically enhanced and irradiated with a nitrogen blanket with U.V. from a medium-strength mercury arc lamp (5 seconds to 150 watts / square meter) of ultra violet radiation. The resulting ho . 48 centimeters long it was then cooled to room temperature and rolled up. The coating had a good use, resistance to stain and solvent and excellent bp 1 lo radiation. EXAMPLE 2 A dry mix containing 1.- PVC suspension resin (Oxy 160) lOO.Opbw 2. - Di et acplato de tet raet ilenglicol (SR 209) 50.0? Bw 3. - Urethane and tpmeti loipropane ethoxylated pacp lathe, 3: 1 by weight (U26253) IS.Opbw mixture 4. - Heat stabilizer (BZ 512) 4.0? Bw . - Fotoi niciador (Trgacure 184) 2.0pbw 6. - Drying agent (Cab-0-S? L) l .Opbw 7.- Drying agent (Oxy 625) 2.5? Bw was prepared as follows. The suspension resin was heated to 50 ° C ± 5 ° C while stirring in a Henschel mixer. the liquid components 2 to 5 were gradually added to the core where the temperature rose to approximately 80 ° C (± 5 ° C). After the liquid was absorbed by the resin, the dried mixture was cooled to about 65 ° C, at which temperature the drying agents were mixed. The mixture was then calendered at a temperature of 185 ° C to a thickness of 10 ml, laminated and simultane- ously enhanced on a vmilo sheet which was then irradiated under a nitrogen blanket with radiation from a mercury arc lamp. of average power (5 seconds at 150 watt / meter2). The sheet was further cooled and cut into slabs of various sizes. The coating had good use, stain and solvency resistance and excellent gloss retention EXAMPLE 3 A mixture containing i.- PVC suspension resin (Oxy 160) lOO.Ophw 2. - Tetraethylenglycol dimethacrylate (SR 209) SO.Opbw 3.- Urethane urethane and t-platelet hydrochloride efoxylate, mixture of 3: 1 by weight (U26253) lS.Opbw 4. - Heat stabilizer (BZ 512) 4.0? Bw . - Photoimager (Trgacure 184) 2.0? Bw 6.- Lubricant (stearic acid) l .Opbw was prepared as follows. All ingredients were loaded in a Banbury mixer and mixed under sufficient pressure, high rotor speed and temperature to produce a hot viscous paste that was extruded or calendered at a temperature of 185 ° C to a thickness of 10 ° C. , laminated and enhanced simultaneously on a substrate. The substrates were vinyl slab sheets that were then irradiated under a nitrogen blanket and further processed as in Example 2.

EXAMPLE 4 The impact of the components and the curing conditions on the physical properties of the coatings was studied using the components of example 1. The results of these studies are briefly described in table 1. Composition A had only components 2, 3 and 5 (acrylic monomer, urethane gum, and photometer) and He cured only by U.V. Compositions B and C were complete compositions of Example 1 and were cured by thermal fusion only (B) and by thermal fusion followed by U.V. (O. Films were prepared on a release paper that was removed prior to measurements.) Tension strength was measured using samples of 2.54 x 7.62 cm with a Lloyd strain gauge. * Solvent strength was measured using a machine for carving Taber and metí] ethyl ketone (25 cycles).

TABLE 1 Composition Strength Thickness Elongation Resistance T / d ten- [] solvent film Tml] s on í k g l A. 6 - 0 excellent fragile B. 9 10.89 460 po re 2.66 B. 9 3.9 450 poor 0.96 C. 7 27.22 25 excellent 8.57 C. 8 39.92 25 excellent 8.76 C. 6 18.23 25 excellent 6.7 3 b The above results clearly show that the film prepared from the components that can be linked only (acrylic mono-ion + urethane olomer) does not have sufficient mechanical strength and flexibility. (A) Adding the PVC resin and curing the composition by thermal fusion alone, without radiation curing, results in a highly flexible coating that achieves an acceptable tensile strength but that lends a poor solvent resistance. (B) Curing the same composition by thermal fusion and U.V. It results in good tensile strength, acceptable flexibility and excellent solvent resistance.

EXAMPLE 5 Several acrylic monomers or met acr * were evaluated? urethane ores and olí gomeros by direct substitution in the basic formulation of example i. The results of these evaluations are briefly described-) in Tables 2 and 3. The stain resistance was given using wax-like man or shoes for coffee shoes Kiwi, mustard, iodine ink and asphalt sealer *. The rollers were applied for 1 hour, 24 hours and 7 days at room temperature.

TABLE 2 Monomer Viscosity Liberation Color Resistor of the revet i - a a c i *? 11 co nnot nomo r ro n t o r stains Cornent ap os Functional Monkeys SR-339 light mist good yellow SR-285 very poor poor poor melts in reo i SE -395 400cps i nguna a an 1 the good cracks in foundry SE- 506 just cl ro good smell, cracks Diameter SR-344 high poor poor bl reco re v pp < or SR-306 poor poor milky poor SR-259 very poor poor slightly cl milky ring vo it or Pont aacri latos SR-399 ex paddling- poor slightly poor viscosity mind high am n 1 or rnuy a ta Me + acp l SR-242 rnuy poor high cracked in cast iron SE-23 good poor milky good tixot ropí co SR-2100 fair milky poor SE - 54 very high Dimetacri latos SR-252 poor SR-239 poor SR-206 just pobro fog good smell 11 ge ra 1 i ger'o SR-209 underneath a clear better good irenet acp l to < :, R-350 just good or poor TABLE 3 Olí gome ros de u re t ano CM-966 high cla or pobro CN- 66E75high clear poor U26253 very high clear good The evaluation indicates that most of the onofunctional acp lates dissolve the PVC resin quickly, resulting in high viscosity compositions. Several products, such as SR-506 (isoborm 1 ac acrylate), provide acceptable coatings for floor applications. Some functional devices (eg, SR-344 and SR-306) and functional m acylates (e.g., SR-399) tend to produce compositions having high viscosities and films that are colored or milky. Some of these acplates also show an incompatibility with the basic composition, resulting in vomit on the surface of the cured coating. Most of the evaluated acrees make acceptable films and can be used in the compositions of the invention. Of these, SR-209, SR-506 and SR-423 are considered as the most suitable for floor applications. Those with high viscosities can be modified by the addition of low viscosity acrylics or methacrylates.

Claims (3)

1. NOVELTY OF THE INVENTION CLAIMS ] .- A radiation-curable composite composition comprising a PVC resin that is subsurfacely filled with internal or external plastifiers, an acrylic or methacrylic compound, and a radiation-reactive oligomer.
2. 2. A composition according to claim 1, further characterized in that the urethane oligomer reactive with radiation comprises an aeric or rnetacplica portion fixed to a urethane prepolymer.
3. 3. A composition according to claim 1, further characterized in that the urethane oligomer reactant with radiation is based on a polycarbonate polyol ali (-atic, 4"). A coating composition curable with radiation of 35 to 140 parts by weight of a PVC emulsion resin with a relative viscosity between 2.05 and 3.40, from 30 to 80 parts by weight of an acrylic or methacrylic compound, from 0.5 to 65 parts by weight of a reactive jeweler oligomer with radiation, from 0.5 to 10 parts by weight of a heat stabilizer and from 0.1 to 10 parts by weight of a photoimage 5. The composition according to claim 4, further characterized in that said emulsion resin No PVC is free subs + ancialmon + oo Complemente de P Last ifi cadoi * es i nt o rno or xtor no "6. A curéable coating composition with radiation of 75 140 parts on weight of a resin of h PVC suspension with a relative viscosity 1.56 and 2.52, from 35 to 80 parts by weight of an acrylic or metallic compound, from 0.5 to 65 parts by weight of a reactive urethane odorant with radiation, from 0.5 to 10 parts by weight of a heat exchanger. * and from 0.25 to 15 parts by weight of a LO photoi ni ciado r. 7. The composition according to claim 6, further characterized in that said PVC suspension resin is free substi- tially or completely from internal or external plasticizers. 8. A process for coating a material, said process comprising the following steps: a) applying to the material a coating composition comprising a ream of PVC, an acrylic or netacrylic compound and a trace of? Reactive reagent with radiation; b) heat up 20 curing * the coating composition with heat; and c) irradiating the composition for radiation curing the coating composition. 9. A procedure according to claim 8, further characterized in that the PVC resin is a PVC suspension ream, the coating composition is cured with heat and formed into a laminar * before being applied. To the material, the laminar * is applied to the material and after it is cured with radiation. 10. A process according to claim 8, further characterized in that the PVC resin is a PVC suspension resin and the coating composition is applied to the material before being cured with heat * and cured with radiation. 11. - A method according to claim 8, further characterized in that the PVC ream is a PVC emulsion resin and the coating composition is applied to the material before it is heat cured and cured with radiation. 1.2. - A process according to claim 8, further characterized in that the material to be coated comprises a foamable PVC plast isol, the coating composition which is applied to the non-foamed PVC plasti sol and heated to cure the composition 13.- A process according to claim 12, further characterized in that after heating but before irradiation, the foamed plastisol and the cured coating composition are enhanced. heat 14. A process according to claim 8, further characterized in that the PVC resin is a PVC emulsion ream with a relative viscosity in R + 2.05 and 3.40 and the components of the coating composition. they are mixed to form a paste of low viscosity and are released from any enclosed year before heating the composition. a r * e? vindication 8, further characterized in that the PVC resin is a PVC suspension resin having a relative viscosity between 1.56 and 2.52 and the components of the composition are mixed with heating to form a dry powder before heating the composition. 16. A method according to claim 8, further characterized in that the urethane oligomer not reactive with radiation is based on a polio! from pol i c rbonato al i á + i co. 17. A method according to claim 8, further characterized in that the PVC resin is substantially or completely free of internal or external materials. 10.- An article comprising a material coated with a composition cured with heat * and cured. with radiation comprising a ream of PVC that is substantially free from all internal or external plas- tifiers, an acrylic or reactive compound, and a urethane filter reactive with radiation. 19. An article according to claim 18, further characterized in that the substrate is a felt covered with a layer of thermoplastic vinyl. 20. - An article according to claim 19, character *? Furthermore, the coating has a thickness of approximately 0.25 mm (10 ml). 21. An article according to claim 18, further characterized in that it is in the form of a flooring material comprising a substrate and an upper coating, said top coating prepared by thermal fusion and curing with a coating composition comprising from 35 to 140 parts by weight of a PVC emulsion resin, from 30 to 80 parts by weight of an acrylic or metacpionic compound and from 4 to 65 parts by weight of an oil of? radiation curable retainer 22. An article according to claim 18, further characterized in that it is in the form of a flooring material comprising a substrate and an upper coating, said top coating prepared by thermal fusion and radiation curing. of a coating composition comprising from 75 to 140 parts by weight of a PVC suspension ream, from 35 to 80 parts by weight of a chiral or rnetacrylic compound and from 4 to 65 parts by weight of a urethane oligomer reactive with radiation. 23. A heat-curable and radiation-curable coating composition comprising a PVC resin that is substantially substantially free of internal or external plasticizers, and an acrylic or acrylic compound. 24. - A method for coating a material, said process comprising the following steps: a) applying * to the material a heat-curable coating composition * and curable with radiation that comprises a PVC resin that is substantially or completely free from internal or external plasticizers, and an acrylic or ethacrylic compound; b) heating to heat cure the coating composition; and c) irradiating the composition to radiation cure the coating composition. 25. A process according to the indication 24, further characterized in that the PVC resin is a PVC suspension resin, the coating composition is heat cured and formed into a sheet before applying it to a material, the Sheet is applied to the material and cured with radiation afterwards. 26.- A procedure in accordance with claim 24, further characterized in that the PVC resin is a PVC suspension resin and the coating composition is applied to the material before curing-the condensation and radiation. 27. A method according to claim 24, further characterized in that the PVC resin is a PVC emulsion ream and the coating composition is applied to the material before curing with heat and radiation. 28.- An article comprising a coated material 4b with a Lamina formed by the curing composition with caLor * and radiation curing of claim 23. 29.- A flexible sheet curable with radiation, transp recnte composed of a PVC resin that is free substantially lalrnent eo completely of plasticators , I released with an acrylic or methacrylic compound. 30. An article that complies with a material covered with a flexible sheet that is cur'able with radiation, transparently composed of a PVC resin that is completely free of inert plastics, dissolved with an acrylic compound or etacplico