MXPA99002106A - Floor, wall or ceiling covering - Google Patents

Abstract

A floor, wall or ceiling covering which comprises one or more substantially random interpolymers prepared by polymerizing one or more&agr;-olefin monomers with one or more vinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinylidene monomers, and optionally with other polymerizable ethylenically unsaturated monomer(s). The floor, wall or ceiling covering has a good balance of properties, such as sufficient flexibility and conformability to uneven or contoured surfaces for efficient application to floors, walls, or ceilings, sufficient scratch resistance, sufficient indentation resistance, indentation recovery and/or sufficient abrasion resistance.

Description

RECU BRI MY FLOOR ENVIRONMENT, WALL OR ROOF FIELD OF THE I NVENTION This invention relates to floor, wall or ceiling coatings. The present invention relates particularly to floor, wall or ceiling coatings made of one or more polymeric layers.

BACKGROUND OF THE INVENTION Materials for floor and wall coverings should have a wide variety of properties, which sometimes are not compatible. An important property of materials for floor and wall coverings is a good conformability to uneven or contoured surfaces to allow efficient application of the material to floors and walls. Particularly important for the materials used for floor coverings are good resistance to wear, abrasion, scratches and crevices and good slit recovery to reduce scratches and visible cracks in furniture and rolling objects, such as office chairs. Materials for floor and wall coverings should also allow the inclusion of a high amount of a usual filler to allow the production of floor and wall coatings of a wide range of hardness. The desired hardness of a flooring material varies widely depending on where the floor covering is used, for example, in public or private buildings or in the type of rooms where floor coverings are used. The desired hardness of a material for floors it also varies widely depending on its mode of application, for example if it is applied in the form of endless sheets or in the form of tiles. Well-known floor coatings are based on polyvinyl chloride (PVC). PVC-based materials have many desirable properties, such as good fill acceptance, flexibility and scratch resistance. However, in more recent years attention has been focused on the disadvantages of PVC-based flooring material, such as its chlorine content, which forms hydrogen chloride upon combustion. Therefore, a lot of effort has been made by the expert technicians to find replacements for PVC-based floor, wall or ceiling coverings. German patent application DE-A-43 24 137 discusses the advantages and disadvantages of various PVC-free floor coatings. He argues that floor coatings based on ethylene / vinyl acetate copolymers are not expensive and useful in a wide variety of applications, but that their residual content of vinyl acetate comonomer and their relatively low thermal stability requires special precautions in production of floor coverings. Floor coverings based on low density ethylene / butene or ethylene / 1-ketene copolymers are also mentioned. It is argued that these copolymers allow high filling, which also allows the control of the flexibility and hardness of the floor. On the other hand, it is said that it is difficult to provide these copolymers with a lacquer or a topcoat to improve their wear resistance, due to insufficient adhesion between the olefinic copolymer and the lacquer or finishing layer. To solve these problems, DE-A-43 24 127 suggests a multilayer synthetic board, wherein at least one layer contains an ethylene / acrylate copolymer. Unfortunately, the ethylene / acrylate copolymer is tacky in the production process and provides low abrasion resistance. WO 96/04419 describes a sheet material suitable for use in or as a floor covering, which comprises a polyalkylene resin in intimate admixture with at least one additive comprising a filler. The polyalkylene resin has a relatively narrow molecular weight distribution (MWD) and a small amount of long chain branches. It is produced by a simple site catalyzed polymerization of at least one linear, branched or cyclic alkene having from 2 to 20 carbon atoms. This sheet material has good properties, such as excellent abrasion resistance and high mechanical strength. However, drag recovery and scratch resistance of the sheet material is not very good in general. Obviously no current simple material can fully satisfy the wide range of required and desired properties of floor and wall coverings, which depend on how and where the floor, wall or ceiling covering is applied and used and which are often even incompatible. . Therefore, the desired properties are prioritized based on the desired end use of the floor and wall coverings and the materials are selected from according to it. To increase the variety of materials and material properties which are suitable for floor, wall and ceiling coatings, it would be highly desirable to provide floor, wall and ceiling coatings based on other polymers than those used in the prior art. It would be particularly convenient to provide floor, wall and ceiling coatings, which have a good balance of the desired properties, particularly sufficient flexibility and conformability for uneven or contoured surfaces for efficient application to floors, walls or ceilings, sufficient scratch resistance, Sufficient slit resistance, slit recovery and / or sufficient abrasion resistance.

BRIEF DESCRIPTION OF THE INVENTION In one aspect, the present invention relates to a floor, wall or ceiling covering, which comprises one or more substantially random interpolymers prepared by polymerizing one or more α-olefin monomers with one or more monomers. vinylidene aromatics and / or one or more aliphatic or cycloaliphatic vinylidene monomers clogged, and optionally with one or more other polymerizable ethylenically unsaturated monomers. In another aspect, the present invention relates to the use of the aforementioned substantially random interpolymer (s) to produce floor, wall or ceiling coatings.

DETAILED DESCRIPTION OF THE INVENTION By the term "floor covering", as used herein, is meant an article with a length and width which are substantially greater than its thickness, such as a sheet, tile or board, which is useful for covering at least a portion of a floor, which is adhered to the floor by means of static pressure or a fastening agent, such as an adhesive system. "Substantially greater" generally means at least 10 times greater, preferably at least 50 times greater, more preferably at least 100 times greater. By the term "wall covering" or "roof covering" as used herein, is meant an aforementioned article, such as a sheet, tile or board, which is useful to cover at least a portion of a wall or ceiling and which is adhered to the wall or ceiling by means of a fastening agent, such as an adhesive system, nails or screws. The term "interpolymer" is used herein to mean a polymer, wherein at least two different monomers are polymerized to make the interpolymer. The term "copolymer" is used herein to denote a polymer, wherein at least two different monomers are polymerized to make the copolymer. The interpolymers employed in the present invention include, but are not limited to, substantially random interpolymers prepared by polymerizing one or more α-olefin monomers with one or more vinylidene aromatic monomers and / or one or more monomers of aliphatic or clogged cycloaliphatic vinylidene, and optionally with another or other polymerizable ethylenically unsaturated monomers. Suitable α-olefin monomers include, for example, α-olefin monomers containing from 2 to about 20, preferably from 2 to about 12, more preferably from 2 to about 8 carbon atoms. Such preferred monomers include ethylene, propylene, butene-1,4-methyl-1-pentene, hexene-1 and octene-1. Most preferred are ethylene or a combination of ethylene with C2-8-α-olefins. These α-olefins do not contain an aromatic portion. Suitable vinylidene aromatic monomers, which can be used to prepare the interpolymers employed in the filled polymer compositions of the present invention include, for example, those represented by the following formula: Ar (CH2) n R1 - C = C (R2) 2 wherein R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to about 4 carbon atoms. carbon, preferably hydrogen or methyl; Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C 1-4 alkyl, and C 4 haloalkyl; and n has a value from zero to about 4, preferably from zero to 2, most preferably zero. Exemplary monovinylidene aromatic monomers include styrene, vinyl toluene, α-methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds, and the like. Such particularly suitable monomers include styrene and derivatives substituted with lower alkyl or halogen thereof. Preferred monomers include styrene, α-methyl styrene, styrene derivatives substituted with phenyl ring or lower alkyl - (C-C4), such as, for example, ortho-, meta-, and para-methylstyrene, the halogenated ring styrenes , para-vinyl toluene or mixtures thereof and the like. A most preferred aromatic monovinylidene monomer is styrene. By the term "clogged aliphatic or cycloaliphatic vinylidene monomers", it is meant additive polymerizable vinylidene monomers corresponding to the formula: A1 R1 C = C (R2) 2 wherein A1 is an aliphatic or cycloaliphatic, sterically bulky substituent of up to 20 carbons, R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to about 4 carbon atoms, preferably hydrogen or methyl; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to about 4 carbon atoms, preferably hydrogen or methyl; or alternatively R1 and A1 together form a ring system. By the term "sterically bulky" is meant that the monomer bearing this substituent is normally incapable of addition polymerization by standard Ziegler-Natta polymerization catalysts in a comparable ratio to ethylene polymerizations. A-olefin monomers containing from 2 to about 20 carbon atoms and having a linear aliphatic structure such as propylene, butene-1, hexene-1 and octene-1 are not considered as clogged aliphatic monomers. The preferred aliphatic or clogged cycloaliphatic vinylidene compounds are monomers in which one of the carbon atoms bearing the ethylenic unsaturation is tertiary or substituted quaternary. Examples of such substituents include cyclic aliphatic groups, such as cyclohexyl, cyclohexenyl, cyclooctenyl, substituted alkyl or aryl ring derivatives thereof, tert-butyl, norbornyl, and the like. The most preferred aliphatic or cycloaliphatic cysteine vinylidene compounds are the various substituted isomeric vinyl ring derivatives of cyclohexene and substituted cyclohexenes, and 5-ethylidene-2-norbornene. Particularly suitable are 1 -, 3-, and 4-vinylcyclohexene.

The interpolymers of one or more α-olefins and one or more monovinylidene aromatic monomers and / or one or more aliphatic or clogged cycloaliphatic vinylidene monomers employed in the present invention are substantially random polymers. These interpolymers usually contain from about 0.5 to about 65, preferably from about 1 to about 55, more preferably from about 2 to about 50, most preferably from about 20 to about 50, particularly from about 30 to about 50 mole percent of at least an aromatic vinylidene monomer and / or aliphatic or cycloaliphatic vinylidene monomer clogged and from about 35 to about 99.5, preferably from about 45 to about 99, more preferably from about 50 to about 98, most preferably from about 50 to about 80, particularly from about 50 to about 70 percent mole of at least one aliphatic α-olefin having from 2 to about 20 carbon atoms. Another or other polymerizable ethylenically unsaturated monomers include deformed ring olefins, such as norbornene and norbornenes substituted with C? -10 alkyl or C6? Aryl, with an exemplary ethylene / styrene / norbornene interpolymer. The number average molecular weight (Mn) of the interpolymers is usually greater than about 5,000, preferably from about 20,000 to about 1,000,000, more preferably from about 50,000 to about 500,000. The melt index l2 according to Method A of ASTM D 1238, condition E, is generally from about 0.01 to about 50 g / 10 min. , preferably from about 0.01 to about 20 g / 10 min. , more preferably from about 0.1 to about 10 g / 10 min. , and most preferably from about 0.5 to about 5 g / 10 min. The glass transition temperature (Tg) of the interpolymers is preferably from about -40 ° C to about + 35 ° C, preferably from about 0 ° C to about + 30 ° C, most preferably from about + 10 ° C up to approximately + 25 ° C, measured according to differential mechanical tracking (DMS). The density of the interpolymers preferably is from about 0.95 to about 1.1 1 g / cm3, more preferably from about 0.96 to about 1.05 g / cm3, most preferably from about 0.97 to about 1.03 g / cm3. Particularly preferred α-olefin / vinylidene aromatic interpolymers contain from about 30 to about 50 mole percent of at least one interpolymerized vinylidene aromatic monomer and a Tg from about 15 ° C to about 25 ° C. Polymerizations and removal of unreacted monomer at temperatures above the auto-polymerization temperature of the respective monomers may result in the formation of some amounts of homopolymer polymerization products, resulting from the polymerization of free radicals. For example, in preparing the substantially random interpolymer, an amount of atactic vinylidene aromatic homopolymer may be formed due to the homopolymerization of the aromatic vinylidene monomer at elevated temperatures. The aromatic vinylidene homopolymer can be separated from the interpolymer, if desired, by extraction techniques such as selective precipitation of the solution with a non-solvent either for the interpolymer or the aromatic vinylidene homopolymer. For the purposes of the present invention, it is preferred that no more than 20 percent, preferably less than 15 percent by weight, be present, based on the total weight of the aromatic vinylidene homopolymer interpolymers.

Substantially random interpolymers can be modified by grafting, hydrogenation, typical functionalization, or other reactions well known to those skilled in the art. The polymers can be easily sulfonated or chlorinated to provide functionalized derivatives according to established techniques. Substantially random interpolymers can be prepared as described in U.S. Application No. 07 / 545,403 filed July 3, 1990 (corresponding to EP-A-0 416, 815) by James C. Stevens et al. , and in the allowed US application number 08 / 469,828, filed on June 6, 1995, all incorporated herein by reference in their entirety. Preferred operating conditions for such polymerization reactions are pressures from Atmospheric temperatures up to 3,000 atmospheres and temperatures from -30 ° C to 200 ° C. Examples of suitable catalysts and methods for preparing the substantially random interpolymers are described in U.S. Application No. 07 / 545,403, filed July 3, 1990 (corresponding to EP-A-416,815); US Serial Application No. 547,718, filed July 3, 1990, (corresponding to EP-A-468,651); US Application No. 07 / 702,475, filed May 20, 1991 (corresponding to EP-A-514,828); US Application No. 07 / 876,268, filed May 1, 1992 (corresponding to EP-A-520,732); US Serial Application No. 884,966, filed May 15, 1992 (corresponding to WO 93/23412); U.S. Patent No. 5,374,696, filed January 21, 1993; US Serial Application No. 34,434, filed March 19, 1993 (corresponding to WO 94/01647); US Application No. 08/241, 523, filed May 12, 1994 (corresponding to WO 94/06834 and EP 0,705,269); as well as the US patents: 5,055,438; 5,057,475; 5,096,867; 5,064,802; 5, 132, 380; and 5, 189, 192; 5,321, 106; 5,347,024; 5,350,723; 5,374,696; 5,399,635; 5,460,993 and 5,556,928, all patents and applications incorporated herein by reference in their entirety. The substantially random aromatic α-olefin / vinylidene aromatic interpolymers can also be prepared by the methods described by John G. Bradfute et al. (W. R. Grace &Co.) in WO 95/32095; by R. B. Pannell (Exxon Chemical Patents, Inc.) in WO 94/00500; and in Plastics Technology, page 25 (September 1992), all incorporated herein by reference in their entirety. Also suitable are substantially random interpolymers which comprise at least one a-olefin / aromatic vinyl / vinyl aromatic / α-olefin tetrad described in US application No. 08 / 708,809, filed September 4, 1996 by Francis J Timmers et al. These interpolymers contain additional signals with intensities greater than three times the peak-to-peak noise. These signals appear in the range of chemical change 43.75 to 44.25 ppm and 38.0 to 38.5 ppm. Specifically, the highest peaks are observed at 44.1, 43.9 and 38.2 ppm. A proton test NMR experiment indicates that the signals in the chemical change region 43.75 to 44.25 ppm are methine carbons and the signals in the 38.0 to 38.5 ppm region are methylene carbons. In order to determine the 13-NMR carbon chemical changes of the described interpolymers, the following procedures and conditions are employed. A polymer solution of five to ten percent by weight in a mixture consisting of 50 percent by volume of 1,1, 2,2-tetrachloroethane-d 2 and 50 percent by volume of chromium trisdacetylacetonate 0.10 molar in 1, 2 is prepared. , 4-trichlorobenzene. The NMR spectra are obtained at 130 ° C using a reverse gate decoupling sequence, a pulse width of 90 ° and a pulse delay of five seconds or more. The spectra are referred to as the methylene signal isolated from the polymer assigned at 30,000 ppm.

It is believed that these new signals are due to sequences involving two vinyl aromatic monomers from head to tail preceded and followed by at least one α-olefin insert, eg, a ethylene / styrene / styrene / ethylene tetrad, in where the styrene monomer insertions of said tetrads occur exclusively in a 1, 2 (head-to-tail) manner. One skilled in the art understands that for such tetrads involving an aromatic vinyl monomer other than styrene and an α-olefin other than ethylene that the ethylene tetrad / vinyl aromatic monomer / vinyl aromatic monomer / ethylene will give an increase to the peaks carbon-13 NMR similar, but with slightly different chemical changes. These interpolymers are prepared by conducting the polymerization at temperatures from about -30 ° C to about 250 ° C in the presence of such catalysts, such as those represented by the formula (MR'2 wherein: each Cp is independently, each occurrence, a substituted cyclopentadienyl group p-linked to M; E is C or Si; M is a group IV metal, preferably Zr or Hf, most preferably Zr; each R is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl or hydrocarbylsilyl, containing up to about 30, preferably from 1 to about 20, more preferably from 1 to about 10 carbon atoms or silicon; each R 'is independently, each occurrence, H, halo, hydrocarbyl, hydrocarbyloxy, silahydrocarbyl, hydrocarbylsilyl containing up to about 30, preferably from 1 to about 20, more preferably from 1 to about 10 carbon or silicon atoms, or two R groups 'together can be a 1, 3-butadiene substituted with C 1 -10 hydrocarbyl; it's 1 or 2; and optionally, but preferably in the presence of an activating cocatalyst, such as tris (pentafluorophenyl) borane or methylalumoxane (MAO). Particularly, suitable substituted cyclopentadienyl groups include those illustrated by the formula: wherein each R is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl or Isilyl hydrocarbyl, containing up to about 30, preferably from 1 to about 20 more preferably from 1 to about 10 carbon or silicon atoms, or two R groups together form a divalent derivative of such a group. Preferably, R independently, each occurrence is (including all isomers where appropriate) hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl, or (where appropriate) two such R groups are link together forming a fused ring system, such as indenyl, flueorenyl, tetrahydroindenyl, tetrahydrofluorenyl or octahydrofluorenyl. Particularly preferred catalysts include, for example, racemic (dimethylsilanediyl (2-methyl-4-phenylindenyl)) zirconium dichloride, 1,4-diphenyl-1,3-butadiene (dimethylsilanediyl (2-methyl-4-phenylindenyl)) racemic zirconium, di-C1-4 alkyl (racemic dimethylsilanediyl (2-methyl-4-phenylindenyl)) zirconium, di-C1-4 racemic (dimethylsilanediyl (2-methyl-4-phenylindenyl)) zirconium, or any combination thereof and similar. Additional preparative methods for the interpolymer in the present invention have been described in the literature. Longo and Grassi (Makromol, Chem., Volume 191, pages 2387 to 2396 [1990]) and D'Anniello et al. (Journal of Applied Polymer Science, Volume 58, pages 1701 to 1706 [1995]) reported the use of a catalytic system based on methylalumoxane (MAO) and cyclopentadienyltitanium trichloride (CpTiCI3) to prepare an ethylene-styrene copolymer. Xu and Lin (Polymer Preprints, Am. Chem. Soc, Div. Polym. Chem.) Volume 35, pages 686, 687 [1994]) have reported copolymerization using a MgCl2 / TiCl / NdCI3 / AI (iBu) 3 catalyst for give random copolymers of styrene and propylene. Lu et al (Journal of Applied Polymer Science, volume 53, pages 1453 to 1460 [1994]) have described the copolymerization of ethylene and styrene using a TiCl / NdCI3 / MgCl2 / AI (Et) 3 catalyst. Sernetz and Mulhaupt, (Macromol. Chem. Phys., V. 197, pages 1071 to 1083, 1997) have described the influence of polymerization conditions on the copolymerization of styrene with ethylene using Ziegler's catalysts.

Natta from Me2Si (Me Cp) (N-tert-butyl) TiCl2 / methylaluminoxane. The manufacture of α-olefin / aromatic vinyl monomer interpolymers, such as propylene / styrene and butene / styrene, is described in U.S. Patent No. 5,244,996, issued to Mitsui Petrochemical Industries Ltd. All the methods described above for preparing the component of interpolymer are incorporated herein by reference.

The floor, wall or ceiling covering of the present invention preferably contains from about 5 to about 100 percent, more preferably from about 10 to about 100 percent, most preferably from about 40 to about 98 percent, of the substantially random interpolymer, based on the total weight of the floor, wall or ceiling covering. The floor, wall or ceiling covering of the present invention may contain one or more different polymers, in addition to one or more of the substantially random interpolymers described above. If present, their amount is generally up to about 90 percent, preferably from about 5 to about 80 percent, more preferably from about 15 to about 60 percent, most preferably from about 20 to about 50 percent, based on the total weight of the coating of floor, wall or ceiling. The floor, wall or ceiling covering of the present invention may be monolayer or multilayer. In monolayer coatings of floor, wall or ceiling, such additional polymer or optional polymers are mixed with the substantially randomly described interpolymer (s). In the multilayer coating of floor, wall or ceiling, such or such additional, optional polymers may be comprised in it and / or in a different layer than the substantially random interpolymer (s). Preferred additional, optional polymers are aromatic monovinylidene polymers or styrenic block copolymers. Additional, optional, most preferred polymers are homopolymers or interpolymers of aliphatic α-olefins having from 2 to about 20 carbon atoms, or α-olefins having from 2 to about 20 carbon atoms and containing polar groups. Suitable monovinylidene aromatic polymers include homopolymers or interpolymers of one or more monovinylidene aromatic monomers, or interpolymers of one or more monovinylidene aromatic monomers or more monovinylidene aromatic monomers and one or more interpolymerizable monomers therewith other than an α-olefin aliphatic Suitable monovinylidene aromatic monomers are represented by the following formula: Ar R1 C = CH: where R and Ar have the meanings declared in formula I above. Examples of monovinylidene aromatic monomers are those listed under formula I above, particularly styrene. Examples of suitable interpolymerizable comonomers that a monovinylidene aromatic monomer include, for example, conjugated C4-C6 dienes, especially butadiene or isoprene, N-phenyl maleimide, acrylamide, ethylenically unsaturated nitrile monomers such as, acrylonitrile and methacrylonitrile, monocarboxylic acids - and ethylenically unsaturated difunctionals and derivatives thereof, such as esters and, in the case of difunctional acids, anhydrides, such as acrylic acid, C4-alkyl acrylates or methacrylates, such as n-butyl acrylate and methyl methacrylate, maleic anhydride, etc. In some cases, it is also desirable to copolymerize a crosslinking monomer, such as divinyl benzene in the aromatic monovinylidene polymer. Polymers of monovinylidene aromatic monomers with other interpolymerizable comonomers contain, polymerized therein, at least 50 percent by weight and, preferably, at least 90 percent by weight of one or more monovinylidene aromatic monomers. Styrenic block polymers are also useful as an additional polymer, optional in the floor, wall or ceiling coating of the present invention. The term "block copolymer" is used herein to mean elastomers having at least one block segment of a hard polymer unit and at least one block segment of a rubber monomer unit. However, the term is not intended to include thermoelastic ethylene interpolymers which are, in general, random polymers. Preferred block copolymers contain hard segments of styrenic-type polymers in combination with segments of saturated or unsaturated gum monomers. The structure of the block copolymers useful in the present invention is not critical and may be of the linear or radial type, either diblock or triblock, or any combination thereof. Suitable unsaturated block copolymers include those represented by the following formula: A-B-R (-B-A) n or Ax- (BA-) and-BA wherein each A is a polymer block comprising a monovinylidene aromatic monomer, preferably styrene, and each B is a polymer block comprising a conjugated diene, preferably isoprene or butadiene, and optionally a monovinylidene aromatic monomer, preferably styrene; R is the remainder of a multifunctional coupling agent; n is an integer from 1 to about 5; x is zero or 1; and y is a number from zero to about 4. Methods for the preparation of such block copolymers are known in the art. Suitable catalysts for the preparation of block copolymers useful with unsaturated rubber monomer units include lithium based catalysts and especially lithium alkyls. U.S. Patent No. 3, 595,942 describes suitable methods for the hydrogenation of block copolymers with unsaturated rubber monomer units to form block copolymers with saturated rubber monomer units. The structure of the polymers is determined by their polymerization methods. For example, the linear polymers result from the sequential introduction of the desired gum monomer into the reaction vessel when initiators such as lithium or dilithiostilylbenzene alkyls and the like are used, or by coupling a two-segment block copolymer with a coupling agent. difunctional Branched structures, on the other hand, can be obtained by the use of suitable coupling agents having a functionality with respect to block copolymers with units of unsaturated rubber monomers of three or more. The coupling can be done with multifunctional coupling agents, such as dihaloalkanes or alkenes and divinyl benzene, as well as with certain polar compounds, such as silicon halides, siloxanes or esters of monohydric alcohols with carboxylic acids. The presence of any coupling residue in the polymer can be ignored for a proper description of the block copolymers forming a part of the composition of this invention. Suitable block copolymers having unsaturated rubber monomer units include, but are not limited to, styrene-butadiene (SB), styrene-isoprene (Sl), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), α-methylstyrene-butadiene-α-methylstyrene and α-methylstyrene-isoprene-α-methylstyrene, and the like.

The styrenic portion of the block copolymer is preferably a polymer or interpolymer of styrene and its analogs and homologs, including α-methylstyrene and ring-substituted styrenes, particularly styrene rings methylated with rings. The preferred styrenics are styrene and α-methylstyrene, and styrene is particularly preferred. Block copolymers with unsaturated rubber monomer units may comprise homopolymers of butadiene or isoprene, or may comprise copolymers of one or both of these two dienes with a less amount of styrenic monomer. Preferred block copolymers with saturated rubber monomer units comprise at least one segment of a styrenic unit and at least one segment of an ethylene-butene or ethylene-propylene copolymer. Preferred examples of such block copolymers with saturated rubber monomer units include styrene / ethylene-butene copolymers, styrene / ethylene-propylene copolymers, styrene / ethylene-butene / styrene (SEBS) copolymers, styrene / ethylene-copolymers propylene / styrene (SEPS), and the like. The hydrogenation of block copolymers with unsaturated rubber monomer units is preferably effected by the use of a catalyst comprising the reaction products of an aluminum alkyl compound with nickel or cobalt carboxylates or alkoxides under conditions such as to hydrogenate almost completely at least 80 percent of the double aliphatic ligatures, while hydrogenating no more than about 25 percent of the double styrenic aromatic ligatures. The preferred block copolymers they are those where at least 99 percent of the double aliphatic ligatures are hydrogenated, while less than 5 percent of the double aromatic ligatures are hydrogenated. The proportion of the styrenic blocks is generally between about 8 and 65 percent by weight of the total weight of the block copolymer. Preferably, the block copolymers contain from 10 to 35 weight percent of styrenic block segments and from 90 to 65 weight percent of rubber monomer block segments, based on the total weight of the block copolymer. The average molecular weights of the individual blocks may vary within certain limits. In most cases, the styrenic block segments will have number average molecular weights in the range from about 5,000 to about 125,000, preferably from about 7,000 to about 60,000, while the rubber monomer block segments will have molecular weights average in the range of about 10,000 to about 300,000, preferably from about 30,000 to about 150,000. The total average molecular weight of the block copolymer is usually in the range of from about 25,000 to about 250,000, preferably from about 35,000 to about 200,000. Additionally, the various block copolymers suitable for use in the present invention can be modified by incorporation of grafts of minor amounts of functional groups, such as, for example, maleic anhydride by any of the methods well known in the art. Block copolymers useful in the present invention are commercially available, such as, for example, those supplied by Shell Chemical Company under the designation KRATON ™ and supplied by Dexco Polymers under the designation VECTORM®. Preferred additional, optional polymers are homopolymers or interpolymers of aliphatic α-olefins having from 2 to about 20, preferably from 2 to about 18, more preferably 2 to about 12 carbon atoms, or α-olefins having from 2 to about 20 , preferably 2 to about 18, more preferably 2 to about 12 carbon atoms and containing polar groups. Suitable aliphatic α-olefin monomers, which introduce polar groups into the polymer include, for example, ethylenically unsaturated nitriles, such as, acrylonitrile, methacrylonitrile, ethacrylonitrile, etc.; ethylenically unsaturated anhydrides, such as maleic anhydride; ethylenically unsaturated amides such as acrylamide, methacrylamide, etc.; ethylenically unsaturated carboxylic acids (both mono- and difunctional), such as acrylic acid and methacrylic acid, etc.; esters (especially lower alkyl esters, for example C ^ Ce) of ethylenically unsaturated carboxylic acids such as methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, methacrylate or n-butyl acrylate, 2-ethylhexyl acrylate, etc.; ethylenically unsaturated dicarboxylic acid imides, such as N- alkyl or N-aryl maleimides, such as N-phenyl maleimide, etc. Preferably, such monomers containing polar groups are acrylic acid, vinyl acetate, maleic anhydride and acrylonitrile. The halogen groups that can be included in the polymers of the aliphatic α-olefin monomers include fluorine, chlorine and bromine; Preferably such polymers are chlorinated polyethylenes (CPEs) or polyvinyl chloride. Preferred olefinic polymers for use in the present invention are homopolymers or interpolymers of an aliphatic α-olefin, including cycloaliphatic, having from 2 to 18 carbon atoms. Suitable examples are ethylene or propylene homopolymers, and interpolymers of two or more α-olefin monomers. Other preferred olefinic polymers are interpolymers of ethylene and one or more other α-olefins having from 3 to 8 carbon atoms. Preferred comonomers include 1-butene, 4-methyl-1-pentene, 1 -hexene, and 1-ketene. The olefinic polymer may also contain, in addition to the α-olefin, one or more non-aromatic monomers interpolymerizable therewith. Such additional interpolymerizable monomers include, for example, C-C20 dienes, preferably butadiene or ethylene-2-norbronone. The olefinic polymers can be further characterized by their degree of long or short chain branching and the distribution thereof. A class of olefinic polymers is generally produced by a high pressure polymerization process using a free radical initiator, resulting in low density polyethylene with traditional long chain branching (LDPE). The LDPE used in this composition usually has a density of less than 0.94 g / cc (ASTM D 792) and a melt index from 0.01 to 100, and preferably from 0.1 to 50 grams per 10 minutes (as determined by the ASTM D Test Method) 1238, condition I). Another class is linear olefin polymers, which have an absence of long chain branching, such as traditional linear low density polyethylene polymers (heterogeneous LLDPE) or linear high density polyethylene (HDPE) polymers made using polymerization processes from Ziegler (e.g., U.S. Patent No. 4,076,698 (Anderson et al.), sometimes called heterogeneous polymers HDPE consists primarily of long linear polyethylene chains The HDPE employed in the present composition usually has a density of at least 0.94. grams per cubic centimeter (g / cc) as determined by ASTM Test Method D 1505, and a melt index (ASTM-1238, condition I) in the range from 0.01 to 100, and preferably from 0.1 to 50 grams for 10 minutes The heterogeneous LLDPE employed in the present composition generally has a density from 0.85 to 0.94 g / cc (ASTM D 792), and a fume index. (ASTM-1238, condition I) in the range from 0.01 to 100, and preferably from 0.1 to 50 grams per 10 minutes. Preferably, the LLDPE is an interpolymer of ethylene and one or more different α-olefins having from 3 to 18 carbon atoms, more preferably from 3 to 8 carbon atoms. The Preferred comonomers include 1-butene, 4-methyl-1-pentene, 1 -hexene, and 1-ketene. An additional class is that of uniformly branched or homogeneous polymers (homogeneous LLDPE). The homogeneous polymers do not contain long chain branches and only have branches derived from the monomers (if they have more than two carbon atoms). Homogeneous polymers include those made as described in US Patent 3,645,992 (Elston), and those made using single-site catalysts in a reactor having relatively high olefin concentrations [as described in U.S. Patent Nos. 5,026,798 and 5,055,438 ( Canich)]. The uniformly branched / homogeneous polymers are those polymers in which the comonomer is randomly distributed within a given interpolymer molecule, and wherein the interpolymer molecules have a similar ethylene / comonomer ratio within that interpolymer. The homogeneous LLDPE employed in the present composition generally has a density from 0.85 to 0.94 g / cc (ASTM D 792), and a melt index (ASTM-1238, condition I) in the range from 0.01 to 100, and preferably from 0.1 to 50 grams per 10 minutes. Preferably, the LLDPE is an interpolymer of ethylene and one or more different α-olefins having from 3 to 18 carbon atoms, more preferably from 3 to 8 carbon atoms. Preferred comonomers include 1-butene, 4-methyl-1-pentene, 1 -hexene and 1-ketene.

Additionally, there is the class of substantially linear olefin polymers (SLOP) that can be advantageously used in the component (B) of the mixtures of the present invention. These polymers have a processability similar to LDPE, but the strength and hardness of LLDPE. Similar to traditional homogeneous polymers, the substantially linear ethylene / α-olefin interpolymers have only a single melting peak, as opposed to conventional, heterogeneous linear polymerized ethylene / α-olefin copolymers from Ziegler, which have two or more fusion peaks (determined using differential scanning calorimetry). Substantially linear olefin polymers are described in U.S. Patent Nos. 5,380,810; 5,272,236 and 5,278,272, which are incorporated herein by reference. The density of the SLOP as measured according to ASTM D-792 is generally from 0.85 g / cc to 0.97 g7cc, preferably from 0.85 g / cc to 0.955 g7cc, and especially from 0.85 g / cc to 0.92 g7cc. The melt index, according to ASTM D-1238, Condition of 190 ° C / 2.16 kg (also known as l2), of the SLOP is generally from 0.01 g / 10 min to 1000 g / 10 min. , preferably from 0.01 g / 10 min to 100 g / 10 min. , and especially from 0.01 g / 10 min to 10 g / 10 min. Also included are the ultra low molecular weight ethylene polymers and ethylene / α-olefin interpolymers described in WO patent application no. 97/01 181 entitled Ultra-low Molecular Weight Polymers, filed January 22, 1997, which is incorporated herein by reference. These ethylene / α-olefin interpolymers have an index of fusion l2 greater than 1, 000, or a number average molecular weight (Mn) less than 1 1, 000. The most preferred homopolymers or interpolymers of aliphatic α-olefins having from 2 to 20 carbon atoms and optionally containing polar groups are ethylene homopolymers; propylene homopolymers, copolymers of ethylene and at least other α-olefins containing from 4 to about 8 carbon atoms; copolymers of propylene and at least other α-olefins containing from 4 to about 8 carbon atoms; copolymers of ethylene and at least one of acrylic acid, vinyl acetate, maleic anhydride or acrylonitrile; copolymers of propylene and at least one of acrylic acid, vinyl acetate, maleic anhydride or acrylonitrile; and terpolymers of ethylene, propylene and a diene. Especially preferred are LDPE, HDPE, heterogeneous and homogeneous LLDPE, SLOP, polypropylene (PP), especially isotactic polypropylene and hardened polypropylenes of rubber, or ethylene-propylene (EP) interpolymers, or ethylene-vinyl acetate copolymers, or copolymers of ethylene-acrylic acid, or any combination thereof. Particularly, a mixture comprising from about 5 to about 99 percent, preferably from about 10 to about 95 percent, more preferably from about 20 to about 80 percent, of the substantially random interpolymer (s) described above, and from about 95 to about 1 percent, preferably from about 90 up about 5 percent, more preferably from about 80 to about 20 percent, of one or more of the above-described homopolymers or interpolymers of aliphatic α-olefins having from 2 to about 20 carbon atoms or α-olefins having from 2 to about 20 atoms of carbon and containing polar groups, based on the total weight of the mixture. It has been found that floor, wall or ceiling coatings made of or containing such blends as a top layer exhibit surprisingly good abrasion resistance. In a preferred aspect of the present invention, the mixture comprises from about 50 to about 99 percent, preferably from about 60 to about 95 percent, more preferably from about 70 to about 90 percent, of the substantially random interpolymer (s) described above, and from 1 to about 50, preferably from about 5 to about 40 percent, most preferably from about 10 to about 30 percent of one or more of the above-described homopolymers or interpolymers of aliphatic α-olefins having from 2 to 20 carbon atoms, or α-olefins having from 2 to about 20 carbon atoms and containing polar groups, based on in the total weight of the mixture. Floor, wall or ceiling coatings containing such blends generally exhibit good crevice resistance at high load and excellent scratch resistance.

Moreover, floor, wall or ceiling coatings containing such mixtures generally exhibit good abrasion resistance. The floor, wall or ceiling covering of the present invention may contain a filler. If present, their amount is generally up to about 95 percent, preferably from about 10 to about 90, more preferably from about 30 to about 85 percent, based on the total weight of the floor, wall or ceiling covering. The preferred amount of filler varies greatly, depending on the desired stiffness and mode of application of the floor, wall or ceiling covering. Preferably, the floor, wall or ceiling laminates do not contain a filler. However, if they contain a filler, the amount of the filler is preferably from about 10 to about 70 percent, more preferably from about 15 to about 50 percent, based on the total weight of the laminate. Preferably, floor tiles, wall tiles or ceiling tiles contain from about 50 to about 95 percent, more preferably from about 70 to about 90 percent of a fill, based on the weight of the floor, wall or ceiling covering. Surprisingly the α-olefin-vinylidene interpolymers exhibit high compatibility with a wide variety of fillers. Useful fillers include organic and inorganic fillers, such as sawdust, wood fillers, such as wood flour or wood fibers, paper fibers, corn scrim, straw, cotton, carbon black or graphite, talc, calcium carbonate , "flyash", alumina tridrate, glass fibers, marble powder, cement powder, clay, feldspar, silica or glass, smoked silica, alumina, magnesium oxide, zinc oxide, barium sulfate, aluminum silicate, silicate of calcium, titanium dioxide, titanates, glass or gis microspheres. Of these fillers, barium sulfate, talc, calcium carbonate, barium sulfate, silica / glass, glass fibers, alumina and titanium dioxide, and mixtures thereof are preferred. The term "a filler", as used herein, includes a mixture of different fillers. The floor, wall or ceiling covering of the present invention is preferably substantially free of halogen-containing compounds, such as polyvinyl chloride, polyvinylidene chloride, or halogen-containing flame retardants. For the term "substantially free of halogen-containing compounds" is meant that the halogen-containing compounds usually amount to more than about 10 percent, preferably not more than about 5 percent, more preferably not more than about 2 percent, most preferably not more than about 1 percent, based on the total weight of the floor, wall or ceiling covering. Most preferably, the floor, wall or ceiling covering of the present invention does not contain any measurable amount of halogen-containing compounds. The floor, wall or ceiling covering of the present invention may contain one or more additives, for example, antioxidants, such as phosphites or clogged phenols; light stabilizers, such as blocked amines; plasticizers, such as dioctylphthalate or soybean oil epoxidized; viscosity agents, such as known hydrocarbon viscosity agents; waxes, such as polyethylene waxes; processing aids, such as, stearic acid or a metal salt thereof; crosslinking agents, such as peroxides or silanes; dyes or pigments to the extent that they do not interfere with good conformability for uneven or contoured surfaces, scratch resistance and / or slit recovery of the floor, wall or ceiling covering of the present invention. The additives are employed in functionally equivalent amounts known to those skilled in the art., generally in amounts of up to about 30, preferably from about 0.01 to about 5, more preferably from about 0.02 to about 1 weight percent, based on the weight of the floor, wall or ceiling covering. Generally, the floor, wall or ceiling covering of the present invention has a thickness from about 0.025 mm to about 25 mm, preferably from about 0.1 mm to about 10 mm. Preferably, the floor coverings have a thickness from about 1 mm to about 10 mm, more preferably from about 1 mm to about 5 mm, most preferably from about 1.5 mm to about 4 mm. Preferably, the wall coatings have a thickness of from about 0.1 to about 3 mm, more preferably from about 0.5 to about 2 mm, very preferably from about 0.5 to about 1.5 mm. In a preferred embodiment of the present invention, the floor, wall or ceiling covering of the present invention is a monolayer structure, which contains the above-described substantially random interpolymer (s) and optional additive (s). The thickness of such a monolayer structure is preferably from about 0.025 mm to about 15 mm, more preferably from about 1.5 mm to about 4 mm. In another preferred embodiment of the present invention, the floor, wall or ceiling covering contains at least two layers, wherein at least one layer (A) comprises one or more substantially random interpolymers described above. The layer (s) (A) generally contain from about 5 percent to about 100 percent, preferably from about 25 percent to about 100 percent, more preferably from about 40 percent to about 100 percent, most preferably from about 80 percent to about 100 percent , of the substantially random interpolymer (s), based on the total weight of the layer (s) A. The layer (s) (A) may comprise one or more additional, optional polymers and / or other optional additives, such as a filler, as described before. If a layer (A) comprises an optional additional polymer, the mixtures described above are preferred. The amount of a fill, if present, it is generally from 0 percent to about 80 percent, preferably from 0 percent to about 60 percent, more preferably from about 20 percent to about 60 percent, based on the total weight of the layer (s) (A). The thickness of the layer (A) is preferably from about 0.025 mm to about 2 mm, preferably from about 0.060 mm to about 1 mm, more preferably from about 0. 1 mm to about 1 mm. The layer (A) may represent the upper layer, the volume layer and / or the lower layer or the floor, wall or ceiling covering of the present invention. Regardless of whether the layer (A) is the upper layer, volume or lower, it improves the conformability of the floor, wall or ceiling covering material for floors or walls, which allows an easier application and which allows the coating Floor, wall or ceiling remain flat on the floor or wall. Additionally, the layer (A) generally provides good slit resistance for the multilayer structure, regardless of whether the layer (A) represents the top layer, of volume or less. Preferably, the layer (A) represents the upper layer. Provides excellent resistance to scratches to the multi-layer structure. Preferably, the floor, wall or ceiling covering of the present invention contains a layer (A) described above and one or more additional polymer layers (B). The preferred polymers in such additional layer or polymer layers (B) are the aromatic polymers of monovinylidene described above, styrenic block copolymers, or more preferably, homopolymers or interpolymers of aliphatic α-olefins having from 2 to about 20 carbon atoms or α-olefins having from 2 to about 20 carbon atoms and containing polar groups. Alternatively, layer (B) may comprise one or more substantially random interpolymers described above, wherein the average molar content of the vinylidene monomer component in the interpolymer (s) in layer (B) is different from the average molar content of the vinylidene monomer component in the interpolymer (s) in layer (A). The layer (s) (B) generally contain from about 5 percent to about 100 percent, preferably from about 15 percent to about 100 percent, more preferably from about 40 percent to about 90 percent, most preferably from about 60 percent to about 80 percent, of the polymers described, based on the total weight of the layer (s) (B). The layer (s) (B) may comprise one or more additional, optional polymers and / or one or more other optional additives, such as a filler, as described above. The amount of a filler, if present, is generally from about 10 percent to about 90 percent, preferably from 10 percent to 75 percent, more preferably from about 30 percent to about 50 percent, based on the total weight of the layers (B).

The thickness ratio between layer (A) and layer (B) is preferably from about 0.01: 1 to about 10: 1, more preferably from about 0. 1: 1 to about 5: 1, most preferably from about 0.2: 1 to approximately 5: 1. The floor, wall or ceiling covering of the present invention may comprise one or more additional layers, which are common in floor, wall or ceiling coatings, such as one or more layers of adhesive and / or one or more decorative layers. . The decorative layer can be arranged in the upper part of the layer (A), however, it is preferably arranged between the layer (A) and the layer (B). The substantially random interpolymer (s) described above can be combined with optional additives and processed for the floor and wall coating of the present invention by any suitable means known in the art, such as, but not limited to, Banbury mixing, extrusion amalgamation , roller milling, calendering, compression molding, injection molding and / or sheet extrusion. The temperatures useful for processing the substantially random interpolymer (s) in combination with optional additives for the floor, wall or ceiling coating of the present invention are generally from about 1 00 ° C to about 300 ° C, preferably from about 120 ° C to about 250 ° C, more preferably from about 140 ° C to about 200 ° C.

The floor, wall or ceiling covering of the present invention may be foamed or may comprise one or more layers of foam.

Specifically, the layer or layers containing the substantially random interpolymer (s) described above and / or one or more of the additional polymer layers described above, if present, can be foamed. The foam layer or layers can be produced by an extrusion process or from expandable or foamable particles, moldable foam particles, or beads from which a sheet is formed by expansion and / or coalescence and welding of these particles. The foam structure can be made by a conventional extrusion foaming process. The structure is generally prepared by heating a polymer material to form a fused or plasticized polymer material, incorporating in it a known blowing agent to form a foamable gel, and extruding the gel through a die to form the foam product . Before being mixed with the blowing agent, the polymer material is heated to a temperature at or above its glass transition temperature or melting point. The blowing agent can be incorporated or mixed into the fused polymer material by any means known in the art, such as with an extruder, mixer or beater. The blowing agent is mixed with the polymer material fused at an elevated pressure, sufficient to prevent substantial expansion of the fused polymer material and to generally disperse the blowing agent homogeneously therein. Optionally, a core former in the fused or dry mixed polymer can be mixed with the polymer material before plasticizing or merging. The foamable gel is usually cooled to a temperature normally at a lower temperature to optimize the physical characteristics of the foam structure. The gel is extruded or transported through a die of desired shape to a zone of reduced or reduced pressure to form the foam structure. The die may have a substantially rectangular hole to produce a sheet of the desired width and height. Alternatively, the die may have multiple orifices to produce polymer filaments, which may be cut into beads. The lower pressure zone is at a lower pressure than that in which the foamable gel is maintained before extrusion through the die. The lower pressure may be superatmospheric or subatmospheric (vacuum), but preferably at an atmospheric level. The foam structure can also be formed into foam beads suitable for molding into articles. To make the foam beads, discrete resin particles such as granulated resin pellets are suspended in a liquid medium, in which they are substantially insoluble, such as water.; they are impregnated with a blowing agent by introducing the blowing agent into the liquid medium at a high pressure and temperature in an autoclave or other pressure vessel; and they are rapidly discharged into the atmosphere or a region of reduced pressure to expand to form the foam beads. This process is taught well in U.S. Patent Nos. 4,379,859 and 4,464,484, which are incorporated herein by reference.

The foam beads can then be molded by any means known in the art, such as loading the foam beads into the mold, compressing the mold to compress the beads, and heating the beads, such as with steam, to effect coalescence and welding. the pearls to form the article. Optionally, the beads can be impregnated with air or with another blowing agent at a high pressure and temperature before being loaded into the mold. In addition, the pearls can be heated before loading. The foam beads can then be molded to sheets by a suitable molding method known in the art. Some of the methods are shown in U.S. Patent Nos. 3,504,068 and 3,953,558. Various additives may be incorporated into the foam structure, such as stability control agents, core forming agents, inorganic fillers, pigments, antioxidants, acid cleaners, ultraviolet absorbers, flame retardants, processing aids and extrusion aids. Some of the additives are described in more detail before. Particularly preferred are floor laminates, floor tiles, wall laminates and wall tiles. They are useful in private and public buildings. They can also be used to coat floors outside buildings, such as balconies and terraces. The floor, wall, and particularly roof coatings of the present invention are also useful as sound insulating materials. The floor, wall or ceiling coatings of the present inventions are also useful in geological areas, for example, in caves or tunnels as a replacement for PVC.

The floor, wall or ceiling coatings of the present invention have a number of properties, which make them particularly suitable for the intended end use. Depending on the types and amounts chosen of substantially random interpolymer (s) and optional additives, the floor and wall coverings of the present invention have some or all of these properties, such as, good slit resistance, slit recovery. , good flexibility and conformability on contoured or uneven surfaces, good resistance to scratches and / or good resistance to abrasion. Moreover, the floor, wall or ceiling covering of the present invention may be substantially free of halogen-containing compounds. Additionally, in general no coupling agent is required when a filler is included in the floor, wall or ceiling covering. Surprisingly, the floor, wall or ceiling covering of the present invention, which contains a substantially random interpolymer described above, can generally comprise a filler content of 70 percent by weight or more, in many cases still 80 percent by weight or more, and usually up to 95 percent by weight without requiring the presence of a coupling agent and still exhibiting good filler support and good solid state properties. This is unexpected, since many of the above-mentioned substantially random interpolymers are greatly disrupted.

Commonly common adhesives, such as acrylic or styrene / butadiene based adhesives, can be used to fix floor, wall or ceiling coatings on floors, walls or ceilings. Generally, the use of adhesion promoters is not necessary, such as surface oxidation via flame or corona treatment or acrylic primers in combination with these adhesives. The following examples are provided to illustrate the present invention. The examples are not intended to limit the scope of the present invention and should not be construed in that way. The amounts are in parts by weight or percentages by weight unless otherwise indicated.

TESTS The properties of polymers and mixtures are determined by the following test procedures.

A) Test methods for all examples Melt index (Ml) is determined by ASTM D-1238 (1 979), Condition E (1 90 ° C, 2.1 6 kg). Hardness is measured using a Hardness Tester for Cutting A and D according to DI N 53505. B) Test methods for Examples 1 to 34 Stress force properties, secant modulus and elongation are measured using ASTM D 638, Type C .

For the slit test, ASTM F 142-93 (Standard Test Method for Resilient Floor Slit-McBurney Test) and a modified test were used. In the modified test, a load of 64 kg is applied via a cylindrical foot of 4.5 mm in diameter. The load is applied for 10 minutes and the initial crack is measured. The residual gap is measured after 60 minutes. For the modified test, the slits are reported as a percentage of initial plate thickness. For the residual crack, the sample is given a "failure" rating if the cylindrical cleft foot cuts and permanently damages the surface. Scratch test is performed using a Scratch Tester Universal Erichson equipped with a 90 ° - 180 μm diameter style.

A charge of 0.1 to 1.0 N is applied to this style, and the resulting scratch width is measured after 30 days by a Perthen Surface Profiler. The width and depth of the scratch are expressed in micrometers.

Abrasion of Taber is measured in accordance with ASTM F-510. Flexural module is measured using ASTM D 790-95A. C) Test methods for Examples 35 to 83. Abrasion DI N is determined according to DI N 53516, measured at 10N. The Franke bending stiffness is measured according to DI N 53121 at a temperature of 22 ° C and in the relaxation times indicated in Tables 7 to 9 below. Ultimate tensile strength and elongation are measured according to DI N 53504, specimen S2, 50 mm / min cross-head speed.

The roller drive is measured by passing a 50 mm diameter roller loaded with a 25 kg mass on a strip of 26 cm x 2 cm floor material with a frequency of 21 cycles / minute. The drag is measured after 20,000 cycles (16 h) and after 8 h of recovery. The coefficient of friction is measured according to ISO 8295 modified by using a floor cleaning cloth. The scratch depth, the visual scratch classification and the scratch detection limit are measured by means of a triangular blade in which a load between 1 N and 14 N is applied. The visual classification of scratch indicates on which charge the scratch can be seen. The limit of detection indicates in which charge the scratch can be felt with the finger. The resistance to the slit, that is, the original slit after 150 min. of compression, the final slit after a relaxation time of 150 min and percentage of recovery are measured according to DIN 51955. The compression set is measured according to DI N 53517 at 23 ° C after 504 h of time of relaxation.

Preparation of ethylene / styrene interpolymers ESI-1. ESI-2, ESI-4, ESI-5. ESI-6 v ESI-7 Description of the reactor The single reactor used is a continuously stirred tank reactor of 22.7 I, jacketed with oil, autoclave (CSTR). A magnetically coupled stirrer with Lightning A-320 propellers provides mixing. The reactor runs full liquid at 3,275 kPa. The process flow is in the background and outside the top. A heat transfer oil is circulated through the jacket of the reactor to remove some of the heat of reaction. After the output of the reactor, it is arranged that the micromotion flow meter measures solution and flow density. All lines at the reactor outlet are steam traced at 344.7 kPa and isolated.

Procedure Ethylbenzene solvent is supplied to the mini-plant at 207 kPa. The feed to the reactor is measured by a Micro-Motion mass flow meter. The variable speed diaphragm pump controls the feeding speed. At the discharge of the solvent pump a side stream is taken to provide discharge flows for the catalyst injection line (0.45 kg / h) and the reactor stirrer (0.34 kg / h). These flows are measured by differential pressure flow meters and controlled by manual adjustment of micro-flow needle valves. A non-inhibited styrene monomer is supplied to the mini-plant at 207 kPa. The feed of the reactor is measured by a Micro-Motion mass flow meter. A variable speed diaphragm pump controls the feeding speed. The styrene stream is mixed with the remaining solvent stream. Ethylene is supplied to the mini-plant at 4, 137 kPa. The ethylene stream is measured by a Micro-Motion mass flow meter just before the Research valve controlling the flow. A Brooks flow meter / controllers is used to deliver hydrogen into the ethylene stream at the outlet of the ethylene control valve. The ethylene / hydrogen mixture is combined with the solvent / styrene stream at room temperature. The temperature of the solvent / monomer is reduced as it enters the reactor at approximately 5 ° C by a glycol exchanger at -5 ° C in the jacket. This current enters the bottom of the reactor. The three-component catalyst system and its solvent discharge also enters the reactor at the bottom, but through a gate different from the monomer stream. To prepare ESI-1, ESI-2 and ESI-4, ESI-5, ESI-6 and ESI-7, 1,3-pentadiene (t-butylamide) dimethyl (tetramethylcyclopentadiene) silanetitanium (II) is used. as a modified titanium and methylaluminoxane catalyst Type 3A (MMAO-3A, commercially available from Akzo) is used as a second catalyst component. The boron cocatalysts used are tris (pentafluorophenyl) borane (to prepare ESI-1 and ESI-2) or bis-hydrogenated tallow alkyl methacrylate tetrakis (pentafluorophenyl) borate respectively (to prepare ESI-4, ESI-5, ESI-6 and ESI-7). To prepare ESI-1, the molar ratio between the boron cocatalyst and the titanium catalyst is 3: 1 and the molar ratio between MMAO-3A and the titanium catalyst is 8: 1. To prepare ESI-2 and ESI-4 , the molar ratio between the boron cocatalyst and the titanium catalyst is 2: 1 and the molar ratio between MMAO-3A and the titanium catalyst is 5: 1. To prepare ESI-5, ESI-6 and ESI-7, The molar ratio between the boron cocatalyst and the titanium catalyst is 1.25: 1 and the molar ratio between MMAO-3A and the titanium catalyst is 12: 1. The preparation of the catalyst components takes place in an inert atmosphere glove box. The diluted components are placed in cushioned cylinders and charged to the catalyst run tanks in the process area. From these run tanks, the catalyst is pressed with piston pumps and the flow is measured with Micro-Motion mass flow meters. These streams combine with each other and the catalyst discharge solvent just before entering through a simple injection line into the reactor. The polymerization is stopped with the addition of catalyst neutralizer (water mixed with solvent) in the product line of the reactor after the micromotion flow meter by measuring the density of the solution. Other polymer additives can be added with the catalyst neutralizer. A static mixer in the line provides the dispersion of the catalyst neutralizer and additives in the reactor effluent stream. This current then enters the post reactor heaters that provide additional energy for the instantaneous evaporation of solvent removal. This instantaneous evaporation occurs as the effluent from the post reactor heater exits and the pressure drops from 3,275 kPa to approximately 250 mm absolute pressure in the reactor pressure control valve. This evaporated polymer instantly enters a devolatilizer coated with hot oil. Approximately 85 percent of the volatiles are removed from the polymer in the devolatilizer. The volatiles leave the top of the devolatilizer. The current condenses with a glycol-enriched exchanger, the suction of a vacuum pump enters and is discharged with a glycol jacket solvent and styrene / ethylene separation vessel. The solvent and styrene are removed from the bottom of the container and ethylene from the top. The ethylene stream was measured with a Micro-Motion mass flow meter and analyzed for the composition. The measurement of de-fumed ethylene plus a calculation of the gases dissolved in the solvent / styrene stream are used to calculate the conversion of ethylene. The polymer separated in the devolatilizer is pumped out with a gear pump to a devolatilization vacuum extruder ZSK-30. The dried polymer leaves the extruder as a single filament. This filament cools as it is pulled through a water bath. The excess water is blown from the filament with air and the filament is cut into pellets with a filament cutter. The amounts of monomer and polymerization conditions are given in Table 1 A. The polymer properties of ESI-1 to ESI-8 are given in Table 1 C below.

Table 1A Preparation of ethylene / styrene interpolymer ESI-3 The polymer is prepared in a stirred, semi-continuous batch reactor of 1514 liters. The reaction mixture consists of approximately 946 liters of styrene and a solvent comprising a mixture of cyclohexane (85 weight percent) and isopentane (15 weight percent). Before the addition, the solvent, styrene and ethylene are purified to remove water and oxygen. The inhibitor in styrene is also removed. The inerts are removed by purging the container with ethylene. The container is then pressurized to a set point with ethylene. Hydrogen is added to control the molecular weight. The temperature of the container is controlled to the set point by varying the water temperature of the jacket in the container. Prior to polymerization, the vessel is heated to the desired run temperature and the catalyst components, ie (tert-butylamido) dimethyl (tetramethyl-? 5-) catalyst. cyclopentadienyl) silane dimethyl titanium (IV), CAS # 135072-62-7, Tris (pentafluorenyl) boron, CAS # 001 109-15-5, modified methylaluminoxane Type 3A, CAS # 146905-79-5, are flow controlled, on a molar proportion basis of 1/3/5 respectively, they are combined and added to the container. After initiation, polymerization with ethylene supplied to the reactor as required to maintain the container pressure is allowed to proceed. In some cases, hydrogen is added to the upper space of the reactor to maintain a molar ratio with respect to the ethylene concentration. At the end of the run, the catalyst flow is stopped, the ethylene is removed from the reactor, then approximately 1000 ppm of antioxidant lrganox ™ 1010 is added to the solution and the polymer is isolated from the solution. The resulting polymers are isolated from the solution by steam extraction in a vessel. In the case of steam-extracted material, additional processing is required in equipment similar to the extruder to reduce residual moisture and any unreacted styrene. The amounts of monomer and polymerization conditions are given in Table 1B.

Table 1 B Ethylene / styrene interpolymer preparation ESI-8 ESI-8 is prepared by dry blending 80 weight percent of the ethylene / styrene interpolymer ESI-5 and 20 weight percent of the ethylene / styrene interpolymer ESI-6.

Table 1 C ") na * = not analyzed TABLE 2: Other materials used in the Examples Abbreviation Product name fusion index Density (g / 10 min) (g / cc) ITP-2 AFFINITY ™ DSH 1500.00 1 .0 0.902 (ethylene-1-ketene copolymer) ITP-3 AFFINITY SM 8400 30.0 0.871 (ethylene-1-ketene copolymer) ITP- 4 AFFI NITY SM 1300 30.0 0.902 (ethylene-1-ketene copolymer) VP 8770 AFFINITYMR VP 8770 1 .0 0.885 (ethylene-1-ketene copolymer) LD 1 50 Low density polyethylene 0.25 0.921 HD 53050E High density polyethylene l5 = 0.3 0.952 HD 35060E High density polyethylene 0.29 0.96 PE-g-MAH Dow XU-60769.04 2.5 0.955 (maleic anhydride graft polyethylene containing 1.0 percent maleic acid) CaCO3 Pfizer ATF-40 (ground limestone, 40 mesh) Oil SHELLFLEXM R 371 Examples 1 to 33 In Examples 1 to 33, plates are prepared via the following steps: 1) mixed in Haake's bowl, 2) ground with rollers, and 3) compression molded into plates. A Haake mixer equipped with a Rheomiz 3000 bowl is used. All the components of the mixture are added to the mixer, and the rotor is operated at 1 90 ° C and 40 rpm for 10 minutes to 15 minutes. The material is removed from the Haake, and fed to a Farrel two-roll mill of 1 524 cm diameter x 30.48 cm width set at a surface temperature of 1 75 ° C. The lamp is taken either after a wrap at 1 80 ° or allowed to wrap 540 ° before being released. The sheet is then cut and compression molded into plates 3.1 mm thick x 1 1/6 mm x 1 1/6 mm with a Pasadena Hydrauiics I ncorporated (PHI) press. The press is operated at 205 ° C in a minimum pressure preheating mode for 3 minutes, and then pressed up to 1.5 tons for 2 minutes. The plates are then removed from the heat and cooled to 1.5 tons for 3 minutes.

The properties of the compression molded plates are measured as indicated above. Tables 3, 4 and 5 list the compositions and physical properties resulting from Examples 1 to 31 according to the present invention and Comparative Examples 32 and 33 (not within the scope of the present invention, but from the prior art. ), for formulations of 0 percent fill, 60 percent fill, and 85 percent fill, respectively.

Table 3 4-.

Table 3 (Continued) ** Scratch "cured" *** Loss not measurable nt = not tested Examples 1 to 8 in Table 3 illustrate that floor, wall or ceiling coatings comprising a substantially random interpolymer described above, have a good balance of properties, such as low flexural modulus (which means high flexibility), sufficient resistance to slit and scratches and, compared to the PVC material of comparative example 34, improved abrasion resistance. The products of Examples 1 to 8 are useful as a homogeneous uncoated floor covering or as a single layer in a heterogeneous structure. In addition, the exceptional scratch resistance of ethylene / styrene interpolymers with at least about 60 weight percent (about 30 mole percent) of interpolymerized styrene, as in Example 3, makes the material suitable as a surface layer or wear of the floor covering of the present invention.

Table 4 ^ 1 Table 4 (Continued) 8 nt = not tested Examples 9 to 18 illustrate that no additive or polymeric coupling agent is required to achieve good solid state and backfill properties. The products of Examples 9 to 18 are useful as a filled homogeneous floor covering or as a single layer in a heterogeneous structure. The products of Examples 9 to 18 are especially suitable for floor laminate products.

Table 5 or nt = not tested The plates of Examples 19 to 31 have considerably greater scratch resistance than the plates of Comparative Examples 32 to 33. The exceptional scratch resistance of ethylene / styrene interpolymers with at least about 60 weight percent (approx. 30 percent mole) of interpolymerized styrene, as in Examples 21, 21 and 23, makes the material especially suitable for flooring material structures. Examples 19 to 29 illustrate that no additive or polymeric coupling agent is required to achieve good solid state and fill hold properties. The plate of Example 21 shows an exceptional combination of flexibility and slit resistance, and is useful in or as a floor tile product with good ability to be installed and good conformability to contoured and uneven surfaces.

Comparative Example 34 The properties of a high quality flexible PV material, which is commercially available from Armstrong under the commercial designation "Imperial" tile and has a thickness of 3,175 mm, are measured as in Examples 1 to 33. The module flexion is 696 MPa, the slit at 14 kg load and 1 min is 254 micrometers, the slit at 14 kg load and 10 min is 305 micrometers, the initial slit at 64 kg load is 1 1 percent of the total thickness and the Residual slit at 64 kg load is 4 percent of the total thickness. Taber abrasion is 40 mg / 100 rev. Taber abrasion of all floor, wall or wall coverings The roof of Examples 1 to 25 and 27 to 30 according to the present invention show a substantially lower abrasion than that of the comparative PVC material (the Taber abrasion of Examples 26 and 31 was not tested).

Examples 35 to 44 In examples 38 to 42, sheets of 2 mm thickness are prepared according to the following method: A mold is used consisting of a steel plate covered with a Teflon ™ material and a frame of 28 cm x 28 x m x 0.2 cm Powder or granules of the appropriate polymer are filled in the mold. The mass of the filled polymer in the frame is the volume of the mold, that is, 156.8 cm3, x polymer density + 10 percent. The mold is closed with a steel plate and pressed at elevated temperature. In comparative example 38, the material of layer (B), as described below, is pre-pressed for 6 min at a machine pressure of 8 x 105 Pa and for 5 min at 100 x 105 Pa at a temperature of 190 ° C. The mold is cooled from 150 ° C to 95 ° C in a period of 3 min 15 s (minimum) to 4 min 12 s (maximum). In Examples 39 to 42, the ESI material is pre-pressed for 5 min at a machine pressure of 8 x 105 Pa and for 3 min at 200 x 105 Pa at a temperature of 175 ° C. The mold is placed between a lower plate and steel upper plate cooled with water, and cooled to room temperature within 5 min. In Examples 35 to 37, multilayer sheets are prepared, which consist of - a layer A) made of an ESI listed in Table 7 ahead of a thickness of 0.5 mm and - a layer B) of a thickness of 1.5 mm and made from a mixture of 49 percent of a polyolefin plastomer AffinityMR EG 8150, 27 percent HDPE 53050E, 10 percent LDPE 150, all available from THE DOW CHEMICAL COMPANY, and 14 percent Lupolen UHM 201, commercially available from BASF. 1.5 mm thick sheets of layer material B) (examples 35 to 37) or ESI (examples 43 and 44) are prepared as described above for examples 38 to 42. The sheets are preheated without pressing on a plate steel. The steel plate is heated to 160 ° C to 170 ° C in the case of layer B) and to 120 ° C to 130 ° C in the case of ESI. An ESI film of 0.5 mm thickness is pressed on the preheated sheet. In the case of a layer B) of 1.5 mm, the pressure is 5 min at 3 x 105 Pa and 3 min at 10 x 105 Pa. In the case of an ESI layer of 1.5 mm the pressure is 1 min at 3 x 105 Pa and 1 min at 15 x 105 Pa. The multilayer film produced is cooled to room temperature within 5 min. The compositions of the monolayer and multilayer sheets of Examples 35 to 37 and 39 to 44 and comparative example 38 are listed in Table 6 below.

Table 6 Comparative example Table 6 illustrates that the floor, wall or ceiling coatings of the present invention containing a substantially random interpolymer described above have a Franke bending rigidity considerably less than the sheet of Comparative Example 38, which contains a mixture of polyethylenes. Additionally, the floor, wall or ceiling coatings of the present invention achieve a very low stiffness value after a very short time. Surprisingly, Franke's bending stiffness of the multilayer sheets of Examples 35 to 37 is considerably less than what might have been expected based on Franke's bending stiffness of the individual layers of a comparative thickness, although the layer of ESI is only 25 percent of the total thickness of the lamp.

Examples 39. 41 v 45 to 83 In Examples 45 to 56 and 59 to 83, sheets 2 mm thick are prepared as in Examples 38 to 42. The PVC floor material of comparative example 57 has a thickness of 2 mm. mm. It is a high quality PVC flooring material and contains 30 percent by weight filler. It is commercially available under the Tarkett Eminent designation. The polyolefin flooring material of comparative example 58 has a thickness of 2 mm. It is a high quality polyolefin flooring material based on the AffinityM R polyolefin plastomer, polypropylene and polyethylene. Corresponds to the flooring material, which is commercially available under the Tarkett SuperNova designation, but does not contain a polyurethane coating. The usefulness of the sheets as floor coverings is proved. The composition of the sheets and their physical properties are listed in Tables 7 to 9 below.

Table 7 EC Table 7 (Continued) Comparative example Table 8 ^ 1 o Table 8 (Continued) Comparative example Table 9 t Table 9 (Continued) -4 Comparative example The comparison between a) examples 39 and 45 to 50, b) examples 39 and 51 to 56, c) examples 41, 59 to 63 and 50, and d) examples 41, 64 to 68 and 60, illustrate that a mixture of an interpolymer substantially randomly described above and a homopolymer or interpolymer of aliphatic α-olefin (s) having from 2 to about 20 carbon atoms, have a much lower abrasion than would be expected, based on the measurements of the individual components of mix. Examples 45, 59 and 64 illustrate that 20 percent of the polyolefin is sufficient to reduce the abrasion of the mixture to 2/3 or even considerably less, compared to the abrasion of an ethylene / styrene interpolymer alone in Examples 39 and 41 . When an ethylene / styrene interpolymer is mixed with HDPE, as in Examples 51 to 55 and 64 to 68, the abrasion of the mixture is even less than the abrasion of each individual component in Examples 39, 41 and Comparative Example 56. These findings are confirmed by comparing a) Examples 41 and 71 to 74, b) examples 41 and 75 to 78 and c) examples 39 and 79 to 81. The comparison between examples 39, 41, 70, 82 and comparative examples 57 and 58 illustrate the excellent scratch resistance of floor coatings of the present invention, compared to known floor coatings.

Claims (10)

REIVI NDICATIONS

1 . A floor, wall or roof covering comprising one or more substantially random interpolymers prepared by polymerizing one or more α-olefin monomers with one or more vinylidene aromatic monomers, and / or one or more cysteine or aliphatic or cycloaliphatic vinylidene monomers, and optionally with one or more other polymerizable ethylenically unsaturated monomers.

2. The floor, wall or ceiling covering of claim 1, wherein said one or more interpolymers contain interpoles bristling from 35 to 99.5 mole percent of one or more α-olefin monomers and from 0.5 to 65 mole percent of one or more vinylidene aromatic monomers, and / or one or more aliphatic or cycloaliphatic vinylidene monomers clogged, and optionally another or other polymerizable ethylenically unsaturated monomers.

3. The floor, wall or ceiling covering of claim 1 or claim 2, wherein said one or more substantially random interpolymers contain one or more tetrada sequences consisting of a-olefin / aromatic vinylidene monomer / aromatic monomer vinylidene / α-olefin detectable by 13 C NMR spectroscopy, wherein the monomer insertions of said tetrads occur exclusively in a 1, 2 (head-to-tail) manner.

4. The floor, wall or ceiling covering of any of claims 1 to 3, wherein said one or more interpolymers substantially random materials contain from 80 to 50 percent mole of one or more α-olefin monomers and from 20 to 50 percent mole of one or more vinylidene aromatic monomers, and / or one or more aliphatic or cycloaliphatic vinylidene monomers clogged, and optionally one or more other polymerizable ethylenically unsaturated monomers.

5. The floor, wall or ceiling covering of any one of claims 1 to 4 containing a filler in an amount up to 95 percent, based on the total weight of the floor, wall or ceiling covering.

6. The floor covering of claim 5 in the form of floor tiles and containing from 50 to 95 percent of a fill, based on the weight of the floor tiles. The floor, wall or ceiling covering of any of claims 1 to 6, wherein the amount of said one or more substantially random interpolymers is from 5 to 100 percent, based on the total weight of the floor, wall or wall covering. ceiling. The floor, wall or ceiling covering of any one of claims 1 to 7, comprising up to 90 percent of one or more polymers different from said or said substantially random interpolymers, based on the total weight of the floor, wall or ceiling covering . 9. The floor, wall or ceiling covering of any of claims 1 to 8, comprising a mixture from 5 to 99 per cent of said one or more substantially random interpolymers and 95 to 1 weight percent of one or more homopolymers or interpolymers of aliphatic α-olefins, having from 2 to 20 carbon atoms, or α-olefins having from 2 to 20 carbon atoms and containing polar groups, based on the total weight of the mixture. 10. The floor, wall or ceiling covering of claim 9, comprising a mixture of from 5 to 99 percent of said one or more substantially random interpolymers and 95 to 1 percent by weight of one or more polymers selected from the group consisting of homopolymers of ethylene; propylene homopolymers, copolymers of ethylene and at least one different α-olefin containing from 4 to 8 carbon atoms; propylene copolymers and at least one different α-olefin containing from 4 to 8 carbon atoms; copolymers of ethylene and at least one of acrylic acid, vinyl acetate, maleic anhydride or acrylonitrile; copolymers of propylene and at least one of acrylic acid, vinyl acetate, maleic anhydride or acrylonitrile; and terpolymers of ethylene, propylene and a diene. eleven . The floor, wall or ceiling covering of any of claims 1 to 10 containing at least two layers, wherein the at least one layer (A) comprises said one or more substantially random interpolymers. The floor, wall or ceiling covering of claim 1, wherein the thickness of said layer (A) is from 25 μm to 2 mm. The floor, wall or ceiling covering of claim 1 or claim 12, wherein said layer (A) contains from 25 to 100 percent said or said substantially random interpolymers, based on the total weight of the layer (A). The floor, wall or ceiling covering of any of claims 1 to 13, wherein said layer (A) and one or more additional polymer layers (B). 15. The floor, wall or ceiling covering of claim 14, wherein the thickness ratio between layer (A) and layer (s) (B) is from 0.01: 1 to 10: 1. floor, wall or ceiling of claim 13 or claim 14, wherein said layer (B) comprises one or more homopolymers or interpolymers of aliphatic α-olefins having from 2 to 20 carbon atoms, or α-olefins having from 2 to 20 carbon atoms and containing polar groups. The floor, wall or ceiling covering of claim 14 or claim 15, wherein said layer (B) contains an ethylene or propylene homopolymer; or a copolymer of ethylene or propylene and at least one different α-olefin containing from 4 to 8 carbon atoms; or a copolymer of ethylene or propylene and at least one of acrylic acid, vinyl acetate, maleic anhydride or acrylonitrile; or a terpolymer of ethylene, propylene and a diene. 18. A floor, wall or ceiling covering of any of claims 14 to 17, wherein the layer (A) and the layer (B) each comprise said one or more substantially random interpolymers, wherein the average molar content of the component of vinylidene monomer in the interpolymer (s) in layer (B) is different from average molar content of the vinylidene monomer component in the interpolymer or layers in layer (A). 19. The floor, wall or ceiling covering of any of claims 1 to 18, said layer (A) comprising the top layer. 20. The use of a substantially random interpolymer prepared by polymerizing one or more α-olefin monomers with one or more vinylidene aromatic monomers, and / or one or more aliphatic or cycloaliphatic vinylidene monomers clogged, and optionally with one or more other monomers Polymerizable ethylenically unsaturated to produce floor, wall or ceiling coatings.