WO2012017235A1

WO2012017235A1 - Covered floors and methods of adhering flooring to a floor

Info

Publication number: WO2012017235A1
Application number: PCT/GB2011/051461
Authority: WO
Inventors: Warrick James David Allen; James Leonard Rolfe; Andrea Duffy
Original assignee: Novel Polymer Solutions Ltd
Current assignee: Novel Polymer Solutions Ltd
Priority date: 2010-08-02
Filing date: 2011-08-02
Publication date: 2012-02-09
Anticipated expiration: 2013-02-02

Abstract

According to the invention there is provided a covered floor including: a floor; flooring of the type having an underside at least partially formed from a polymeric material, the flooring at least partially overlaying the floor; a polymeric coating on the underside of the flooring; optionally, an intermediate layer adhered to the floor; and an adhesive layer on the underside of the flooring, the adhesive layer adhering the flooring to the floor, optionally via the intermediate layer; in which the polymeric coating acts to promote adhesion of the adhesive layer to the floor or the intermediate layer, and is formed by polymerising a polymeric precursor which includes a group of sub-formula (I) where R¹ is i) CR^a, where R^a is hydrogen or alkyl, ii) a group S(0)_pR¹³, or SiR¹⁴ where R¹³ and R¹⁴ are independently selected from hydrogen or hydrocarbyl, p is 0, 1 or 2 and q is 1 or 2, iii) C(O)N, S(O)₂N, C(0)ON, CH₂ON, or CH=CHR^CN where R^c is an electron withdrawing group, or iv) OC(0)CH, C(0)OCH or S(0)₂CH; in which R¹² is selected from hydrogen, halo, nitro, hydrocarbyl, optionally substituted or interposed with functional groups, or formula (II) R² and R³ are independently selected from (CR⁷R⁸)n, or a group CR⁹R^10, CR⁷R⁸CR⁹R¹⁰ or CR⁹R¹⁰CR⁷R⁸ where n is 0, 1 or 2, R⁷ and R⁸ are independently selected from hydrogen, halo or hydrocarbyl, and either one of R⁹or R¹⁰ is hydrogen and the other is an electron withdrawing group, or R⁹and R¹⁰ together form an electron withdrawing group; R⁴ and R⁵ are independently selected from CH or CR¹¹ where CR¹¹ is an electron withdrawing group, the dotted lines indicate the presence or absence of a bond, X¹ is a group CX²X³ where the dotted line bond to which it is attached is absent and a group CX² where the dotted line to which it is attached is present, Y¹ is a group CY²Y³ where the dotted line to which it is attached is absent and a group CY² where the dotted line to which it is attached is present, and X²,X³,Y² and Y³ are independently selected from hydrogen, fluorine or other substituents.

Description

COVERED FLOORS AND METHODS OF ADHERING FLOORING TO A

FLOOR

This invention relates to covered floors comprising a floor and a flooring thereon, and also to methods of adhering flooring to a floor.

It is well known to provide flooring in the form of tiles or sheeting which is adhered to a floor in order to provide a covered floor having desired properties such as durability, appearance and surface finish. Traditionally, polyvinylchloride (PVC) has been used extensively in the manufacture of domestic and industrial flooring. However, there are increasing concerns associated with the use of PVC owing to its potential to cause harm to human health and to the environment. It is well known that PVC typically contains high levels of phthalates and chlorinated paraffins which are employed as plasticisers. In the event of a fire, PVC can release harmful chemical substances such as furans, dioxins and hydrogen chloride. In anticipation of likely changes to legislation surrounding the use of PVC in consumer goods, there is a general desire in many industries to eliminate or at least reduce the use of PVC. Flooring is an example of such an industry, in which a number of manufacturers have developed alternative, PVC-free flooring products. There are now a number of flooring products which are based on thermoplastics, elastomers and rubbers such as styrene butadiene rubbers (SBR) and nitrile butadiene rubbers (NBR). It is desired to be able to adhere such flooring materials using conventional flooring adhesives such as water based acrylic emulsions. However, it is not possible to achieve acceptable levels of adhesion on typical base floors such as concrete and plywood without a pre-treatment step.

Some flooring material can be secured to a floor via an intermediate layer such as a layer of polyurethane foam. The flooring is adhered to the polyurethane foam with an adhesive, and the intermediate layer is separately adhered to the floor. Problems have been encountered in achieving an acceptable level of adhesion to flooring with such an intermediate layer.

From the foregoing discussions, it will be apparent that there is a desire to provide flooring products which do not utilise PVC, but there is a problem with obtaining satisfactory levels of adhesion with these products. It will also be apparent that there is a desire to provide alternative approaches which would eliminate the necessity of employing undesired pre-treatment steps such as surface roughening and corona treatment which may be costly or not wholly effective.

The present invention, in at least some of its embodiments, overcomes the above mentioned problems, and satisfies the above mentioned needs.

According to a first aspect of the invention there is provided a covered floor including:

a floor;

flooring of the type having an underside at least partially formed from a polymeric material, the flooring at least partially overlaying the floor;

a polymeric coating on the underside of the flooring;

optionally, an intermediate layer adhered to the floor; and

an adhesive layer on the underside of the flooring, the adhesive layer adhering the flooring to the floor, optionally via the intermediate layer; in which the polymeric coating acts to promote adhesion of the adhesive layer to the floor or the intermediate layer, and is formed by polymerising a polymeric precursor which includes a group of sub-formula (I)

where R¹ is i) CR^a, where R^a is hydrogen or alkyl, ii) a group S(0)_pR¹³, or SiR¹⁴ where R¹³ and R¹⁴ are independently selected from hydrogen or hydrocarbyl, p is 0, 1 or 2 and q is 1 or 2, iii) C(0)N, S(0)₂N, C(O)ON, CH₂ON, or CH=CHR^CN where R^c is an electron withdrawing group, or iv) OC(0)CH, C(0)OCH or S(0)₂CH; in which R ² is selected from hydrogen, halo, nitro, hydrocarbyl, optionally substituted or interposed with functional groups, or

— R³— R⁵ =Y¹ .

R² and R³ are independently selected from (CR⁷R⁸)_n, or a group CR⁹R¹⁰, CR⁷R⁸CR⁹R¹⁰ or CR⁹R¹⁰CR⁷R⁸ where n is 0, 1 or 2, R⁷ and R⁸ are independently selected from hydrogen, halo, or hydrocarbyl, or alkyl, and either one of R⁹ or R¹⁰ is hydrogen and the other is an electron withdrawing group, or R⁹ and R¹⁰ together form an electron withdrawing group;

R⁴ and R⁵ are independently selected from CH or CR¹¹ where CR¹¹ is an electron withdrawing group,

the dotted lines indicate the presence or absence of a bond, X¹ is a group CX²X³ where the dotted line bond to which it is attached is absent and a group CX² where the dotted line to which it is attached is present, Y¹ is a group CY²Y³ where the dotted line to which it is attached is absent and a group CY² where the dotted line to which it is attached is present, and X²,X³,Y² and Y³ are independently selected from hydrogen, fluorine or other substituents.

The polymeric precursors provided by the invention are preferably utilised with little or no solvents or other VOCs, and hence minimise the environmental impact of the invention. Furthermore, it has been found that polymeric coatings of the invention can provide excellent adhesion promotion on a number of materials which are used to form the undersides of flooring.

For the avoidance of doubt, the term 'polymeric precursor' includes reference to monomers, and also to pre-polymers obtained by partial or pre- polymerisation of one or more monomers. The term 'floor' refers to a basal constructional substrate such as in a room or other compartment of a building.

In many embodiments, the underside of the flooring is directly adhered to the floor, ie, there is no intermediate layer. In these embodiments, the polymeric coating acts to promote adhesion of the adhesive layer directly to the floor. In other embodiments, an intermediate layer is present. The intermediate layer may be formed from a polyurethane or other polymeric layer, and may be in the form of a foam. The intermediate layer may be adhered to the floor using techniques which are well known to the skilled reader.

In certain preferred embodiments the underside consists essentially of the polymeric material.

In other preferred embodiments the underside consists of a mixture of the polymeric material with one or more additives. The mixture may include one or more mineral additives. The polymeric material may be an elastomer, preferably a rubber. The rubber may be natural or synthetic, and may be SBR or NBR rubber. Flooring having an underside at least partially formed from a rubber may be adhered directly to the floor, or via an intermediate layer.

The polymeric material may be a thermoplastic, such as thermoplastic polyolefins (TPOs) or thermoplastic polyurethanes (TPUs). Examples of thermoplastic polyolefins include polypropylene or polyethylene. Although it is advantageous that floors having non-PVC undersides can be adhered to floors, the invention encompasses also floors having an underside which is at least partially formed from PVC.

The adhesive layer may be formed from a water-based adhesive. The use of solvent-based adhesives is also possible.

The adhesive layer may be formed from an acrylic adhesive. Water- based acrylic adhesives are particularly preferred, such as Forbo 540, Uzin KE66 and others which are well known to the skilled reader. It is advantageous that conventional floor adhesives such as these can be used in connection with the invention.

Alternatively, the adhesive layer may be formed from a hot-melt adhesive. Hot-melt adhesives may be used to adhere the floor to an intermediate layer such as a polyurethane or other polymeric layer. The hot-melt adhesive may be formed from a polymeric material. Polyurethane, polyethylene, polypropylene, or polyethylene terephthalate hot-melt adhesives may be utilised.

The floor may be of any conventional kind, such as a concrete, composite or wooden floor. Examples of wooden floors that may be covered with flooring include beech, oak, pine and plywood. Composite floors include cement-based floors such as fibre cement floors.

The flooring may comprise sheeting or a plurality of tiles.

According to a second aspect of the invention there is provided a method of adhering flooring to a floor including the steps of:

providing flooring of the type having an underside at least partially formed from a polymeric material;

providing a polymeric precursor which includes a group of sub-formula (I)

where R is i) CR^a, where R^a is hydrogen or alkyl, ii) a group S(0)_pR¹³, or SiR¹⁴ where R¹³ and R¹⁴ are independently selected from hydrogen or hydrocarbyl, p is 0, 1 or 2 and q is 1 or 2, iii) C(0)N, S(O)₂N, C(0)ON, CH₂ON, or CH=CHR^CN where R^c is an electron withdrawing group, or iv) OC(0)CH, C(0)OCH or S(0)₂CH; in which R ² is selected from hydrogen, halo, nitro, hydrocarbyl, optionally substituted or interposed with functional groups, or

— R³— R⁵=Y¹ .

R² and R³ are independently selected from (CR⁷R⁸)_n, or a group CR⁹R¹⁰, CR⁷R⁸CR⁹R¹⁰ or CR⁹R¹⁰CR⁷R⁸ where n is 0, 1 or 2, R⁷ and R⁸ are independently selected from hydrogen, halo or hydrocarbyl, and either one of R⁹ or R¹⁰ is hydrogen and the other is an electron withdrawing group, or R⁹ and R¹⁰ together form an electron withdrawing group;

R⁴ and R⁵ are independently selected from CH or CR¹ where CR¹¹ is an electron withdrawing group,

the dotted lines indicate the presence or absence of a bond, X¹ is a group CX²X³ where the dotted line bond to which it is attached is absent and a group CX² where the dotted line to which it is attached is present, Y is a group CY²Y³ where the dotted line to which it is attached is absent and a group CY² where the dotted line to which it is attached is present, and X²,X³,Y² and Y³ are independently selected from hydrogen, fluorine or other substituents;

polymerising the polymeric precursor to form a polymeric coating on the underside of the flooring;

optionally, adhering an intermediate layer to the floor;

applying an adhesive layer to the polymeric coating on the underside of the flooring, the floor or, if present, the intermediate layer;

bringing the adhesive layer on the polymeric coating on the underside of the flooring, the floor or, if present, the intermediate layer into contact with the other of the polymeric coating on the underside of the flooring, the floor or, if present, the intermediate layer; and

allowing the adhesive layer to set thereby adhering the flooring to the floor, optionally via the intermediate layer;

in which the polymeric coating acts to promote adhesion of the adhesive layer to the floor or the intermediate layer.

In this way, it is possible to coat undersides formed from low surface energy materials, such as rubbers. Without wishing to be bound by any particular theory, it is believed that at least part of the problem associated with bonding to low surface energy materials lies in the initial requirement of deposited layer to have a surface tension lower than that of the surface energy of the material. Compounds of Formula (I) can be provided which are sufficiently hydrophobic in nature or otherwise suitable to adhere to the low surface energy material, but are nevertheless able to activate the double bond or bonds sufficiently for polymerisation to be able to occur.

It will be apparent to the skilled person that the order of some of the steps may be interchanged. For example, the intermediate layer may be adhered to the floor after the application of the adhesive layer which is formed between the polymeric coating and the intermediate layer.

Typically, the adhesive layer is applied to the floor and then contacted with the polymeric coating on the underside of the flooring in embodiments where there is no intermediate layer. In embodiments where an intermediate layer is present, the adhesive layer may be applied to the intermediate layer and then contacted with the polymeric coating on the underside of the flooring, or the adhesive layer may be applied to the polymeric coating on the underside of the flooring and then contacted with the intermediate layer.

Preferably, the polymeric precursor is polymerised by exposure to ultraviolet radiation. Alternative polymerisation methods include the application of heat (which may be in the form of IR radiation), where necessary in the presence of an initiator, by the application of other sorts of initiator such as chemical initiators, or by initiation using an electron beam. The expression "chemical initiator" as used herein refers to compounds which can initiate polymerisation such as free radical initiators and ion initiators such as cationic or anionic initiators as are understood in the art. Radiation or electron beam induced polymerisation is suitably effected in the substantial absence of a solvent. As used herein, the expression "in the substantial absence of solvent" means that there is either no solvent present or there is insufficient solvent present to completely dissolve the reagents, although a small amount of a diluent may be present to allow the reagents to flow.

In the preferred embodiments in which the monomer is polymerised by exposure to ultraviolet radiation, polymerisation may take place either spontaneously or in the presence of a suitable initiator. Examples of suitable initiators include 2, 2' - azobisisobutyronitrile (AIBN), aromatic ketones such as benzophenones in particular acetophenone; chlorinated acetophenones such as di- or tri-chloracetophenone; dialkoxyacetophenones such as dimethoxyacetophenones (sold under the trade name "Irgacure 651 ") dialkylhydroxyacetophenones such as dimethylhydroxyacetophenone (sold under the trade name "Darocure 1 173"); substituted dialkylhydroxyacetophenone alkyl ethers such compounds of formula

where R^y is alkyl and in particular 2, 2-dimethylethyl, R^x is hydroxyl or halogen such as chloro, and R^p and R^q are independently selected from alkyl or halogen such as chloro (examples of which are sold under the trade names "Darocure 1 16" and "Trigonal P1 "); 1-benzoylcyclohexanol-2 (sold under the trade name "Irgacure 184"); benzoin or derivatives such as benzoin acetate, benzoin alkyl ethers in particular benzoin butyl ether, dialkoxybenzoins such as dimethoxybenzoin or deoxybenzoin; dibenzyl ketone; acyloxime esters such as methyl or ethyl esters of acyloxime (sold under the trade name "Quantaqure PDO"); acylphosphine oxides, acylphosphonates such as dialkylacylphosphonate, ketosulphides for example of formula

where R^z is alkyl and Ar is an aryl group; dibenzoyl disulphides such as 4, 4'- dialkylbenzoyldisulphide; diphenyldithiocarbonate; benzophenone; 4, 4'-bis (N, N-dialkyamino) benzophenone; fluorenone; thioxanthone; benzil; or a compound of formula

where Ar is an aryl group such as phenyl and R^z is alkyl such as methyl (sold under the trade name "Speedcure BMDS"), or an initiator of the type sold under the trade name 'Irgacure 127'.

As used herein, the term "alkyl" refers to straight or branched chain alkyl groups, suitably containing up to 20 and preferably up to 6 carbon atoms. The terms "alkenyl" and "alkynyl" refer to unsaturated straight or branched chains which include for example from 2-20 carbon atoms, for example from 2 to 6 carbon atoms. Chains may include one or more double to triple bonds respectively. In addition, the term "aryl" refers to aromatic groups such as phenyl or naphthyl.

The term "hydrocarbyl" refers to any structure comprising carbon and hydrogen atoms. For example, these may be alkyl, alkenyl, alkynyl, aryl such as phenyl or napthyl, arylalkyl, cycloalkyl, cycloalkenyl or cycloalkynyl. Suitably they will contain up to 20 and preferably up to 10 carbon atoms. The term "heterocylyl" includes aromatic or non-aromatic rings, for example containing from 4 to 20, suitably from 5 to 10 ring atoms, at least one of which is a heteroatom such as oxygen, sulphur or nitrogen. Examples of such groups include furyl, thienyl, pyrrolyl, pyrrolidinyl, imidazolyl, triazolyl, thiazolyl, tetrazolyl, oxazolyl, isoxazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, benzthiazolyl, benzoxazolyl, benzothienyl or benzofuryl.

The term "functional group" refers to reactive groups such as halo, cyano, nitro, oxo, C(0)_nR^a, OR^a, S(0)_tR^a, NR^bR^c, OC(0)NR^bR^c, C(0)NR^bR^c, OC(O) NR^bR^c, -NR⁷C(0)_nR⁶, -NR^aCONR R^c, - C=NOR^a, -N=CR^bR^c, S(0)_tNR^bR^c, C(S)_nR^a, C(S)OR^a, C(S)NR^bR^c or - NR^bS(0)_tR^a where R^a, R^b and R^c are independently selected from hydrogen or optionally substituted hydrocarbyl, or R^b and R^c together form an optionally substituted ring which optionally contains further heteroatoms such as S(0)_s, oxygen and nitrogen, n is an integer of 1 or 2, t is 0 or an integer of 1 -3. In particular, the functional groups are groups such as halo, cyano, nitro, oxo, C(0)_nR^a, OR^a, S(0)_tR^a, NR^bR^c, OC(0)NR^bR^c, C(0)NR^bR^c, OC(0)NR^bR^c, -NR⁷C(0)_nR⁶, -NR^aCONR^bR^c, - NR^aCSNR^bR^c, C=NOR^a, -N=CR^bR°, S(0)_tNR^bR°, or -NR^bS(0)_tR^a where R^a, R^b and R^c , n and t are as defined above. The term "heteroatom" as used herein refers to non-carbon atoms such as oxygen, nitrogen or sulphur atoms. Where the nitrogen atoms are present, they will generally be present as part of an amino residue so that they will be substituted for example by hydrogen or alkyl.

The term "amide" is generally understood to refer to a group of formula C(0)NR^aR^b where R^a and R^b are hydrogen or an optionally substituted hydrocarbyl group. Similarly, the term "sulphonamide" will refer to a group of formula S(0)₂NR^aR^b. Suitable groups R^a include hydrogen or methyl, in particular hydrogen.

The nature of any electron withdrawing group or groups additional to the amine moiety used in any particular case will depend upon its position in relation to the double bond it is required to activate, as well as the nature of any other functional groups within the compound. The term "electron withdrawing group" includes within its scope atomic substituents such as halo, e.g. fluoro, chloro and bromo, and also molecular substituents such as nitrile, trifluoromethyl, acyl such as acetyl, nitro, or carbonyl.

In the group of sub-formula (I), X¹ and, where present, Y¹ preferably represents CX² X³ and CY² Y³ respectively, and the dotted bonds are absent.

Preferably R¹³ and R¹⁴, when present, are alkyl groups, most preferably Ci to C₃ alkyl groups.

Advantageously, R^c, when present, is a carbonyl group or phenyl substituted at the ortho and/or para positions by an electron withdrawing substituent such as nitro.

Preferably, R⁷ and R⁸ are independently selected from fluoro, chloro or alkyl or H. In the case of alkyl, methyl is most preferred.

Preferably, X², X³, Y² and Y³ are all hydrogen.

It is possible that at least one, and possibly all, of X², X³, Y² and Y³ is a substituent other than hydrogen or fluorine. Preferably at least one, and possible all, of X², X³, Y² and Y³ is an optionally substituted hydrocarbyl group. In such embodiments, it is preferred that at least one, and most preferably all, of X², X³, Y² and Y³ is an optionally substituted alkyl group. Particularly preferred examples are Ci to C₄ alkyl groups, especially methyl or ethyl. Embodiments in which X², X³, Y² and/or Y³ are alkyl groups are able to polymerise when exposed to radiation without the presence of an initiator. Alternatively, at least one, and preferably all, of X², X³, Y² and Y³ are aryl and/or heterocyclic, such as pyridyl, pyrimidinyl, or a pyridine or pyrimidine containing group.

In preferred embodiments, R¹² is -R³ -R⁵ =. Y¹, X¹ and Y are groups CX²X³ and CY¹Y² respectively and the dotted lines represent an absence of a bond. In these embodiments, the polymerisation may proceed by a cyclopolymerisation reaction.

A preferred group of polymeric precursors for use in the method of the invention are compounds of formula (II)

and in particular compounds of formula (HA)

where r is an integer of 1 or more and R is one or more of a bridging group, an optionally substituted hydrocarbyl group, a perhaloalkyi group, a siloxane group, an amide, or a partially polymerised chain containing repeat units.

Preferably, r is , 2, 3 or 4.

In preferred embodiments of formula (II), R¹ is S(0)₂N or C(O)N. Thus, the polymeric precursor may be a compound of structure (III)

where R is C(O) or S(0)₂.

Advantageously, the polymeric precursor is a compound of structure (IV)

[IV] Where in the compounds of formulae (II) to (IV), r is 1 , compounds can be readily polymerised to form a variety of polymer types depending upon the nature of the group R⁶.

Where in the compounds of formulae (II) to (IV), r is greater than one, polymerisation can result in polymer networks. On polymerisation of these compounds, networks are formed whose properties maybe selected depending upon the precise nature of the R⁶ group, the amount of chain terminator present and the polymerisation conditions employed. Some examples of bridging groups can be found in WO 00/06610.

Preferably, R⁶ comprises a straight or branched chain hydrocarbyl group, optionally substituted or interposed with functional groups. Advantageously, the straight or branched chain hydrocarbyl is interposed or substituted with one or more of an amine moiety, C(O) or COOH.

In some embodiments, the polymeric precursor is a monomer in which R⁶ is a straight or branched chain hydrocarbyl interposed with an amine moiety, or a pre-polymer obtained by pre-polymerisation of said monomer. Preferably, the monomer is a straight or branched chain alkyl group having 1 to 30 carbon atoms, optionally interposed with a cyclic group. In particular in preferred embodiments, the monomer is a compound of formula (V)

where R^1b is H or C_s H_2s +i , p is 1 to 10, 9 is 0 to 10 and s is 1 to 10. other preferred embodiments, the monomer is a compound of formula

[VI] where t and u are independently 1 to 10 and R¹⁶ is H or C_sH_2s+i , where s is 1 to 10.

In other preferred embodiments, the polymeric precursor is a monomer in which R⁶ is a straight or branched chain hydrocarbyl substituted with a COOH end group, or a pre-polymer obtained by pre-polymerisation of said monomer. The monomer may be a straight or branched chain alkyl group having 1 to 30 carbon atoms, optionally interposed with a cyclic group. Advantageously, the monomer is a compound of formula (VII)

where v is 1 to 20.

In alternative embodiments, the polymeric precursor is a monomer in which R⁶ is a straight or branched chain alkyl group having 1 to 30 carbon atoms, or a pre-polymer obtained by pre-polymerisation of said monomer.

In other embodiments still, the polymeric precursor is a monomer in which, R⁶ is a partially or per-halogenated straight or branched chain alkyl group having 1 to 30 carbon atoms, or a pre-polymer obtained by pre-polymerisation of said monomer. Preferably, the alkyl group is per-halogenated. It is preferred that the alkyl group is fluorinated, most preferably per-fluorinated.

In other embodiments still, the polymeric precursor is a monomer in which R ⁵ is CO and R⁶ terminates in one or more amine moieties forming a urea structure, or a pre-polymer obtained by pre-polymerisation of said monomer.

In yet further embodiments, the polymeric precursor is a monomer of structure (VIII)

where R⁶ is a straight or branched chained hydrocarbyl group, optionally substituted or interposed with functional groups, and r is an integer of two or more, or a pre-polymer obtained by a pre-polymerisation of said monomer. Preferably, r is two or three.

In other embodiments, R¹⁵ is hydrogen or hydrocarbyl, and thus the compound of formula (I) does not include the group -R³-R⁵=Y¹. In these embodiments, a preferred class of the compound of formula (I) is represented as structure (X)

where R¹⁶ is selected from hydrogen, halo, nitro, or hydrocarbyl, optionally substituted or interposed with functional groups, only. A particularly preferred compound of formula (X) is a compound of formula (XI)

International Publications WO 00/06610, WO 00/06533, WO 00/06658, WO 01/36510, WO 01/40874, WO 01/74919, WO 2007/012860, WO 2008/001 102, and WO 2009/063211 , the contents of all of which are herein incorporated by reference, disclose a general class of polymers obtained from the polymerisation of a number of compounds which possess one or more dienyl groups. The Applicant's co-pending UK patent applications 1012954.2 and 1016664.3 provide further details concerning the synthesis and polymerisation of some examples of the classes of monomers described herein.

The polymerisation of the polymeric precursor may produce a homopolymer. Alternatively, the step of polymerising the polymeric precursor may produce a copolymer, the polymeric precursor being mixed with one or more other polymeric precursors. The other polymeric precursor may be according to any of the formulae described herein. Alternatively, the co- monomer may be of a different class of compounds. The polymeric precursor may be copolymerised with a cross-linker. In these embodiments, the polymeric precursor may be reacted with a compound of formula (XII)

where R¹, R², R⁴, R ¹² and X¹ are as defined in relation to formula (I), r is an integer of 2 or more, and R⁶ is a bridging group of valency r or a bond. Preferably, r is 2. The use of a compound of formula (XII) is particularly advantageous when the polymeric precursor does not include the group -R³ -R⁵: Y . However, embodiments of polymeric precursors which include the group - R³ -R⁵=Y¹ may also be reacted with a compound of formula (XII).

The compound of formula (XII) may be a compound of formula (XIII)

In preferred embodiments, the polymeric precursor is: N, N- diallylhexanamide, N, N-Diallyl-3-(propylamino)propanamide, N, N-Diallyl-2(- butyl-diallylcarbamoylmethylamino)acetamide; a co-monomer mixture including N, N-diallylhexanamide, N, N-Diallyl-3-(propyIamino)propanamide, or N, N- Diallyl-2(-butyl-diallylcarbamoylmethylamino)acetamide. Alternatively, the polymeric precursor may be a pre-polymer obtained by a pre-polymerisation of any of these substances. Preferred co-monomer mixtures comprise: N, N-Diallyl- 3-(propylamino)propanamide / N, N, N', N'-tetraallylethanediamide; and N, N- diallylhexanamide / N, N-Diallyl-2(-butyl- diallylcarbamoylmethylamino)acetamide.

The polymeric precursor may contain one or more additives, such as a wetting agent. A siloxane wetting agent may be used.

The monomer or co-monomers may be pre-polymerised to produce a pre- polymer. Typically, a thermal initiator is used and pre-polymerisation is performed at an elevated temperature above ambient temperature.

In practice, the polymeric precursor is generally applied to the flooring and then polymerised. However, in principle the polymeric precursor might be polymerised and then brought into contact with the flooring to form a polymeric coating thereon.

Whilst the invention has been described above, it extends to any inventive combination of sub-combination of the features set out above or in the following description, drawings or claims.

Embodiments of covered floors, floors and floorings in accordance with the invention will now be described with reference to the single accompanying Figure, which is a cross-sectional view of a covered floor of the invention.

The Figure shows an example of a covered floor of the invention, depicted generally at 10, which comprises a floor 12 in the form of a permanently installed base substrate, and an adhesive layer 14 formed on the floor 12. The adhesive layer 14 adheres the floor 12 to flooring 16. The flooring 16 comprises a main flooring structure 16a having an underside 16b. On the underside 16b there is formed a polymeric coating 16c of the type described herein. The polymeric coating 16c acts to promote adhesion between the flooring 16 and the adhesive layer 14. Polymeric coatings of the invention have been found to promote excellent adhesion of various conventional flooring materials to conventional floors such as fibre cement board and beech wood floors using conventional flooring adhesives.

Unless otherwise stated, all percentages described below are wt%.

Example 1

Adhesion promotion of SBR rubber flooring to water based adhesives using a copolymer of N, N-Diallyl-3-(propylamino)propanamide and N, N, N', N'-Tetraallylethanediamide

A mixture of N, N-Diallyl-3-(propylamino)propanamide ( 060.5g) and N, N, N', N'-Tetraallylethanediamide (79.5g) was heated to 80°C and maintained at this temperature with constant stirring. To this mixture a concentrate of Vazo 67 (DuPont) thermal initiator (75. Og) dissolved in N, N-Diallyl-3 propylamino)propanamide (264.75g) and N, N, N', N'-Tetraallylethanediamide (20.25g) was added dropwise over 6 hours with stirring and the reaction temperature maintained at 80°C. After addition of the concentrate the reaction was left for a further 12 hours at this temperature with constant stirring and then left to cool to room temperature to yield a viscous brown oil. ITX photoinitiator (45. Og) and ethyl 4-dimethylaminobenzoate synergist (30. Og) were then added and fully dissolved into the reaction product.

A layer of this formulation was coated onto a sheet of SBR rubber flooring at a coating weight of approximately 2gsm and cured using a focused 200W/cm UV source with an iron doped mercury bulb at a belt speed of 4 metres/minute. Synthesis of N, N-DialIyl-3-(propylamino)propanamide

3-bromopropionylchloride in dichloromethane (1 :1 v/v) was added drop wise to a slight molar excess of diallylamine in dichloromethane (DCM) at ~10°C over 2 hours with constant stirring. This was then washed in dilute HCI and DCM and the organic fraction retained. The solution of product in DCM was then purified by column chromatography using silica (60A) and the dichloromethane removed to yield the 3-bromo-N,N-diaIlylpropylamide intermediate; a yellow liquid (density ~ 1.27g/cm³). Yield 70%+.

Intermediate from 1 (30g, 129mmoles) was added to THF (1 :1 v/v). This was then added dropwise over 2 hours into a stirred, refluxing mixture of 1 - propylamine ( 43.1 g, 0.730 mmoles), potassium carbonate (90g, 0.652mmoles) and THF (133.6g, 1.850mmoles). The reflux was then left to cool over 1 hour with constant stirring.

The cooled reaction mixture was washed in water (400ml), dissolving the potassium carbonate and leaving a clear, yellow organic top layer, which was decanted off. This layer was then washed again in water, separated and dried to yield a yellow liquid. Yield ~ 65%.

Synthesis of Ν,Ν,Ν',Ν',-tetraallylethanediamide

The target molecule is shown below

Fresh, dry oxaloyl chloride (CIOOCCOOCI) (1 10 mmoles) was placed into a 3-necked round bottomed (RB) flask with 200 ml of dry dichloromethane. Freshly distilled diallylamine (220mmoles) was added to triethylamine (220mmoles), further diluted (1 :1 v/v) in dry dichloromethane then added into a dropping funnel and placed onto the reaction flask. Nitrogen gas was pumped through the vessel through the other two necks. To neutralise HCI produced, the waste gas was bubbled through a CaC0₃ solution. The reaction vessel was then placed into a salt water/ice bath and once the contents were cooled the diallylamine/triethylamine/ dichloromethane was added dropwise to the oxaloyl chloride solution with continual magnetic stirring of the mixture. The temperature was monitored and maintained between 5-10°C. The dropping of the diallylamine and triethylamine was stopped after three hours and the reaction was left to stir for another hour. Thin layer chromatography using ethyl acetate and an alumina was used to monitor the reaction comparing starting material to the product. Iodine was used to develop the plate and the reaction product could be seen as a spot that had been eluted much further than the starting material.

To remove the amine chloride and excess diallylamine the reaction liquor was washed in 3M HCI. The monomer stayed in the dichloromethane fraction and was removed using a separating funnel. For 20g of monomer in 200 ml dichloromethane, 2 washes of 100ml HCI were used. The solvent was then removed in a rotary evaporator.

The product was added to dichloromethane (1 :1 v/v) and passed through a silica gel (Merck, grade 60 for chromatography) column with dichloromethane as the eluent. Some yellow coloration was left in the column which yielded, after removal of the eluent, a very pale yellow oil. The product Ν,Ν,Ν',Ν',- tetraallylethanediamide was produced in -70% yield.

Example 2

Adhesion promotion of a poly(urethane) hot-melt adhesive and PUR foam laminate to Nitrile-Butadiene Rubber (NBR) using an adhesion promotion layer consisting of a polymer made with N, N-Diallyl-2(-butyl- diallylcarbamoylmethylamino)acetamide

N, N-Diallyl-2-(butyl-diallylcarbamoylmethylamino)acetamide (890. Og) was pre-heated to 80°C after which a mixture of thermal initiator Vazo 67 (DuPont) (10. Og) in N, N-Diallyl-2-(butyl-diallylcarbamoylmethylamino)acetamide (100.0g) was added over 2 hours with the temperature maintained at 80°C with constant stirring and under a nitrogen atmosphere. This reaction was left to react for a further 14 hours under the same conditions and then left to cool to room temperature.

The photoinitiator 2-isopropyl thioxanthone (ITX) (31.8g) and synergist ethyl 4-(dimethylamino) benzoate (EDB) (21.2g) were then added and fully dissolved into the mixture prior to use.

This formulation was then coated onto the underside of NBR rubber flooring using a reverse roller method to approximately 2 grams per square metre coat weight and cured under a 200W/cm UV lamp using an iron doped mercury bulb.

A moisture curing MDI based polyurethane hot melt (100% solids) was then deposited at 160°C onto the adhesion promoted NBR at a coating weight between 70 - 80 g/m². Immediately afterwards a PUR foam sheet was laminated onto the hot melt coating under pressure and allowed to cool to room temperature.

The PUR foam sheet can be adhered to a floor using techniques which are well known to the skilled reader.

Synthesis of N, N-Diallyl-2-(butyl-diallylcarbamoylmethylamino)acetamide

intermediate

Et₃N

1-butylamine

THF, reflux

A5B

Chloroacetyl chloride (98%, 212g, 1.883 moles) and dichloromethane (397.5g, 4.680 moles) were added to a reaction vessel and cooled to 5°C. N,N- diallylamine (freshly distilled, 402.57g, 4.143 moles) was added to dichloromethane (397.5g, 4.680moles) and this mixture was then added dropwise to the chloroacetyl chloride mixture over several hours with constant stirring with the temperature kept below 10°C. The reaction mixture was then left to reach room temperature and then washed in water (1.51). The organic phase was washed again in water, followed by separation of the organic phase. Solvent and volatiles were then removed from the organic phase under vacuum to yield a yellow oil, which was further purified by column chromatography with ethyl acetate eluent and silica. Eluent was removed under vacuum to yield a yellow oil. The yield was ~78%.

N,N-Diallyl-2-chloroacetamide (intermediate) (86.75g, 0.500moles), triethylamine (154.38g, 1 .500moles) and tetrahydrofuran (222.25g, 3.082moles) were charged into a reaction flask with 1 -butylamine (99%, 18.29g, 0.250moles) added dropwise over 15 minutes with constant stirring. The temperature of the reaction was brought to reflux and maintained for 4 hours. The reaction was then cooled to room temperature followed by filtration of the triethylamine hydrochloride salt from the reaction liquor. After removal of solvent under vacuum the product was added to dichloromethane (200ml) and then washed twice in water (300ml). The organic phase was separated, dried with magnesium sulfate and filtered. This was followed by removal of solvent under vacuum to yield a pale yellow oil. The yield was ~ 88%.

Example 3

Adhesion promotion of a solvent free acrylate dispersion floor adhesive to Styrene-Butadiene Rubber (SBR) using an adhesion

promotion layer consisting of a polymer made with N, N-Diallyl-2(-butyl- diallylcarbamoylmethylamino)acetamide

N, N-Diallyl-2-(butyl-diallylcarbamoylmethylamino)acetamide (890. Og) was pre-heated to 80°C after which a mixture of thermal initiator Vazo 67 (DuPont) (10. Og) in N, N-Diallyl-2-(butyl-diallylcarbamoylmethylamino)acetamide (100.0g) was added over 2 hours with the temperature maintained at 80°C with constant stirring and under a nitrogen atmosphere. This reaction was left to react for a further 14 hours under the same conditions and then left to cool to room temperature. The photo initiator 2-isopropyl thioxanthone (ITX) (31.8g) and synergist ethyl 4-(dimethylamino) benzoate (EDB) (21 .2g) were then added and fully dissolved into the mixture prior to use.

This formulation was then coated onto the underside of SBR rubber flooring using a reverse roller method to approximately 2 grams per square metre coat weight and cured under a 200W/cm UV lamp using an iron doped mercury bulb.

The treated SBR was then bonded to wooden flooring that had been coated with a solvent free acrylate dispersion adhesive at a coating weight of 350g/m² using a spreading trowel. Approximately 5 minutes was left between spreading of adhesive and bonding to the rubber with an even force applied to the SBR surface once it had been laid onto the wooden flooring.

Example 4

Adhesion promotion of Styrene-Butadiene Rubber (SBR) flooring to a water based acrylic dispersion adhesive using an adhesion promotion layer consisting of a polymer made with N, N-Diallyl-2(-butyl- diallylcarbamoylmethylamino)acetamide and N,N-diallylhexanamide

A mixture of N, N-Diallyl-2-(butyl-diallylcarbamoylmethylamino)acetamide (57. Og), N,N-diallylhexanamide (38. Og), isopropylthioxanthone photoinitiator (ITX) (3.0g) and ethyl dimethyl benzoate synergist (EDB) (2.0g) was warmed gently and stirred until all the solids were fully dissolved. This formulation was then coated onto the underside of SBR rubber flooring using a reverse roller method to approximately 3 grams per square metre coat weight and cured under a 200W/cm UV lamp using an iron doped mercury bulb. The treated SBR was then bonded to wooden flooring that had been coated with a water based acrylic dispersion adhesive at a coating weight of 350g/m² using a spreading trowel. Approximately 15 minutes was left between spreading of adhesive and bonding to the rubber with an even force applied to the SBR surface once it had been laid onto the wooden flooring.

Synthesis of N,N-Diallylhexanamide

Diallylamine (99%, 37g, 381 mmoles), triethylamine (99%, 40g, 396mmoles) and dichloromethane (99+%, 50ml) were mixed and added dropwise to a cooled (0°C ) mixture of hexanoyl chloride (99%+, 50g, 371 mmoles) in dichloromethane (99+%, 200ml) . Temperature was maintained between 0-10 °C with continuous stirring for several hours to allow all of the diallylamine mixture to be added. The reaction mixture was then left to come to room temperature.

The reaction mixture was then washed in dilute HCI (3M, 500ml) and the organic layer separated. Washing of the organic layer was repeated in water or weak brine, followed by drying of the organic layer with anhydrous magnesium sulphate .Dichloromethane and other volatiles were then removed under vacuum to produce a pale yellow liquid, which was then purified further by column chromatography using silica gel (60A ) and dichloromethane as eluent to yield an almost colourless oil. Yield = 70%.

Example 5

Adhesion promotion of an acrylate coated rubber to a water based acrylic dispersion adhesive using a layer consisting of a polymer made with N, N-Diallyl-3-(propylamino)propanamide and Ν,Ν,Ν',Ν'- tetraallylethanediamide

A mixture of N, N-Diallyl-3-(propylamino)propanamide and Ν,Ν,Ν',Ν'- tetraallylethanediamide was made in the ratio 93 : 7 by weight, respectively. To this mixture the photoinitiator 'Irgacure127' (Ciba SC) was added at 3% by weight and dissolved thoroughly.

This mixture was then coated as a thin layer, of approximately 4g/m² coating weight , onto the back of a piece of acrylate coated rubber flooring using a roller method. A 200W/cm UV lamp using an iron doped mercury bulb was then used to cure the coating.

A solvent free acrylate dispersion adhesive was spread onto at a plywood floor section at a coating weight of 300g/m² using a spreading trowel. Approximately 20 minutes was left between spreading of adhesive and bonding it to the treated underside of the rubber flooring, after which an even pressure was then applied across the sample.

Example 6

Adhesion promotion of a mineral filled thermoplastic polymer flooring to a water based acrylic dispersion adhesive using an adhesion promotion layer consisting of a polymer made with N, N-Diallyl-2(-butyl- diallylcarbamoylmethylamino)

A formulation containing N,N-Diallyl-2-(butyl- diallylcarbamoylmethylamino)acetamide (95% by weight) isopropylthioxanthone photoinitiator (ITX) (3.0% by weight), ethyl dimethyl benzoate synergist (EDB) (2.0% by weight) and was made with gentle warming during mixing to ensure all initiator and synergist had dissolved. The underside of a piece of flooring, which consisted of a mineral filled thermoplastic polymer, was then coated with this formulation using a reverse roller method to approximately 3 grams per square metre coat weight. This was then cured under a 200W/cm UV lamp using an iron doped mercury bulb.

The coated thermoplastic flooring was then bonded to a beechwood flooring that had been coated with a water based acrylic dispersion adhesive (Thomsit K188E, Henkel) at a coating weight of 300g/m² using a spreading trowel. Approximately 10 minutes was left between spreading of adhesive and bonding to the rubber with an even force applied to the flooring surface once it had been laid onto the wooden flooring.

Example 7

Adhesion promotion of a mineral filled thermoplastic polymer flooring to a water based acrylic dispersion adhesive using an adhesion promotion layer consisting of a polymer made with N, N-Diallyl-2(-butyl- diallylcarbamoylmethylamino)acetamide and a siloxane additive

A formulation containing N,N-Diallyl-2-(butyl- diallylcarbamoylmethylamino)acetamide (94.5% by weight) isopropylthioxanthone photoinitiator (ITX) (3.0% by weight), ethyl dimethyl benzoate synergist (EDB) (2.0% by weight) and polysiloxane wetting agent (TegoRad 2250, Evonik Tego Chemie, 0.5% by weight) was made with gentle warming during mixing to ensure all initiator and synergist had dissolved. The underside of a piece of flooring, which consisted of a mineral filled thermoplastic polymer, was then coated with this formulation using a reverse roller method to approximately 3 grams per square metre coat weight. This was then cured under a 200W/cm UV lamp using an iron doped mercury bulb.

Claims

1. A covered floor including:

a floor;

flooring of the type having an underside at least partially formed polymeric material, the flooring at least partially overlaying the floor;

a polymeric coating on the underside of the flooring; optionally, an intermediate layer adhered to the floor; and

adhesive layer on the underside of the flooring, the adhesive layer adhering the flooring to the floor, optionally via the intermediate layer;

in which the polymeric coating acts to promote adhesion of the adhesive layer to the floor or the intermediate layer, and is formed by polymerising a polymeric precursor which includes a group of sub-formula (I)

where R is i) CR^a, where R^a is hydrogen or alkyl, ii) a group S(0)_pR¹³, or SiR ⁴ where R¹³ and R ⁴ are independently selected from hydrogen or hydrocarbyl, p is 0, 1 or 2 and q is 1 or 2, iii) C(0)N, S(0)₂N, C(O)ON, CH₂ON, or CH=CHR^CN where R^c is an electron withdrawing group, or iv) OC(0)CH, C(0)OCH or S(0)₂CH; in which R¹² is selected from hydrogen, halo, nitro, hydrocarbyl, optionally substituted or interposed with functional groups, or R² and R³ are independently selected from (CR⁷R⁸)_n, or a group CR⁹R¹⁰, CR⁷R⁸CR⁹R¹⁰ or CR⁹R¹⁰CR⁷R⁸ where n is 0, 1 or 2, R⁷ and R⁸ are independently selected from hydrogen, halo or hydrocarbyl, and either one of R⁹ or R¹⁰ is hydrogen and the other is an electron withdrawing group, or R⁹ and R¹⁰ together form an electron withdrawing group;

2. A covered floor according to Claim 1 in which the underside consists essentially of the polymeric material.

3. A covered floor according to Claim 2 in which the underside consists of a mixture of the polymeric material with one or more additives.

4. A covered floor according to Claim 3 in which the mixture includes one or more mineral additives.

5. A covered floor according to any of the preceding claims in which the polymeric material is an elastomer, preferably a rubber.

6. A covered floor according to Claim 5 in which the rubber is SBR or NBR rubber.

7. A covered floor according to any one of Claims 1 to 4 in which the polymeric material is a thermoplastic.

8. A covered floor according to Claim 7 in which the thermoplastic is a polyolefin.

9. A covered floor according to any preceding claim in which the adhesive layer is formed from a water-based adhesive.

10. A covered floor according to any preceding claim in which the adhesive layer is formed from an acrylic adhesive.

1 1 . A covered floor according to any of Claims 1 to 8 in which the adhesive layer is formed from a hot-melt adhesive.

12. A covered floor according to any preceding claim in which the floor is a concrete or a wooden floor.

13. A covered floor according to any preceding claim in which the flooring comprises sheeting or a plurality of tiles.

14. A method of adhering flooring to a floor including the steps of:

providing a polymeric precursor which includes a group of sub- formula (I)

—

where R¹ is i) CR^a, where R^a is hydrogen or alkyl, ii) a group S(0)_pR¹³, or SiR¹⁴ where R¹³ and R ⁴ are independently selected from hydrogen or hydrocarbyl, p is 0, 1 or 2 and q is 1 or 2, iii) C(0)N, S(0)₂N, C(O)ON, CH₂ON, or CH=CHR°N where R^c is an electron withdrawing group, or iv) OC(O)CH, C(0)OCH or S(0)₂CH; in which R¹² is selected from hydrogen, halo, nitro, hydrocarbyl, optionally substituted or interposed with functional groups, or

— R³— R⁵ =Y¹ .

R² and R³ are independently selected from (CR⁷R⁸)_n, or a group CR⁹R¹⁰, CR⁷R⁸CR⁹R¹⁰ or CR⁹R¹⁰CR⁷R⁸ where n is 0, 1 or 2, R⁷ and R⁸ are independently selected from hydrogen, halo or hydrocarbyl, and either one of R⁹ or R ⁰ is hydrogen and the other is an electron withdrawing group, or R⁹ and R¹⁰ together form an electron withdrawing group;

the dotted lines indicate the presence or absence of a bond, X¹ is a group CX²X³ where the dotted line bond to which it is attached is absent and a group CX² where the dotted line to which it is attached is present, Y¹ is a group CY²Y³ where the dotted line to which it is attached is absent and a group CY² where the dotted line to which it is attached is present, and X²,X³,Y² and Y³ are independently selected from hydrogen, fluorine or other substituents;

optionally, adhering an intermediate layer to the floor;

15. A method according to Claim 14 in which the polymeric precursor is a compound of structure (II)

where r is an integer of 1 or more, R⁶ is one or more of a bridging group, an optionally substituted hydrocarbyl group, a perhaloalkyi group, a siloxane group, an amide, or a partially polymerised chain containing repeat units.

16. A method according to Claim 15 in which the polymeric precursor is a compound of structure [III]

where R ⁵ is C(O) or S(0)₂

17. A method according to Claim 16 in which the polymeric precursor is a compound of structure [IV]

18. A method according to Claim 16 or Claim 17 in which R⁶ comprises a straight or branched chain hydrocarbyl group, optionally substituted or interposed with functional groups.

19. A method according to Claim 18 in which the straight or branched chain is interposed or substituted with one or more of an amine moiety, C(O) or COOH.

20. A method according to Claim 19 in which the polymeric precursor is a monomer in which R⁶ is a straight or branched chain hydrocarbyl interposed with an amine moiety, or a pre-polymer obtained by pre-polymerisation of said monomer.

21. A method according to Claim 20 in which the monomer is a straight or branched chain alkyl group having 1 to 30 carbon atoms, optionally interposed with a cyclic group.

22. A method according to Claim 21 in which the monomer is a compound of Formula (V)

where R¹⁶ is H or C_sH₂s +i , p is 1 to 10, q is 0 to 10 and s is 1 to 10.

23. A method according to Claim 21 in which the monomer is a compound of Formula (VI)

[VI] where t and u are independently 1 to 10 and R¹⁶ is H or C_sH_2s+i, where s is 1 to 10.

24. A method according to Claim 19 in which the polymeric precursor is a monomer in which R⁶ is a straight or branched chain hydrocarbyl substituted with a COOH end group, or a pre-polymer obtained by pre-polymerisation of said monomer.

25. A method according to Claim 24 in which the monomer is a straight or branched chain alkyl group having 1 to 30 carbon atoms, optionally interposed with a cyclic group.

26. A method according to Claim 25 in which the monomer is a compound of Formula (VII)

where v is 1 to 20.

27. A method according to Claim 18 in which the polymeric precursor is a monomer in which R⁶ is a straight or branched chain alkyl group having 1 to 30 carbon atoms, or a pre-polymer obtained by pre-polymerisation by said monomer.

28. A method according to Claim 18 in which the polymeric precursor is a monomer in which R⁶ is a partially or per-halogenated straight or branched chain alkyl group having 1 to 30 carbon atoms, or a pre-polymer by pre- polymerisation of said monomer.

29. A method according to Claim 20 in which the polymeric precursor is a monomer in which R¹⁵ is CO and R⁶ terminates in one or more amine moieties thereby forming a urea structure, or a pre-polymer obtained by pre- polymerisation of said monomer.

30. A method according to Claim 16 in which the polymeric precursor is a monomer of structure (VIII)

where R⁶ is a straight or branched chain hydrocarbyl group, optionally substituted or interposed with functional groups, and r is an integer of 2 or more, or a pre-polymer obtained by pre-polymerisation of said monomer.

31. A method according to any one of Claims 14 to 30 in which the polymeric precursor is polymerised by exposure to UV radiation.

32. A method according to any one of Claims 14 to 31 in which the step of allowing the adhesive layer to set includes applying a pressure to the flooring.

33. A method according to Claim 32 in which pressure is applied by moving a roller over the flooring.