MXPA99002385A - Floor finish compositions - Google Patents

Abstract

A monomer useful in the formulation of a radiation curable coatable composition comprises (a) polyfunctional isocyanurate having at least three terminal reactive groups reacted with (b) hydroxyalkyl acrylate and (c) tertiary amine alcohol in a molar ratio of a:b:c of about 1:1-2.5:0. 5-2, wherein b + c is at least 3 and no gtreater than the total number of terminal reactive groups of (a). The monomer is included in a radiation curable coatable composition suitable for use as a floor finish and in a floor finishing system comprising the foregoing coatable composition with a primer. A method for the treatment of a substrate using the floor finish and the floor finishing system is also described.

Description

COMPOSITIONS FOR FINISHING FLOORS DESCRIPTION pg IA INVECTION The present invention relates to a radiation curable (suitable to be applied as a coating) composition suitable for use as a floor finish, with a floor finishing system using the composition, with a method for applying a coating protector to a substrate, to substrates coated with the compositions and to a polyfunctional isocyanurate monomer useful in the formulation of the radiation curable coating compositions.

BACKGROUND PE A I VEN I The polymer compositions of are used in the formulation of various coating compositions such as floor finishes, for example. Typically, commercially available floor finishing compositions are polymer compositions based on an aqueous emulsion comprising one or more organic solvents, plasticizers, coating aids, antifoaming agents, polymer emulsions, waxes, and the like. Typically, these compositions comprise a relatively low content of REF. 29719 solids (for example about 15-35%). The polymeric composition is applied to a floor surface and then allowed to air dry, usually at room temperature and humidity to form a film that serves as a protective barrier against dirt or dust deposited by the floor by pedestrian traffic. , for example. Although many of the commercially available floor finishes have worked well and have experienced at least some commercial success, the finishes available have been less than completely satisfactory for several reasons. For example, when conventional floor finishing compositions are applied to the surface of a floor, various coating applications are typically required to obtain a finish with a suitable appearance. Each successive application of the composition must be dried before additional coatings are applied and / or before pedestrian traffic is allowed through the treated floor. The compositions normally dry at room temperature and with the humidity of the air, so that the drying time depends on the air flow on the floor as well as the relative humidity of the air. Conventional floor finishes are softened when exposed to water for short periods or when exposed to strong chemical cleaners during the wiping operation, for example. In addition, such finishes require almost daily maintenance (eg, polishing) to provide a sustained and desirable appearance. In light of the foregoing, it is desirable to provide a floor finish composition that can be applied in a single application and that immediately dries and hardens in the air to provide a chemically resistant, water resistant, low maintenance and durable finish; which does not require intensive labor maintenance (for example daily) to provide a sustained and desirable appearance. It would also be desirable to provide such a chemically resistant, water resistant, low maintenance and durable finish in a form that can be easily removed from the surface to which it is applied, for example on the floor, comprising conventional vinyl floor tiles, for example. It is known that the irradiation of ethylenically unsaturated compounds in the presence of a photoinitiator induces photopolymerization. As used herein, "photoinitiator" refers to any substance or combination of substances that interact with light to generate free radicals capable of inducing free radical polymerization. Polymerization by photochemical or photoinitiated free radicals occurs when radicals are generated by irradiation of ultraviolet ("UV") and / or visible light from a reaction system polymerizable by free radicals. The absorption of energy by one or more compounds in the system results in the formation of excited species, followed either by the subsequent composition of the species excited in radicals or by interaction of the excited species with a second compound to form radicals derived from both the initially excited compound and the second compound. The exact mechanism for photoinitiation is not always clear and may involve either or both of the ways mentioned above. Photochemical polymerization has been applied in the formation of decorative and / or protective coatings and inks for metal, paper, wood and plastics, as well as for photolithography to produce integrated and printed circuits and in dental curing material. Many of the known applications involve a combination of photopolymerization and crosslinking wherein the crosslinker is typically achieved by the use of ethylenically polyunsaturated monomers. Acrylate-based systems are common, as are those based on unsaturated polyester and styrene. Additionally, the protective finishes curable by UV have been used for "wax-free" vinyl flooring during the sheet manufacturing process to produce gloss as well as abrasion resistance. These protective finishes generally can not be easily removed from the floor to which they are applied using conventional removal methods (for example, by applying a chemical stripping composition with a pad or brush removal). In addition, the curing of these finishes is typically carried out using high intensity light. The lamps have high energy requirements, large energy supplies and generally require duct ventilation to remove ozone. Often, these finishes are cured in an inert atmosphere to eliminate the damaging effects of oxygen in the curing process. Due to the energy requirements indicated above and the rest, the use of UV-curable polymer systems in floor treatment has generally been limited to factory scale processes where the additional costs and charges associated with these can be more easily justified. systems. Other problems that have been observed in the formulation of UV curable systems for pre-existing floors (for example, previously installed in a building). In the application of any type of finish to an existing floor, it is generally preferred that the hardened floor finish does not alter the color of the floor. To accomplish this goal, the finish must be transparent and substantially free of observable color. This objective is especially desired in the maintenance of floors consisting of white floor tiles where an observable color in the hardened finish produces a visible change of color on the floor in a more visible manner. Additionally, to make a floor finish composition acceptable for application in the field, the applied floor finish must also have little odor before curing. It is known, for example, that certain resins containing functional polymerizable vinyl groups, such as acrylate or vinyl ether / maleate, contain an amine or a thiol and are polymerizable in the air by free radical polymerization when exposed to UV or visible light in the presence of a photoinitiator. Although robust, abrasion resistant coatings can be provided using such resins, the resulting coatings typically have color, and the colors vary from yellow to a dark orange or may have an objectionable odor prior to curing. Consequently, these resins are considered unsuitable for use as floor finishes. As mentioned, atmospheric oxygen is known to inhibit photoinitiated polymerization reactions, resulting in little or no cure on the surface of the coating or providing a coating with poor surface properties. Various processing techniques have been proposed to eliminate the effects of oxygen on the reactive resin. One approach is to isolate the coating in a chamber and purge the chamber with an inert gas (for example nitrogen) so that the polymerization reaction proceeds in a substantially oxygen-free environment. Another approach is to initiate the polymerization reaction using intense UV radiation together with high concentrations of photoinitiator in the uncured resin. None of these proposed techniques is practical to provide a floor finishing system for use in a previously installed floor. Although low-intensity, low-cost, light-weight and smaller light sources are capable of operating on batteries or with circuits of 110 volts and 15 amps, which would be preferred, the known UV curable polymer systems have experienced slower speeds of curing and greater inhibition of curing when a low intensity light has been used. There is a perceived need for a long time, and still not resolved, for a coating composition (capable of being applied as a coating) suitable for use as a floor finish that can be easily applied to a substrate, for example a pre-installed floor, and which hardens in the air upon exposure to low radiation. intensity such as ultraviolet light, for example. It is desirable to provide such a coatable composition, preferably without objectionable odor, in a form that can be easily applied to a floor and subsequently hardened to provide a protective coating substantially free of observable color. It is also desirable to provide the above protective coatings in a form that allows them to be removed from the floor (e.g., by a suitable chemical remover), as desired.

BRIEF DESCRIPTION OF THE INVENTION The invention provides a coating composition (capable of being applied as a coating) that can be rapidly cured to the air by exposure to low intensity ultraviolet radiation to provide a durable protective coating for a suitable substrate such as vinyl floor tiles, for example. The resulting coating requires little maintenance and can be easily and quickly removed from the substrate by application of a suitable stripping composition, as set forth herein. In one aspect, the invention provides a monomer useful in the formulation of radiation curable, curable compositions, comprising: (a) a polyfunctional isocyanurate having at least three terminal reactive groups that react with (b) hydroxyalkyl acrylate and ( c) tertiary alcoholamine in a molar ratio of a: b: c from about 1: 1-2.5: 0.5-2, where b + c is at least 3 and not greater than the total number of terminal reactive groups of (a ).

A preferred monomer comprises a compound having the general formula: wherein Ra and R2 are H or CH3; R3 and R can independently be alkyl groups (linear, branched or cyclic) having 1 to 12 carbon atoms, or R3 and R4 can together form a divalent cycloalkanediyl, oxacycloalkanediyl or azacycloalkanediyl linking group having 2 to 12 carbon atoms; and Zj, Z2, Z3, Z4, Z5 and Z6 independently represent divalent groups having from 1 to 18 carbon atoms, preferably alkanediyl groups (linear, branched or cyclic) having from 1 to 18 carbon atoms, more preferably straight chain alkanediyl groups having from 1 to 4 carbon atoms. The above monomer is formulated in radiation curable, curable compositions as a first monomer when combined with a second monomer and an initiator photo. Preferably, the first monomer comprises the reaction product of a trimer of hexane diisocyanate (optionally mixed with an allophanate of hexane diisocyanate), a hydroxyalkyl acrylate and a tertiary alcoholamine. The first monomer is typically present within the composition in an amount of between about 10 and 80% by weight. The second monomer can be selected from any of a variety of polymerizable monomers. Preferably, the second monomer is an acrylate, as further described herein. The second monomer is typically present within the composition in an amount of between about 5 and 90% by weight. In addition to the second monomer, the composition may additionally comprise additional polymerizable monomers that include combinations of 2 or more such monomers. A suitable photoinitiator is included within the composition to facilitate curing by UV radiation. Those initiators suitable in the formation of transparent coatings having a low degree of observable color are preferred. The concentrations of photoinitiator within the composition may vary based on the nature of the other components of the composition and the nature of the photoinitiator. A typical concentration for the photoinitiator is between about 2 and 10% by weight. It will be understood that certain terms have certain meanings, as stated in the following. The terms "ultraviolet radiation" and "UV radiation" are used interchangeably to refer to the light spectrum comprising wavelengths within the range from about 180 nm to 400 nm. The term "coatable composition" (susceptible to being applied as a coating) means a liquid composition that can be applied to a substrate and subsequently solidified (for example by UV curing) to form a hardened coating on the substrate. "Curable by radiation", when referring to the coatable compositions, means that the coatable composition will form a hardened coating upon exposure to radiation such as UV radiation, or visible light (eg, 180 to 800 nm). The term "substrate" refers to any surface on which the coatable compositions of the invention are applied and include, without limitation, vinyl floor tiles (which include tiles previously coated with floor sealant or the like), ceramic tiles, wood , marble and similar. As used herein, the term "acrylate" will be understood to include acrylate and methacrylate species. The term "monomer" refers to any chemical species having at least one free radically polymerizable group (eg, acrylate, methacrylate). The term "tertiary alcoholamine" means to indicate a tertiary amine that includes alcohol functionality. In another aspect, the invention provides a floor finishing system comprising the radiation curable, curable composition described above and a sizing composition, the sizing composition is coatable on a substrate. In this aspect of the invention, the coatable composition is as previously described. The size preferably comprises an acrylated latex with a solids content in water between about 2 and about 40% by weight. The latex is applied to the substrate and dried prior to the application of the coating composition. The size provides a layer on the substrate to which the coatable composition can be attached. In addition, the cured coatable composition is easily removable from the substrate when the latex size is present. In still another aspect of the invention, there is provided a method for applying a protective coating to a substrate, comprising: (A) applying a radiation curable, curable composition to a substrate, the composition comprising: (i) a first monomer comprising: (a) polyfunctional isocyanurate having at least 3 terminal reactive groups, which react with (b) hydroxyalkyl acrylate and (c) tertiary alcoholamine, in a molar ratio of a: b: c of about 1: 1- 2.5: 0.5-2, where b + c is at least 3 and not greater than the total number of terminal reactive groups of (a), (ii) a second monomer, and (iii) a photoinitiator; and (B) hardening the composition to form a protective coating on the substrate by exposing the coating composition to ultraviolet radiation. In this aspect of the invention, the first monomer, the second monomer and the photoinitiator are as previously described. In general, the coating compositions preferably comprise at least about 90% solids (for example less than about 10% solvent).

The hardening of the composition in step (B) can be obtained in air at a prevalent temperature and humidity (for example under ambient conditions). Although high intensity radiation provides a faster cure of the coatable composition and is generally preferred for carrying out the hardening step (B), the coatable compositions can also be cured with low intensity UV radiation. The curing of the coating compositions at low UV intensities can be carried out very quickly (for example less than 30 seconds) using a low intensity radiation source which provides at least one band of wavelengths less than about 300 nm and a second band of between about 300 and 400 nm. Preferably, such a source of low intensity radiation emits a first band of wavelengths centered around 254 nm, and a second band centered between 350 and 370 nm (eg, at about 365 nm) to cure the coating (typically from about 0.03 nm thick) in less than about 30 seconds. A suitable low intensity radiation source is one that provides a radiation intensity between approximately 5 and 15 mW per square centimeter. Preferably, the exposure of the coating to the low intensity radiation is for a period of up to about 30 seconds. The foregoing method may also comprise, prior to the preceding application step (A), applying a sizing composition to the floor and drying the sizing composition to form a sizing coating on the substrate. As discussed above, the preferred sizing composition is an acylated latex, which preferably has a solids content of between about 2 and about 40% by weight.

In still another aspect, the invention provides a coating, which is derived from the above-curable, radiation curable composition. In another aspect, the invention provides a substrate coated with the coating mentioned above. In still another aspect, the invention broadly provides a method for applying a protective coating to a substrate, comprising: (a) applying an acrylate-lacquered latex composition to the substrate; (b) drying the sizing composition to form an acrylated polymer sizing coating on the substrate; (c) applying a radiation curable composition to the sizing coating; and (d) hardening the radiation curable, curable composition by exposing the composition to ultraviolet radiation to form a protective coating on the substrate. The details of the invention will be more fully appreciated by those familiar with the art upon consideration of the remainder of the description which includes the detailed description of the preferred mode and the appended claims.

The preferred embodiment of the invention will now be described. It will be appreciated that the preferred embodiment, although illustrative, should not be considered as unduly limiting the scope of the invention. The coating compositions according to the invention are formulated with a first monomer comprising an isocyanurate. The first preferred monomer is derived from the reaction of a polyfunctional isocyanate, hydroxyalkyl acrylate and tertiary alcoholamine. The compositions of the invention also comprise a second monomer and a photoinitiator. The individual components used in the formulation of the coatable composition will now be described.

FIRST MQNOMERQ In the formulation of radiation curable, curable compositions usable as floor finishes, it is desired that the final product (eg, the final hardened coating) be substantially free of observable color, provide a hard and durable finish, and be removable easily from the substrate to which the composition has been applied. For this end, it has been found that compositions comprising a certain class of polyfunctional isocyanurates will provide the desired coating. The first monomer is preferably prepared from the reaction of polyfunctional isocyanurate, alkylamine (hydroxyalkyl), and a hydroxyalkyl acrylate. In the reaction, about 1 mole of polyfunctional isocyanurate is reacted with from about to about 2.5 moles of hydroxyalkyl acrylate and with from about 0.5 to about 2.0 moles of tertiary alcoholamine. As a result of the preceding preparation, the first monomer comprises: (a) polyfunctional isocyanurate having about 3 terminal reactive groups, which react with (b) hydroxyalkyl acrylate and (c) tertiary alcoholamine in a molar ratio of a: b: c of about 1: 1-2.5: 0.5-2, where b + c is at least 3 and not greater than the total number of terminal reactive groups of (a). The terminal reactive groups of the polyfunctional isocyanurate comprise isocyanate groups (-NC0), each of which is capable of reacting with the hydroxyl groups in both the hydroxyalkyl acrylate and the tertiary amine to form a urethane linkage (-NH-CO-). 0) inside the reaction product. Although the theoretical functionality of the polyfunctional isocyanurate is 3, it will be appreciated that the actual functionality of the polyfunctional isocyanurate may sometimes be less (for example between 2.5 and 3.0), and still be within the scope of the present invention. As a result of the above reaction, the first monomer may comprise a compound having the general formula: wherein Rx and R2 are H or CH3; R3 and R can independently be alkyl groups (linear, branched or cyclic) having 1 to 12 carbon atoms, or R3 and R4 can form, together, a divalent cycloalkanediyl, oxacycloalkanediyl or azacycloalkanediyl linking group, having 2 to 12 carbon atoms; and Z1, Z2, Z3, Z4, Z5 and Z6 independently represent divalent groups having from 1 to 18 carbon atoms, preferably alkanediyl groups (linear, branched or cyclic) having from 1 to 18 carbon atoms, more preferably straight chain alkanediyl groups having from 1 to 4 carbon atoms. The polyfunctional isocyanate trimer in the formation of the polyfunctional isocyanurate is preferably a low viscosity polyfunctional aliphatic polyisocyanate resin. Preferably, the polyfunctional isocyanurate is a trimer of aliphatic diisocyanate and more preferably is a trimer derived from hexamethylene diisocyanate (HDI). In formulating the first monomer, it has been found that the above polyfunctional isocyanurate is important in the formation of transparent and substantially colorless coatings by UV curing. In addition, compositions based on these polyfunctional isocyanurates typically cure rapidly (eg, less than 1 minute) to the air, by exposing them to low intensity UV light. The suitable polyfunctional isocyanurate can be easily synthesized by the oligomerization of diisocyanate (eg, HDI) to provide the foregoing trimer, as is known to those familiar in the art. Suitable products based on HDI derived from isocyanurate are commercially available such as those available under the trade designation DESMODUR N-3300. In addition, allophane trimers derived from the reaction of HDI and butanol are suitable for use in the invention and are commercially available under the trade designations DESMODUR XP 7100 and DESMODUR XP 7040. The isocyanate trimers mentioned above are available from the Industrial Chemicals Division of Bayer. Corporation, Pittsburgh, Pennsylvania. It is preferred that the amount of allophanate be minimized for a better performance of the resulting cured coating. The low viscosity aliphatic diisocyanate diluents can be used in a similar manner, and subjected to the same requirements. To provide a preferred combination of performance characteristics in the finished coating and low viscosity in the coating composition, the DESMODUR XP 7100 monomer is the most preferred. The polyfunctional isocyanurate used herein provides 3 different reactive isocyanate groups extending from the isocyanurate ring. Each of the isocyanate functionalities is capable of reacting with a hydroxyl group with both the tertiary alcoholamine and the hydroxyalkyl acrylate to form the first monomer. Tertiary alcoholamines suitable for use in the invention include acyclic (hydroxyalkyl) dialkyls having from 3 to 30 carbon atoms such as "N, N-dimethylaminoethanol, N, .V-dimethylaminopropanol, N, N-dimethylaminobutanol, N, N-dimethylaminohexanol, N, N-dimethylaminododecanol, N, JV-diet i laminoethanol, N, N-diethylaminopropanol, iV, N-diethylaminobutanol, iV-ethyl-N-methylaminopropanol, N-ethyl-N-hexylaminoethanol, and the like; cyclic (hydroxyalkyl) dialkylamines having from 3 to 30 carbon atoms such as 2-aziridinyl ethanol, 2-azetidinyl ethanol, 2-piperidinoethanol, N-me t-1-4-azacyclohexanol, and the like; polyaminoalcohols having from 3 to 30 carbon atoms such as N-methylpiperazinoethanol, N-butylpiperazinoethanol, N-methylpiperazinobutanol, and the like. (Hydroxyalkyl) of alkylarylamines and (hydroxyalkyl) diarylamines may also be used in the invention, although their use is not preferred due to the tendency of the compositions comprising aromatic amines to change color when cured. The tertiary alcoholamines, which include the foregoing examples thereof, may be synthesized according to known methods, or commercially available from a variety of commercial sources such as Texaco Corp. of Houston, Texas.; Ahsland Chemical Co., of Columbus, Ohio, and Aldrich Chemical Co., of Milwaukee, Wisconsin. In addition to the above tertiary alcoholamines, about 2 moles of the hydroxyalkyl acrylate react with about 1 mole of polyfunctional isocyanurate. The hydroxyl group of the hydroxyalkyl acrylate reacts with isocyanate so that the main reaction product comprises acrylate groups attached or pendent to the isocyanurate ring. The double bonds of these acrylate groups provide reactive sites capable of forming additional bonds with other monomers during the polymerization. Suitable hydroxyalkyl acrylate compounds comprise any of a variety of acrylic compounds including hydroxyalkyl acrylates, N-hydroxyalkyl acrylamides, and the like. Preferred are hydroxyalkyl acrylates, especially hydroxyalkyl acrylates comprising a hydroxyalkyl portion of Cj to C4. A particularly preferred hydroxyalkyl acrylate is 2-hydroxyethyl acrylate, available from Dow Chemical Co., of Midland, Michigan.

SECOND MONOMER The first preceding monomer can be polymerized in a reaction in at least one additional radiation curable monomer ("second monomer"). In the presence of an adequate amount of photoinitiator and upon exposure to ultraviolet radiation, the first monomer and the second monomer react to form a highly crosslinked polymeric coating, suitable as a floor finish or the like. The second monomer can be selected from any of a variety of radiation-sensitive polymerizable monomers including mono-, di- and tri-functional acrylates, as well as acrylates of higher functionality and combinations of the foregoing. Preferably, the second monomer is selected from di- or tri-functional acrylates and combinations thereof. Suitable di- or tri-functional acrylates are commercially available from Sartomer Company, Inc., of West Chester, Pennsylvania. The second or second monomers are chosen to achieve a preferred balance of properties both in the uncured composition as well as in the cured coating. Acrylates suitable for use in the invention include, without limitation, onoacrylates such as tetrahydrofurfuryl acrylate, cyclohexyl acrylate, N-hexyl acrylate, 2-ethoxyethyl acrylate, isodecyl acrylate, 2-methoxyethyl acrylate, 2-acrylate, (2-ethoxyethoxy) ethyl, stearyl acrylate, lauryl acrylate, octyl acrylate, 2-phenoxyethyl acrylate, glycidyl acrylate, isobornyl acrylate, benzyl acrylate, tridecyl acrylate, caprolactone acrylate, nonyl phenol ethoxylated acrylate, acrylate of polypropylene glycol, and the like; diacrylates such as triethylene glycol diacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate , ethoxylated bisphenol A diacrylate, propoxylated neopentyl glycol diacrylate and the like; triacrylates such as trimethylolpropane triaacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glyceryl triacrylate and the like; acrylates of higher functionality such as pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate and the like; metal acrylates such as zinc diacrylate, calcium diacrylate and the like; acrylated oligomers and polymers such as polyurethane mono- and poly-acrylates, polyester mono- and polyacrylates, polyamide mono- and poly-acrylates, polybutadiene mono- and poly-acrylates and the like; and acrylated silicones such as those available under the trade designations "EBECRYL 350" or "EBECRYL 1360" from UCB Radcure of Smyrna, Georgia. The second monomer may comprise substances other than acrylated monomers, preferably substances that readily copolymerize with acrylate monomers such as the first prior acrylated monomer used in the present invention. Suitable materials include N-vinyl monomers such as W-vinylformamide, N-vinylpyrrolidone, N-vinylcarbazole and the like; acrylamide and derivatives thereof such as methylolacrylamide; styrenic monomers such as styrene, α-methylstyrene, vinylpyridine and the like; and other monomers such as vinyl ethers, allyl ethers such as triallyl isocyanurate, allyl acrylate and ether maleate esters, for example. Acrylated substances are preferred for use as the second monomer herein. Most preferred are ethoxylated trimethylolpropane triacrylates such as those commercially available from the Sartomer Company under the trade designations "SR 454", "SR 499", "SR 502", and "SR 9035", and propoxylated diacrylates such as tripropylene glycol diacrylate. As mentioned, the second or second monomers are added to a reaction mixture with the first monomer and polymerized to form transparent, durable and hard coatings of the invention, as described further below. In the reaction mixture, the percentage by weight of the second monomer is typically within the range of from about 5 to about 90%, preferably from about 35 to about 70% by weight, and more preferably from about 45 to about 65% by weight. weight. The first monomer is present within the mixture at a concentration in the range of from about 10 to about 90% by weight, preferably from about 25 to about 60% by weight, and more preferably from about 30 to about 50% by weight .

PHOTOINICITER As mentioned, a photoinitiator is added to the compositions of the invention to initiate the polymerization reaction. Preferred photoinitiators are free radical initiators for ultraviolet curing. In the selection of a photoinitiator suitable for use in the present invention, special attention is paid to the properties of high molar absorptivity (eg extinction coefficient) at maximum power for the light source, low color and low tendency to color after UV exposure, stability of shelf life, low or unpleasant odor and high efficiency for photoinitiation of polymerization. In order to obtain a quick and satisfactory cure of the compositions of the invention, the photoinitiator will preferably have a molar absorptivity (eg, greater than 10000 liter / mol-cm) at a wavelength of the light source, while will have a lower molar absorptivity at another wavelength or second wavelength of the light source (eg, less than 10,000 liters / mol-c). Preferably, the compositions of the invention will contain photoinitiators in concentrations such that the absorbance for a 25 micron film will be greater than or equal to about 2.5 at one wavelength (typically 254 nm) to ensure a rapid surface cure, while the absorbance at a longer wavelength (typically 350-370 nm) will be from about 0.05 to about 0.8, and more preferably from about 0.4 to about 0.6 to ensure rapid and effective part-to-part cure. Photoinitiators useful in the invention include those known to be useful in the UV curing of acrylate polymers. Such initiators include benzophenone and its derivatives: benzoin, α-methylbenzoin, α-phenylbenzoin, α-allylbenzoin, α-benzylbenzoin; benzoin ethers such as benzyldimethyl ketal (commercially available under the trade designation "IRGACURE 651" from Ciba-Geigy of Ardsley, New York), benzoin methyl ether, benzoin ethyl ether, benzoin n-butyl ether; acetophenone and its derivatives such as 2-hydroxy-2-methyl-1-phenyl-1-propanone (commercially available under the trade designation "DAROCUR 1173" from Ciba-Geigy of Ardsley, New York), and 1-hydroxycyclohexylphenyl ketone (HCPK) (commercially available under the trade designation "IRGACURE 184", also from Ciba-Geigy Corporation); 2-methyl-l [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone, commercially available under the trade designation "IRGACURE 907", also from Ciba Geigy Corporation). 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholin) phenyl] -butanone commercially available under the trade designation "IRGACURE 369", also from Ciba Geigy Corporation). Other useful photoinitiators include pivaloin ethyl ether, anisoine ethyl ether; anthraquinones such as anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, 2-bromoanthraquinone, 2-nitroanthraquinone, anthraquinone-1-carboxaldehyde, anthraquinone-2-thiol, 4-cyclohexylantraquinone, 1.4 -dimethylanthraquinone, 1-methoxyanthraquinone, benzaanthraquinone halomethyltriazines, 'onium' salts, for example diazonium salts such as phenyldiazonium hexaflorophosphate and the like; diaryliodonium salts such as ditolylodonium hexafluoroantimonate and the like, sulfonium salts such as triphenylsulfonium tetrafloroborate and the like; titanium complexes such as bis (? 5-2, 4-cyclopentadien-1-yl) bis [2,6-difluoro-3- (l-pyrrol-1-yl) phenyl] -titanium commercially available under the trade designation " CGI 784 DC ", also from Ciba-Geigy Corporation); uranyl salts such as uranyl nitrate, uranyl propionate; halomethylnitrobenzene such as 4-bromomethylnitrobenzene and the like; mono- and bis-acylphosphines such as those available from Ciba-Geigy under the trade designations "IRGACURE 1700", "IRGACURE 1800", "IRGACURE 1850" and "DAROCUR 4265". It is contemplated that other photoinitiators not included herein may also be suitable for use in the present invention. The selection of a suitable photoinitiator is within the skill of those who practice the technique.

A preferred photoinitiator used in this composition is a combination of about 4 parts by weight of benzophenone (based on the total weight of the composition) and one part by weight of N-ethylcarbazole or N-vinylcarbazole. Another preferred photoinitiator is a combination of about 4 parts by weight of benzophenone (based on the total weight of the composition) and one part by weight of benzoinadimethyl ketal. Preferably, the photoinitiator is present in the compositions of the invention at a concentration between about 2 and about 10% by weight, and more preferably between about 4 and about 7% by weight.

OTHER INGREDIENTS Additional optional components may be included within the coatable compositions of the invention. For example, a wetting agent may be added in minor amounts to the coating compositions to facilitate a uniform coating on a suitable substrate. Suitable wetting agents include, for example, fluorinated agents such as those commercially available under the trade designations "FLUORAD FC-431" and "FLUORAD FC-171," both available from Minnesota Mining and Manufacturing Company of St. Paul, Minnesota.

Filler materials can be added to the coatable compositions of the invention to modify the wear properties. Filling materials known to be useful in acrylate clear coating applications can be used in the invention. A preferred filler material is one in which the silica particles are modified with 3-mercaptopropyltrimethoxysilane. Other possible ingredients include defoamers, leveling auxiliaries, additives against normal wear and tear, air release additives, antioxidants, light stabilizers such as benzotriazole light stabilizers, hydrobenzophenone light stabilizers and the like; optical brighteners and other known formulation additives.

PREPARATION AND USE OF RECOVERY COMPOSITIONS In the preparation of the coating compositions (susceptible to be applied as a coating) of the present invention, the first monomer is preferably prepared first and then mixed with the second monomer or monomers, the photoinitiator and the other ingredients. In the preparation of the first monomer, the polyfunctional isocyanurate is first added to a reaction vessel together with a suitable catalyst such as dibutyltin dilaurate. A mixture is prepared by the addition of tertiary alcoholamine and hydroxyalkyl acrylate. A suitable preservative which will not be consumed during the reaction such as, for example, hydroxytoluenebutylated (BHT) can also be added to the reaction mixture. The mixture of tertiary alcoholamine, hydroxyalkyl acrylate and preservatives are added to the reaction vessel (containing the first monomer). The reaction is allowed to proceed to completion under ambient conditions in ai, while controlling the temperature of the reaction mixture, preferably at a temperature below about 40 ° C to avoid premature consumption of the condom. The reaction mixture is then allowed to cool to room temperature. The completion of the reaction can be monitored by appropriate means, such as infrared spectrophotometry. The first monomer prepared in this manner can then be combined in an appropriate reaction vessel with a second monomer, photoinitiator and other optional ingredients to provide the coating compositions of the invention. A particularly preferred coatable composition according to the invention is one comprising about 42 parts by weight of the first monomer (preferably the DESMODUR XP 7100 isocyanurate commercially available from Bayer Corporation), about 48 parts by weight of ethoxylated trimethylolpropane triacrylate (commercially available under the commercial designation "SR-499" of Sartomer Comapny, Inc.), about 5 parts by weight of tripropylene diacrylate, about 5 parts by weight of photoinitiator and about 0.3 parts by weight of a suitable wetting agent (eg FLUORAD FC-171 of Minnesota Mining and Manufacturing Company) and about 0.5 parts of acrylated silicone EBECRYL 350, commercially available from UCB Radcure of Smyrna, Georgia. In order to prolong the storage of the compositions of the invention, inhibitors can be added. A suitable inhibitor can be any material that is known to inhibit polymerization induced by free radicals including, but not limited to, hindered phenols such as hydroxytoluenebutylated (BHT) and its derivatives, hydroquinone and its derivatives such as methylhydroquinone and N-aluminum salt. Nitrosophenylhydroxylamine, commercially available under the designation "Q-1301" from Wako Chemicals USA, Inc., (Richmond, VA). Of these, the aluminum salt of N-nitrosophenylhydroxylamine is preferred. The composition can then be coated on a suitable substrate such as conventional polyvinyl chloride floor tiles, for example. Once coated on the substrate, the coatable composition is exposed to UV light to cure the composition to a hardened protective coating. Suitable light sources can be selected by those familiar with the art. In general, high intensity light sources are preferred to obtain a fast curing of the coating composition. However, in the application of the coating compositions that are installed on the floor, a low intensity UV light may be more practical, and the coating compositions of the invention readily cure by brief exposure to low intensity UV light. In general, a suitable low intensity UV light source emitting at least one band of wavelengths less than about 300 nm. To obtain a faster curing of applied coating, the light source will preferably also emit a second band of wavelengths between about 300 and 400 nm. It has been found that for a coating thickness of about 0.03 mm, a UV light source that emits a narrow band of wavelengths centered at about 254 nm at an intensity (on the coating surface) of about 5-15 is suitable. mW per square centimeter. Preferably, such a low intensity light source also emits a second narrow band of wavelengths centered in the range of .360-370 nm and typically at about 365 nm at the same approximate intensity as already mentioned. At the low level of UV intensity above, the compositions of the present invention will usually cure in less than 30 seconds, preferably in less than 20 seconds. One such light source is that described below in the examples. It will be appreciated that the overall configuration of the light source is outside the scope of the invention. Different sources of light can be used to carry out the curing of the compositions of the invention such as a pulsed xenon flash source, a medium pressure mercury source, a low pressure fluorescent source of mercury and a fluorescent source 300 nm. It is also contemplated that larger wavelength lamps may be used to initiate the polymerization reaction if a suitable photoinitiator is used. When applying the coatable compositions of the invention to a suitable substrate, it is preferred that the composition be applied in a manner which generates a coating no greater than about 1.3 millimeters thick in order to facilitate curing of the composition within the limits of time mentioned before. Coatings of this thickness can be obtained by any of numerous known application techniques such as roller coating, scrubbing, knife coating, curtain coating, spray coating and the like. When applying the above compositions to a substrate, suitable substrates include conventional floor tiles which may or may not be pre-coated or sealed. When the substrate to be coated is vinylp tiles or the like, it is preferred that the substrate is first treated with a size or sealant prior to the application of the compositions of the invention UV curable to the substrate. A sizing treatment of the substrate facilitates the ease with which the UV cured coating can be removed subsequently from the tile or other substrate by a chemical remover formulation, for example. In order to promote adhesion of the curable composition to the substrate, an acrylated latex size is further preferred. The acrylated latex compositions useful herein should have at least one free radical polymerizable group attached to each latex particle, and preferably more than one. The latex is hydrophobic in nature, but may contain certain hydrophilic groups. When the sizing is applied to the substrate, it is desirable to provide a continuous film on the surface of the substrate, adjust the solids content of the sizing as needed to obtain such a film while using the least amount of sizing necessary to produce a barrier layer with the desired adhesion properties. Typically, the solids content in the sizing necessary for a rubbing applicable coating (eg, by hand) will be between about 2 and about 40% by weight, preferably between about 2 and about 20%, and most preferably between about 4. and approximately 15%. A wetting or defoaming agent may be added to the latex emulsion to improve the coating properties. The level or concentration of such additives will depend on the nature of the substrate and the concentration of the latex emulsion. A preferred latex emulsion for use as a sizing herein is the acrylated emulsion commercially available under the trade designation "ROSHIELD 3120" from Rohm and Haas Company, Philadelphia, PA. This emulsion is available with a solids content of about 40.5% by weight, and a suitable size can be prepared by diluting the concentrated emulsion in a weight ratio of the dilution of up to about 9: 1 (water: emulsion). An aqueous sizing formulation comprising a mixture of ROSHIELD 3120 acrylated latex former is preferably further preferred with a second sizing polymer, preferably the ammonium salt of a styrene-maleic anhydride copolymer (SMA) (commercially available with a solids content of 38.5% under the trade designation "SMA 1000A" from Atochem, Inc., of Malvern, Pennsylvania). The SMA is added to the sizing to act as a leveling aid. The weight ratio of the acrylate to the SMA copolymer in the size preferably is between about 7: 1 and about 12: 1, and more preferably is about 10: 1. A small amount of the surfactant may also be included in the sizing. A particularly preferred sizing, having a solids content of about 10% by weight, comprises about 24.4% by weight of the ROSHIELD 3120 acrylated latex, about 73.2% by weight of water, about 2.4% by weight of the SMA 1000A copolymer and about 0.02 % by weight of surfactant or wetting agent such as that commercially available under the trade designation "FLUORAD FC-129" from Minnesota Mining and Manufacturing Company, St., Paul, Minnesota. The size can be applied to the substrate by any suitable method such as rubbing, brushing, spraying and the like. The latex is allowed to dry, typically under ambient conditions, and then the UV curable compositions of the invention can be applied thereon and cured as described herein. Substrates such as PVC tiles, for example, coated with the above acrylated latex sizing and then coated with the UV curable acrylate (e.g., a coatable composition) can be easily removed using a benzyl alcohol remover such as that described below in the Examples. The tiles removed in this way have a very good appearance, with the appearance of removal that occurs on the surface of the tile. The corresponding non-sizing tiles coated with the same UV-curable acrylate are slower to remove and are generally not removed cleanly (eg, on the surface of the substrate). In the aspect of the invention described in the foregoing, the sizing may comprise a component of a floor finishing system that includes both the sizing as well as the coating composition described herein. Although sizes are preferred which comprise the above ROSHIELD 3120 acrylated latex (with or without an SMA copolymer), other commercially available materials such as sizing over certain substrates such as PVC composition floor tiles may also be used. Some suitable sizes include various commercial floor sealers such as those available under the trade designations "CORNERSTONE" (Minnesota Mining and Manufacturing Company, St., Paul, Minnesota), "TOPLINE" (also of Minnesota Mining and Manufacturing Company) and "TECHNIQUE "(SC Johnson of Milwaukee, Wisconsin). It is also contemplated that the foregoing sizing, especially sizing made of ROSHIELD 3120 acrylated latex, can be used in other applications outside the floor finishing technique to be applied to any of a variety of UV polymerizable polymers (e.g. different from the compositions coatings above) to a substrate. Accordingly, the use of sizing provides a system and method for coating a variety of substrates with a UV curable polymer. In such a system and method, the resulting coatings adhere well to the substrate and can also be more easily removed from the substrate by suitable stripping compositions. When a non-acrylated latex size is used, it is preferable to use a size which has a surface tension of at least 40 dynes / cm. The cured coatings of the invention can be removed from the substrates to which they are applied by the application of a suitable remover. Preferably, the remover in a neutral pH formulation comprising a solvent, a coupling agent (for example hydrotrope) and water. If desired, colorants, fragrances and thickening agents can be added to the stripping composition. An effective stripper formulation for the topcoat compositions of the invention includes those set forth below in the test methods.

EXAMPLES The ingredients used in the examples below are identified as follows: DESMODUR N3300 is the commercial designation for a hexane isocyanate trimer available from Bayer Corp., Industrial Chemicals Division. DESMODUR XP 7100 is the commercial designation for an allophanate hexane diisocyanate trimer blend available from Bayer Corp., Industrial Chemicals Division, DESMODUR XP 7040 is the commercial designation of an allophanate hexane diisocyanate trimer mixture available from Bayer Corp., Industrial Chemicals Division, SR 306 is the commercial designation of tripropylene glycol diacrylate, a difunctional acrylate monomer commercially available from Sartomer Co., Inc., of West Chester, PA. SR 335 is the commercial designation for lauryl acrylate, a monofunctional acrylate monomer commercially available from Sartomer Co., Inc., of West Chester, PA. SR 454 is the commercial designation for an ethoxylated trimethylolpropane triacrylate, a trifunctional acrylate monomer commercially available from Sartomer Co., Inc., of West Chester, PA.

SR 499 is the commercial designation for an ethoxylated trimethylolpropane triacrylate, a trifunctional acrylate monomer commercially available from Sartomer Co., Inc., of West Chester, PA.

DAROCUR 1173 is the commercial designation for 2-hydroxy-2-methyl-1-phenylpropan-1-one, a commercially available photoinitiator from Ciba-Geigy, Ardsley, New York, DAROCUR 4265 is the commercial designation for a commercially available acylphosphine photoinitiator of Ciba-Geigy, Ardsley, New York. IRGACURE 184 is the commercial designation for 1- hydroxycyclohexylphenyl ketone, a commercially available photoinitiator from Ciba-Geigy, Ardsley, New York, FLUORAD FC-431 is the commercial designation for a wetting agent available from Minnesota Mining and Manufacturing Company, St. Paul, Minnesota . FLUORAD FC-171 is the commercial designation for a wetting agent available from Minnesota Mining and Manufacturing Company, St. Paul, Minnesota. PVC tile refers to standard floor tiles that comprise polyvinyl chloride that has been removed and cleaned to eliminate the factory finish. Sealed PVC tile refers to standard floor tiles comprising polyvinyl chloride that has been removed and cleaned to remove factory finishes and then coated with a floor or sealer finish. ROSHIELD 3120 is the commercial designation for a commercially available acrylated emulsion from Rohm and Haas Company, Philadelphia, PA with a solids content of 40.5% by weight, as used herein as a sizing by dilution of the concentrate with water at a of dilution of 9: 1 (water: emulsion). EBECRYL 350 is the commercial designation for acrylated silicones commercially available from UCB Radcure of Smyrna, Georgia, TECHNIQUE is the commercial designation of an acrylic floor sealer, commercially available from S.C. Johnson, Milwaukee, Wisconsin. TOPLINE is the commercial designation of a commercially available acrylic floor finish is the commercial designation for a wetting agent available from Minnesota Mining and Manufacturing Company, St. Paul, Minnesota. CORNERSTONE is the commercial designation for a commercially available acrylic floor finish from Minnesota Mining and Manufacturing Company, St. Paul, Minnesota.

PREPARATION PROCEDURES The following procedures were used in the preparation of materials used and described in the Examples.

Preparation of Oligomer A A dry, 5 liter reaction vessel fitted with a drying tube, addition funnel, thermometer and mechanical stirrer is charged with 450.0 g (2.30 equivalents) of hexane diidocyanate trimer (DESMODUR N3300). Four drops of dibutyltin dilaurate are added to the reaction vessel. A mixture is prepared by mixing 68.43 g of 2- (N, N-dimethylamino) ethanol (0.77 equivalents), 178.3 g of 2-hydroxyethyl acrylate (1.54 equivalents) and 0.35 g of methylhydroquinone as a preservative. This mixture is added to the reaction vessel while maintaining the temperature of the contents below 35 ° C. When the mixture has cooled to room temperature, it is isolated by pouring it into a container, the infrared analysis indicates only trace amounts of isocyanate or free alcohol present. This material is very viscous, and a spatula is required to supply it.

Preparation of the Oligomer B A dry 5 liter reaction vessel is placed with a drying tube, addition funnel, thermometer and mechanical stirrer, and charged with 600.0 g (2.93 equivalents) of allophaned hexane diisocyanate trimer (DESMODUR XP 7100) . A mixture is prepared by mixing 87 g of 2- (N, N-dimethylamino) ethanol (0.975 equivalents), 226.7 g of 2-hydroxyethyl acrylate) (1.95 equivalents) and 0.45 g of BHT, as a preservative. 9 drops of dibutyltin dilaurate are added to the reaction vessel. The mixture is added to the reaction vessel while maintaining the temperature of the mixture at a temperature below 30 ° C. When the mixture has cooled to room temperature, it is isolated by pouring it into a container. The infrared analysis indicates only trace amounts of isocyanate or free alcohol present. This material is moderately viscous and is difficult to pour.

Preparation of the Oligomer C A dry 1 liter reaction vessel is placed with a drying tube, addition funnel, thermometer and mechanical stirrer and charged with 642 g (3018 equivalents) of allophaned hexane diisocyanate trimer (DESMODUR XP 7040). 6 drops of dibutyltin dilaurate are added to the reaction vessel. A mixture is prepared by combining 89.7 g of 2- (N, N-dimethylamino) ethanol (1.01 equivalents), 233.7 g of 2-hydroxyethyl acrylate (2012 equivalents) and 0.48 g of BHT as a preservative. This mixture is added to the reaction vessel while maintaining the temperature of the contents below 40 ° C. When the mixture has cooled to room temperature, it was isolated by pouring it into a container. Infrared analysis indicated only trace amounts of isocyanate or free alcohol present. This material has low viscosity and can be easily poured.

Preparation of Modified Silica Particles Silica functionalized with mercapto is prepared. 1076 grams of an aqueous dispersion of colloidal silica having a solids content of 34% by weight at a pH of 3.2 is diluted to 10% total solids (commercially available from Nalco Chemical Company of Naperville, Illinois under the trade designation NALCO 1042 ), with distilled water to provide total 4000 g. To this is added 19.6 g of (3-mercaptopropyl) -trimethoxysilane (available from Aldrich Chemical Company, Milwaukee, Wisconsin). The resulting suspension is heated for 18 hours at 80 ° C with stirring to provide a colorless, translucent suspension, which is used without purification. A portion of the above suspension (50 g) is mixed with 45 g of SR 499 to provide a suspension. The water is removed under vacuum (aspirator / rotary evaporator) at room temperature to provide 50 g of a clear liquid.

GENERAL PROCEDURES Curing Procedure A UV exposures were made using a wheeled cart capable of generating 110 V of energy, which has a front part mounted to a bench facing downwards from 45.7 cm (18 inches) of fluorescent lights over centers of 3.81 cm (1.5 inches) to a distance approximately 2.54 cm (1 inch) from the floor. The lights are cantilevered on the front of the carriage wheels without superficially scratching the finish. A reflective aluminum sheet is mounted behind the lights to reinforce the radiant energy directed towards the coating. The lamps are placed in two sets inside the bench. The first set consists of two 15-watt lights on a 25-watt ballast on the front of the bench. These two lights consist of one (1) 15-watt germicidal light (one low-pressure mercury light emitting at approximately 254 nm) and one (1) black light at 15 watts (365 nm). The second set consists of six (6) 15-watt lights in a 15-watt ballast. The second set is placed on the bench with a space of 5 cm (2 inches) between the two sets of lights. He second set of lights consists of germicidal lights and alternating black lights for a total of six (6) lights in the second set. All germicidal bulbs are commercially available from General Electric under the designation "F15T8". Black light bulbs are also available from General Electric under the designation "F15T8 / BL". The measured power at the surface of the germicidal bulb in the center of the bulb is approximately 11 mW / cm2 for the 25-watt ballast, and approximately 7 mW / cm2 for the 15-watt ballast. The measured power at the bulb surface of black light in the center of the bulb is approximately 7 mW / cm2 for the 25-watt ballast and approximately 4.5 mW / cm2 for the 15-watt ballast. Unless stated otherwise, all samples are cured at a 30-second exposure to the previous light source.

Curad procedure? B Exposures are made using a downward facing bench of 45.7 cm (18") fluorescent lights in the center of 3.8 cm (1.5 inches) at a distance of approximately 2.5 cm (1 inch) from the floor.A reflective aluminum sheet is mounted behind The set of lights consists of six germicidal bulbs.All of the bulbs are commercially available from General Electric under the designation "F15T8." The measured power at the surface of the bulb in The center of the bulb was approximately 7 mW / cm2.

Unless indicated otherwise, all samples were cured in a 30 second exposure to the previous light source.

Coating Procedure A Upon applying the coatable compositions to a substrate such as PVC tiles or sealed PVC tiles, a small volume of the composition, typically about 2-3 grams, was applied to the substrate using a syringe. The composition applied in this way is then coated onto the substrate by using a hand-held portable rubber roll to roll-spread the composition over the desired area of the substrate until a very uniform coating is obtained over the desired area of the substrate. After the composition cured. To determine the weight of the coating, the weight of the coated tile was compared to the initial weight of the tile (i.e., before applying the coating composition).

METHODS PE TEST In the examples that follow, the following test methods were used.

Test Method A (Abrasion Resistance Taber): A square sample of 10.2 x 10.2 cm (4"x 4") of coated material to be tested was prepared. By using a template to accurately place a spot on the coating where the abrasion is expected to occur, an initial brightness reading of 20 ° or 60 ° is obtained for each side (four total readings) using a Byk- meter. Gardner Micro-Tri-Gloss (Byk-Gardner, Silver Spring, MD). The sample is then mounted on a standard Taber Abrasion Tester ((Taber Standard Abrasion Tester) (model No. 503, Teledyne Taber, North Tonawanda, NY) placed with a vacuum device, 500 g weight on wheels and CS wheels The sample is subjected to 100 revolutions and the brightness was measured after the abrasion as above, the gloss retention percent was calculated for each side, and the results averaged.

Test Method B (Scratched Hardness) The scratch hardness was determined using a pencil-type scratch tester Byk-Gardner (Byk-Gardner, Silver Spring, MD). The measurements were reproducible at approximately ± 100 g. The results were generally dependent on the thickness of the substrate and the film.

Test Method C (Removal Time) When testing the coatings of the invention to determine the amount of time necessary to remove a radiation-cured coating from a substrate, the following formulation was used to remove coatings from tile substrates: 68.75 parts of deionized water, 22.50 parts of benzyl alcohol, 5.52 parts of n-actylamine, 3.24 parts of glycolic acid, 0.02 parts of sulfactant or surfactant ("FLUORAD FC-129") from Minnesota Mining and Manufacturing Company). The remover was applied by a dropper on a coating cured in numerous positions in the coating. The removal time was recorded as the time in which 1) the film bubbled over the entire area covered with the remover; or 2) the time necessary for the remover to loosen the coating sufficiently so that manually cleaning the remover applied with a paper towel will result in a clean removed substrate surface. Condition 1 was generally observed for coatings applied on sealed PVC tiles, while condition 2 was generally observed on PVC tiles. The removal time is highly sensitive and depends on the coating thickness as well as the degree of curing for a particular coating. Consequently, caution should be exercised when comparing the results of removal time of coatings having different thicknesses or those that have experienced different degrees of curing.

Test Method D (Brightness Measurements) The brightness measurements were made using a calibrated Byk-Gardner Micro-Tri-Gloss meter (Byk-Gardner, Silver Spring, MD). The readings were taken after cleaning the surface.

Test Method E (Color Measurement) Color measurements were made using a calibrated Datacolor International Microflash 200d spectrophotometer (Datacolor International, Charlotte, NC) in specular mode using a 1.5 cm aperture. All readings were an average of 3 measurements. The color coordinates CIELAB L *, a *, b * and the color shift DE were used here as well-known terms in the color measurements.

EXAMPLES The following non-limiting examples illustrate the preparation, utility and comparative advantages of the present invention. Unless stated otherwise, all percentages are by weight.

EXAMPLES 1-15 Examples 1-15 were prepared and evaluated for durability according to Test Method A. Analysis of the results indicates that formulations with reduced amounts of SR 306 difunctional diacrylate have the best durability. All samples contained 0.3 parts of FC-431 FLUORAD wetting agent and were coated on PVC tiles. They were coated at 26.9 g / m2 (2.5 g / square foot) using Coating Process A and cured using the Curing Procedure A. The formulations of these examples and the abrasion resistance data are set forth in Table 1.

Table 1 Examples 1-15 EXAMPLE 16 A series of samples were prepared based in part on the above data for examples 1 to 15. The samples of example 16 are made with 40 parts of oligomer A, 45 parts of trifunctional acrylate (SR-499), 10 parts of difunctional acrylate. (SR-306), 0.3 parts of wetting agent (FLUORAD FC-431) and photoinitiator. 5 parts of a photoinitiator such as the DAROCUR 1173 material or other photoinitiators are all successfully used, including 3 parts of benzophenone combined with 2 parts of DAROCUR 1173 photoinitiator or IRGACURE 184 photoinitiator. These compositions are coated on sealed PVC tiles to which A coating of sealer size for CORNERSTONE flooring was applied in accordance with Coating Procedure A and cured according to Curing Procedure A. Abrasion resistance, scratch hardness and wear times were determined. removal in accordance with Test Methods A, B and C above. The% retention of brightness at 20 ° for these samples were consistently about 83%. The scratch hardness was approximately 1200 g. The time of removal was less than 5 minutes.

EXAMPLES 17-30 Examples 17 to 30 were prepared and evaluated to determine abrasion resistance, in accordance with Test Method A. Analysis of the results indicates that formulations with reduced amounts of SR 306 difunctional acrylate have the best durability. All samples contained 0.3 parts of wetting agent (FLUORAD FC-431) and were coated on PVC tiles. They were coated at 26.9 g / m2 (2.5 g / square foot) using the Coating Process A and cured using the Curing Procedure A. The compositions of the examples and the abrasion resistance data are set forth in Table 2 Table 2 Examples 17 to 30 EXAMPLE 31 A series of samples were based, partly on the results of Examples 17 to 30. All of these samples consisted of 30 parts of oligomer B, 65 parts of trifunctional acrylate (SR 499), 0.3 parts of wetting agent (FLUORAD FC-431) and 5 parts of photoinitiator. As a photoinitiator, the photoinitiator DAROCUR 1173 was used successfully by itself as well as other photoinitiators that include combinations of benzophenone and photoinitiator DAROCUR 1173, and benzophenone and photoinitiator IRGACURE 184. The samples were coated on a substrate according to Coating Procedure A and cured according to Coating Procedure A. Abrasion resistance was determined, the scratch hardness and the removal time for the cured coatings according to test methods A, B and C. By using a primer system of 5 parts of DAROCUR photoinitiator and an additional part of benzophenone, the resistance to abrasion after 15 seconds irradiation was up to 82% brightness retention at 20 °. The typical scratch hardness of these formulations, when emptied onto a sealed PVC tile (sealed with a poly (vinylidene dichloride) with a polyester film floor sealer as primed, commercially available under the trade designation "TECHNIQUE" from SC Johnson Milwaukee, Wisconsin) is 800-1000 g. When coated over conventional floor finishes, delamination was commonly observed at forces as small as 200 g. The removal time of sealed PVC tiles (when sealed with the floor finish available under the trade designation "CORNERSTONE" commercially available from Minnesota Mining and Manufacturing Company) was approximately 2-3 minutes.

A series of samples were developed based in part on the results of Example 16. These samples consisted of 40 parts of C oligomers, 45 parts of trifunctional acrylate (SR-499), 10 parts of difunctional acrylate (SR 306), parts of photoinitiator and 0.3 parts of wetting agent (FLUORAD FC-431). The photoinitiator DAROCUR 1173 and the other photoinitiators have all been successfully used, including the benzophenone and photoinitiator combinations DAROCUR 1173, and the benzophenone and photoinitiator IRGACURE 184. The samples are coated on a substrate according to Coating Procedure A and they are cured according to the Coating Procedure A. The abrasion resistance, the scratch hardness and the removal time for the cured coatings were determined, according to the test methods A, B and C. The resistance to the abrasion (% gloss retention at 20 °) was consistently 85%, the scratch hardness was 1300 g, and the removal time for sealed PVC tiles (sealed with a commercially available floor sealer under the trade designation) "Cornerstone" by Minnesota Mining and Manufacturing Company) was less than 5 minutes.

EXAMPLES 33-60 Examples 33 to 60 were prepared and evaluated for abrasion resistance according to Test Method A. All samples contained 0.3 parts of wetting agent (FLUORAD FC-431). The formulations of the examples were coated on PVC tiles at a dry coating weight of 26.9 g / m2 (2.5 g / square foot) using Coating Method A and cured using Curing Method A. In Table 3 establish the compositions for Examples 33-60 and the abrasion resistance data. The analysis of the results indicates that the formulations with reduced amounts of the monofunctional acrylate SR-335 have the best durability.

Table 3 Examples 33-60 EXAMPLE 61 A series of samples were developed based in part on the results of Examples 33 to 60. These samples consisted of 177 parts of oligomer A, 102 parts of trifunctional acrylate (SR-454), 21 parts of monofunctional acrylate (SR-). 335), 15 parts of photoinitiator (DAROCUR 1173), 0.3 parts of wetting agent (FLUORAD FC-431). The formulation was coated on PVC tiles, according to Coating Process A and cured according to Curing Procedure A. Data on abrasion resistance, scratch hardness and time of removal were collected for these samples. according to test methods A, B and C. The abrasion resistance shows approximately 74% brightness retention at 20 °. The scratch hardness was greater than 1700 grams. The removal time was approximately 3 minutes.

EXAMPLE 62 A coatable composition comprising 60 parts of oligomer A, 21 parts of trifunctional acrylate monomer (SR-454), 12 parts of caprolactone acrylate, 2.4 parts of photoinitiator (DAROCUR 1173) was prepared. The sample was coated to approximately a thickness of 25.4 μm (1 mil) on PVC tiles using Coating Procedure A and cured for 20 seconds under Curing Procedure B. The resulting coating was tested to determine the time of removal, in accordance with Test Method C, providing a cure time of approximately 8 minutes.

EXAMPLE 63 A coatable composition comprising 60 parts of oligomer A, 20 parts of trifunctional acrylate (SR-454), 20 parts of caprolactone acrylate, 5 parts of photoinitiator (DAROCUR 1173). The composition was coated on PVC tiles using the Coating Procedure A and cured using the Curing Procedure A. The resulting coatings were tested in accordance with the Test Methods A, B and C. The abrasion resistance was about 75% gloss retention at 60 °, the scratch hardness was about 500 g. The removal time of the PVC tiles was approximately 3 minutes.

EXAMPLES 64 AND 65 Examples 64 and 65 were prepared as set forth in Table 4. Example 65 was identical to Example 64 except that Example 65 was prepared with functionalized silica prepared according to the Preparation Procedure set forth above. The compositions were applied as a coating on PVC tiles according to the Coating Process A and cured according to the Curing Procedure A to provide a cured coating of approximately 0.25 mm in thickness. The coatings were tested for abrasion resistance in accordance with Test Method A. Brilliance retention values at 20 ° indicated slightly better abrasion resistance for the coating of Example 65 containing functionalized silica.

Table 4 Example 64 and 65 EXAMPLES 66-71 To determine the effect of visible light on the color of the cured coatings made according to the invention, a premix was prepared. The premix was comprised of 30 parts of C oligomer, 65 parts of trifunctional acrylate (SR-499), 5 parts of photoinitiator as indicated below, 0.3 parts by weight of agent (FLUORAD FC-431). The samples were coated at 26.9 g / m2 (2.5 g / square foot) on whitish PVC tiles and cured using Curing Procedure A except that the curing time was 15 seconds. The cured coatings were exposed to 6 x 15 W Philips F15T8BLB bulbs at a distance of approximately 2.5 cm (1 inch) (approximately 5 mW / cm2, 350-370 nm). Subsequently, the samples were exposed to 6 x 15 W of Philips 15WTLD / 03 bulbs at a distance of approximately 2.5 cm (1 inch) (wavelength of approximately 420 nm). The coordinates L *, a * and b * are reported. The coordinates L * indicate the whiteness, the positive coordinates a * measure the red condition, the positive coordinates b * measure the yellow. The DE values measure the total color deviation, an ED of less than 1-2 is generally imperceptible to the human eye. Based on the data set forth in Table 5, it is evident that UV exposure causes yellowing which is reversible upon exposure to blue light.

Table 5 Examples 66 to 71 EXAMPLES 72-80 An oligomer was prepared as in Preparation of Oligomer B by combining 42 parts of allophaned HDI trimer (DESMODUR XP-7100), 2-hydroxyethyl acrylate, and 2-dimethylamino-ethanol (equivalent ratio of 3: 2: 1). The oligomer was combined with 48 parts of trifunctional acrylate (SR-499), 5 parts of difunctional acrylate (SR-306), 3 parts of benzophenone, 2 parts of DAROCUR 4265 photoinitiator and 0.3 parts by weight of wetting agent (FLUORAD FC-171) to provide a UV curable coatable composition. . For some of the examples EBECRYL 350 acrylated silicone was added to the coatable composition as a release material. The coatable compositions were tested for adhesion to both PVC tiles and sealed PVC tiles. The sealed PVC tiles were prepared by treating them with a sizing or sealant manually applied with gauze to provide a uniform and even coating. The sizing was allowed to dry at room temperature and humidity. The coated composition was then applied to both the sealed PVC tiles and the PVC tiles, according to the Coating Procedure A and then cured with UV, according to the Curing Procedure A using an exposure time of 10 seconds. . After the curing step, cuts were made with a razor through the cured coating and sizing (when present) and inside the tile substrate to form a square grid of 0.32 cm x 0.32 cm (1/8) "x 1/8"). It was applied on the square tape pattern ("SCOTCH Rug and Carpet Tape" available from the Minnesota Mining and Manufacturing Company) with a 2.3 kg roller. The tape then peeled off the tile manually by scraping one end of the tile and pulling the tape back on itself at an angle of approximately 180 °. Adhesion was determined by visual inspection of both the tile and the removed tape to determine the percentage of square sections removed from the tile. A value of 0% adhesion means that the entire coating was removed from the tile, while a 100% adhesion means that none of the coating was removed. In general, all UV cured coatings adhered well to the tile substrate, with better adhesion observed in sealed PVC tiles, especially those sealed with ROSHIELD 3120 latex. The composition of UV curable coatings, the size coat used and the data for the adhesion test are all summarized in Table 6. Unless otherwise indicated, the coatings for these examples comprise 100 parts of the coatable composition without added acrylated silicone.

Table 6 (Examples 72 to 80) Although the preferred embodiments of the invention have been described in detail, it will be understood that changes and modifications can be made in the embodiments described by those familiar with the art without departing from the true spirit and scope of the invention, as set forth in the following claims. . It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects or products to which it refers.

Claims (44)

RBIVIMPICACIOMBiS Having described the invention as above, property is claimed as contained in the following:

1. A monomer useful in the formulation of radiation-curable, coating-curable (radiation-curable) compositions, the monomer is characterized in that it comprises: (a) a polyfunctional isocyanurate having at least three terminal reactive groups that react with (b) acrylate of hydroxyalkyl and (c) tertiary alcoholamine, in a molar ratio of a: b: c from about 1: 1-2.5: 0.5-2, wherein b + c is at least 3 and not greater than the total number of groups terminal reagents of (a).

2. The monomer according to claim 1, characterized in that it comprises a compound having the general formula: where R? and R2 are H ° CH3; R3 and R4 can independently be alkyl groups (linear, branched or cyclic) having from 1 to 12 carbon atoms, or R3 and R4 can form, together, a divalent cycloalkanediyl, oxacycloalkanediyl or azacycloalkanediyl linking group, having 2 to 12 carbon atoms; and Zl r Z2, Z3, Z4, Z5 and Z6 independently represent divalent groups having from 1 to 18 carbon atoms.

3. The monomer in accordance with the claim 2, characterized in that the divalent groups Z1 f Z2, Z3, Z4, Z5 and Z6 comprise alkanediyl groups (linear, branched or cyclic) having from 1 to 18 carbon atoms.

4. The monomer in accordance with the claim 3, characterized in that the alkanediyl groups are straight chain alkanediyl groups having from 1 to 4 carbon atoms.

5. A radiation curable composition, characterized in that it comprises: (a) a first monomer comprising the monomer of claim 1; (b) a second monomer; and (c) a photoinitiator.

6. The coatable composition according to claim 5, characterized in that the first monomer is present within the composition in an amount between about 10% and about 90% by weight.

7. The coatable composition according to claim 5, characterized in that the second monomer comprises an acrylate material.

8. The coatable composition according to claim 7, characterized in that the acrylate material is selected from the group consisting of monofunctional acrylates, difunctional acrylates, trifunctional acrylates, higher acrylates and combinations of the foregoing.

9. The coatable composition according to claim 8, characterized in that the monofunctional acrylates are selected from the group consisting of tetrahydrofurfuryl acrylate, cyclohexyl acrylate, N-hexyl acrylate, 2-ethoxyethyl acrylate, isodecyl acrylate, acrylate. of 2-methoxyethyl, 2- (2-ethoxyethoxy) ethyl acrylate, stearyl acrylate, lauryl acrylate, octyl acrylate, 2-phenoxyethyl acrylate, glyceryl acrylate, isobornyl acrylate, benzyl acrylate, tridecyl acrylate, caprolactone acrylate, nonyl phenol ethoxylated acrylate, polypropylene glycol acrylate, and combinations of the foregoing.

10. The coatable composition according to claim 8, characterized in that the difunctional acrylates are selected from the group consisting of triethylene glycol diacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,3-butylene glycol diacrylate, diacrylate. of 1,4-butanediol, diethylene glycol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, propoxylated neopentyl glycol diacrylate and combinations of the foregoing.

11. The coatable composition according to claim 8, characterized in that the trifunctional acrylates are selected from the group consisting of trimethylolpropane triacrylate, tris (2-hydroxyethyl) isocyanurate triaacrylate, ethoxylated trimethylolpropane triaacrylate, pentaerythritol triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glyceryl triacrylate and combinations of the foregoing.

12. The coatable composition according to claim 8, characterized in that the higher acrylates are selected from the group consisting of combinations of pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, and the like.; metal acrylates such as zinc diacrylate, calcium diacrylate and combinations of the foregoing.

13. The coatable composition according to claim 7, characterized in that the acrylate material is selected from the group consisting of acrylated oligomers, acrylated polymers, acrylated silicones and combinations of the foregoing.

The coatable composition according to claim 13, characterized in that the acrylated polymer is selected from the group consisting of polyurethane monoacrylates, polyurethane polyacrylates, polyester monoacrylates, polyester polyacrylates, polyamide monoacrylates, polyamide polyacrylates, monoacrylates of polybutadiene, polybutadiene polyacrylates and combinations of the above.

15. The coatable composition according to claim 5, characterized in that the second monomer is present within the composition in an amount between about 5% and about 90% by weight.

16. The coatable composition, according to claim 5, characterized in that the photoinitiator comprises benzophenone in an amount of between about 2% and about 10% by weight.

17. The coatable composition according to claim 5, characterized in that it also comprises silica particles modified with 3-mercaptopropyldimethoxy-silane.

18. A coating, characterized in that it is derived from the coating composition according to claim 5.

19. A floor finishing system, characterized in that it comprises: the coating composition according to claim 5; and a sizing composition.

20. The floor finishing system, according to claim 19, characterized in that the sizing comprises an acrylate latex having a solids content of between about 2 and about 40% by weight.

21. A method for applying a protective coating to a substrate, characterized in that it comprises: (A) applying a radiation curable, curable composition to a substrate, the composition comprising: (i) a first monomer comprising: (a) isocyanurate polyfunctional having at least 3 terminal reactive groups, which react with (b) hydroxyalkyl acrylate and (c) tertiary alcoholamine, in a molar ratio of a: b: c of about 1: 1-2.5: 0.5-2, in where b + c is at least 3 and not greater than the total number of terminal reactive groups of (a), (ii) a second monomer, which comprises a radiation curable material, and (iii) a photoinitiator; and (B) hardening the composition to form a protective coating on the substrate by exposing the coating composition to ultraviolet radiation.

22. The method according to claim 21, characterized in that the first monomer comprises a compound having the general formula: wherein Rx and R2 are H or CH3; R3 and R4 can independently be alkyl groups (linear, branched or cyclic) having from 1 to 12 carbon atoms, or R3 and R4 can form, together, a divalent cycloalkanediyl, oxacycloalkanediyl or azacycloalkanediyl linking group, having 2 to 12 carbon atoms; and Zlr Z2, Z3, Z4, Z5 and Z6 independently represent divalent groups having from 1 to 18 carbon atoms.

23. The method according to claim 21, characterized in that it further comprises, before step (A), applying a sizing composition to the floor and drying the sizing composition to form a sizing coating on the substrate.

24. The method according to claim 23, characterized in that the sizing composition comprises an acrylated latex having a solids content of between about 2 and about 40% by weight.

25. The method according to claim 21, characterized in that it further comprises, before step (A), preparing the first monomer by reacting a polyfunctional isocyanurate with a tertiary alcoholamine and at least one hydroxyalkyl acrylate.

26. The method according to claim 25, characterized in that the polyfunctional isocyanurate is a trimer of hexamethylene diisocyanate or an allophane trimer derived from the reaction of hexamethylene diisocyanate and butanol.

27. The method according to claim 25, characterized in that the tertiary alcoholamine is selected from the group consisting of acyclic tertiary dialkylamino alcohols having from 3 to 30 carbon atoms, alicyclic tertiary amino alcohols having from 3 to 30 carbon atoms, polyamino alcohols having from 3 to 30 carbon atoms, aromatic alcoholamines and combinations of the above.

The method according to claim 27, characterized in that the acyclic tertiary dialkylamino alcohols having from 3 to 30 carbon atoms are selected from the group consisting of W, N-dimethylaminoethanol, N, N-dimethylaminopropanol, N, N-dimethylaminobutanol , N, N-dimethylaminohexanol, N, N-dimethylaminododecanol, N, N-diethylaminoethanol, N, N-di and il ami nopropane l, N, N-diethylaminobutanol, W-ethyl-iV-methylaminopropanol, N-ethyl-N- Hexylaminoethanol, and combinations of the above.

29. The method according to claim 27, characterized in that the alicyclic tertiary aminoalcohols having from 3 to 30 carbon atoms are selected from the group consisting of 2-aziridinyl ethanol, 2-azetidinyl ethanol, 2-piperidinoethanol, N-methyl-4 -azacyclohexanol and combinations of the above.

30. The method according to claim 27, characterized in that the polyamino alcohols having from 3 to 30 carbon atoms are selected from the group consisting of N-methylpiperazinoethanol, N-butylpiperazinoethanol, N-methylpiperazinobutanol, and combinations of the foregoing.

31. The method according to claim 25, characterized in that the hydroxyalkyl acrylate is 2-hydroxyethyl acrylate.

32. The method according to claim 21, characterized in that the second monomer comprises an acrylate material.

33. The method of compliance with the claim 32, characterized in that the acrylate material is selected from the group consisting of monofunctional acrylates, difunctional acrylates, trifunctional acrylates, higher acrylates and combinations of the foregoing.

34. The method of compliance with the claim 33, characterized in that the monofunctional acrylates are selected from the group consisting of tetrahydrofurfuryl acrylate, cyclohexyl acrylate, N-hexyl acrylate, 2-ethoxyethyl acrylate, isodecyl acrylate, 2-methoxyethyl acrylate, 2- (2-acrylate. ethoxyethoxy) ethyl, stearyl acrylate, lauryl acrylate, octyl acrylate, 2-phenoxyethyl acrylate, glycidyl acrylate, isobornyl acrylate, benzyl acrylate, tridecyl acrylate, caprolactone acrylate, nonyl phenol ethoxylate acrylate, polypropylene glycol acrylate , and combinations of the above.

35. The method according to claim 33, characterized in that the difunctional acrylates are selected from the group consisting of triethylene glycol diacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,3-butylene glycol diacrylate, diacrylate 1 , 4-butanediol, diethylene glycol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, propoxylated neopentyl glycol diacrylate and combinations of the foregoing.

36. The method according to claim 33, characterized in that the trifunctional acrylates are selected from the group consisting of trimethylolpropane triacrylates, tris (2-hydroxyethyl) isocyanurate triacrylate, ethoxylated trimethylolpropane triaacrylate, pentaerythritol triacrylate, propoxylated trimethylolpropane triacrylate. , propoxylated glyceryl triacrylate and combinations of the above.

37. The method according to claim 33, characterized in that the higher acrylates are selected from the group consisting of pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate and the like; metal acrylates such as zinc diacrylate, calcium diacrylate and combinations of the foregoing.

38. The method according to claim 32, characterized in that the acrylate material is selected from the group consisting of acrylated oligomer, acrylated polymer, acrylated silicone and combinations of the foregoing.

39. The method according to claim 38, characterized in that the acrylated polymer is selected from the group consisting of polyurethane monoacrylate, polyurethane polyacrylates, polyester monoacrylates, polyester polyacrylates, polyamide monoacrylates, polyamide polyacrylates, polybutadiene monoacrylates , polybutadiene polyacrylates and combinations of the above.

40. The method of compliance with the claim 21, characterized in that the second monomer is present within the coatable composition in an amount between about 5% and about 90% by weight.

41. The method according to claim 21, characterized in that the photoinitiator comprises benzophenone combined with a carbazole derivative, the photoinitiator present in the composition is in an amount between about 2% and about 10% by weight.

42. The method according to claim 21, characterized in that the curing of the composition comprises exposing the composition to ultraviolet radiation for a period of less than about 30 seconds.

43. The method according to claim 42, characterized in that the ultraviolet radiation comprises a first band of wavelengths less than about 300 nm and a second band of wavelengths of between about 300 and 400 nm, and wherein the radiation Ultraviolet is emitted from a source at an intensity of between about 5 and about 15 mW / cm2.

44. A substrate, characterized in that it is treated in accordance with the method of claim 21.