CN1196751C - Floor finish compositions - Google Patents

Abstract

The present invention relates to a monomer which is useful to a formula of a composition which can be irradiated, solidified and coated. The monomer comprises multifunctional isocyanurate (a) which has at least three end groups which can be reacted with acrylic hydroxyalkyl ester (b) and tertiary amine alcohol (c), wherein the molar ratio of a to b to c is about 1: 1 to2.5: 0.5 to 2, and the value of the total amount of b and c is at least 3 but not greater than the total number of the termination reaction group of (a). The monomer can be contained in compositions which can be used as floor surface paint and can be irradiated, solidified and coated, and can also be contained in a floor surface paint system which comprises priming paint and the composition which can be coated. The present invention also describes a method for processing substrate by using the floor surface paint and the floor surface paint system.

Description

Floor finish composition

The present invention relates to radiation-curable coatable compositions suitable for use as floor finishes, floor finish systems using the compositions, methods of applying protective coatings to substrates, substrates coated with the compositions, and methods for use in The multifunctional isocyanurate monomer formulates the radiation curable coatable composition.

Background of the Invention

The polymer compositions can be used to formulate various coating compositions, such as floor finishes. Typical floor finish compositions marketed are aqueous emulsion-based polymer compositions including one or more organic solvents, plasticizers, coating auxiliaries, defoamers, polymer emulsions, waxes, and the like. These compositions generally include relatively low levels of solids (eg, about 15-35%). This polymer composition is applied to a floor surface and then allowed to dry in air, usually at ambient temperature and humidity, to form a film that acts as a protective shield from the deposition of dust as pedestrians walk on the floor.

While many commercially available floor finishes perform well and have achieved at least some commercial success, commercially available finishes are not entirely satisfactory for various reasons. For example, when applying common floor finish compositions to a floor surface, several coat applications are typically required to achieve a suitable looking finish. Each application of the composition must be dried before another application and/or before allowing pedestrians to walk on the treated floor. The composition is generally dried at ambient temperature and humidity, so the drying time will depend on the airflow over the floor and the relative humidity of the air. Ordinary floor finishes soften when exposed to water for short periods of time or to strong chemical cleaners during scrubbing operations. Furthermore, such finishes require almost daily maintenance (eg, polishing), providing a long-lasting, desirable appearance.

In light of the foregoing, it is desired to provide a floor finish composition which can be applied once and immediately air-dries and hardens to provide a long-lasting, low maintenance, water-resistant, chemical-resistant finish without the need for Labor is maintained frequently (eg, daily) to provide the long-lasting and desired look. It is also desired to be in a form that can be easily removed from the surface to which it is applied, for example from flooring materials including common vinyl floor tiles. Provides such a long-lasting, low maintenance, water and chemical resistant finish.

Irradiation of ethylenically unsaturated compounds in the presence of photoinitiators is known to induce photopolymerization. Herein, "photoinitiator" refers to any substance or combination of such substances that can interact with light to generate free radicals that can induce free radical polymerization. Photochemical or photoinitiated free radical polymerization occurs when free radicals are generated by ultraviolet ("UV") and/or visible light irradiation of a free radical polymerization reaction system. The absorption of energy by one or more compounds in the system results in the formation of a stimulator, which then decomposes into free radicals, or the stimulator interacts with a second compound to form a free radicals of the two compounds. The exact mechanism of photoinitiation is not always clear and may involve one or both of the above pathways.

Photochemical polymerization has been applied to form decorative and/or protective coatings and inks for metals, paper, wood, and plastics, as well as in photolithography for the manufacture of integrated circuits and printed circuits, and in the curing of dental materials. Many known applications involve a combination of photopolymerization and crosslinking, usually through the use of ethylenically polyunsaturated monomers. Acrylic based systems are commonly used, as well as unsaturated polyester and styrene based systems.

Additionally, a UV-curable protective topcoat has been applied to the vinyl "wax-free" flooring during the sheet's manufacturing process, providing gloss and abrasion resistance. These protective finishes are generally not easily stripped from the flooring material to which they are applied by conventional stripping methods such as by applying a chemical stripping composition with a stripping pad or brush. Also, high intensity light is typically used to cure these topcoats. These lamps have high power requirements and large power supplies, generally requiring ducted exhaust to remove the ozone. These topcoats are often cured in an inert atmosphere to overcome the degrading effects of oxygen during the curing process. Due to the aforementioned power requirements etc., the use of UV-curable polymer systems in the treatment of flooring materials is limited to industrial scale processes where the expense and other loads associated with these systems are more justified.

There are other problems in formulating UV-curable systems for use on pre-existing floors, such as pre-installed in buildings. When applying any type of finish over an existing floor, it is generally desirable that the hardened floor finish not change the color of the floor. To achieve this, the topcoat should be transparent with essentially no observable color. This is particularly the case in the maintenance of floors made of white floor tiles, where the visible color in the hardening finish produces a more noticeable visible discolouration on the floor. Additionally, for a floor finish composition to be suitable for use in the field, the applied floor finish should have low odor prior to curing.

It is known that some resins containing vinyl groups with polymerizable functionality, such as acrylates or vinyl ethers/maleates containing amines or thiols, when irradiated with UV or visible light in the presence of photoinitiators, Polymerization in air is possible by free radical polymerization. Although hard rub-resistant coatings can be provided with such resins, the resulting coatings are often colored, ranging from yellow to dark orange in color, or have an offensive odor prior to curing. Therefore, these resins are considered unsuitable for use as floor finishes.

As noted above, oxygen in the air is known to inhibit photoinitiated polymerization, resulting in little or no curing of the coating surface, or providing coatings with poor surface properties.

A number of treatment techniques have been proposed to eliminate the effect of oxygen on reactive resins. One method is to isolate the coating in a chamber and fill the chamber with an inert gas such as nitrogen to allow the polymerization to proceed in an environment substantially free of oxygen. Another approach is to use intense UV radiation combined with high levels of photoinitiators in the uncured resin to initiate polymerization. Neither of the proposed methods is practical for providing a floor finish system for use on pre-installed floors. Known UV-curable polymer systems when using low-intensity light are available in In actual operation, the curing speed is slower and the inhibition of curing is higher.

There is a long-felt need for a coatable composition suitable for use as a floor finish that can be conveniently applied to a substrate, such as a pre-installed floor, and cured in air by exposure to low intensity (eg, ultraviolet light) radiation. It would be desirable to provide a coatable composition which preferably has no objectionable odour, which can be conveniently applied to floors and subsequently cured to provide a protective coating with substantially no observable color. It is also desirable to provide the above-mentioned protective coating which can be removed from the floor if desired (eg by a suitable chemical stripper).

Summary of the invention

The present invention provides coatable compositions which are rapidly cured in air upon exposure to low intensity ultraviolet light and which provide durable protective coatings for suitable substrates, such as vinyl floor tiles. The resulting coating requires little maintenance and is quickly and easily stripped from the substrate by application of a suitable stripping composition, as described below.

One aspect of the present invention provides monomers useful in formulating radiation-curable coating compositions comprising (a) a polyfunctional isocyanurate having at least three (c) The terminal group reacted by tertiary amino alcohol, the molar ratio of a:b:c is about 1:1-2.5:0.5-2, wherein b+e is at least 3 and not greater than the terminal reactive group of (a) total.

Preferred monomers include compounds having the general formula:

in:

R ₁ and R ₂ are H or CH ₃ ;

R ₃ and R ₄ are each an alkyl group (straight chain, branched chain or ring) with 1-12 carbon atoms, or R ₃ and R ₄ together form a divalent cycloalkanediyl group with 2-12 carbon atoms (cycloalkanediyl), oxacycloalkanediyl or azacyclanediyl bridging group; and

Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ and Z ₆ each represent a divalent group with 1-18 carbon atoms, preferably an alkanediyl group with 1-18 carbon atoms (straight chain, branched chain or ring), preferably straight-chain alkanediyl having 1 to 4 carbon atoms.

The foregoing monomers are mixed as a first monomer with a second monomer and a photoinitiator, and formulated into a radiation-curable coatable composition. Preferred first monomers include the reaction product of a trimer of hexane diisocyanate (optionally mixed with an allophanate of hexane diisocyanate), a hydroxyalkyl acrylate and a tertiary amino alcohol. The first monomer is generally present in the composition in an amount from about 10% to about 80% by weight. The second monomer is selected from any polymerizable monomer. Preferred second monomers are acrylates, as further described herein. The second monomer is generally present in the composition in an amount of from about 5% to about 90% by weight. In addition to the second monomer, the composition may also include other polymerizable monomers, and two or more such monomers may be included. A suitable photoinitiator is included in the composition to facilitate curing by UV radiation. Preferred photoinitiators are those suitable for forming clear coats with less visible color. The concentration of photoinitiator in the composition will vary with the nature of the other components of the composition and with the nature of the photoinitiator itself. The photoinitiator concentration is generally between about 2-10% by weight.

It is to be understood that some of the terms used herein have certain meanings and that "ultraviolet radiation" and "UV radiation" are used interchangeably to refer to the spectrum comprising wavelengths in the range of about 180-400 nm. "Coatable composition" means a liquid composition that can be applied to a substrate and subsequently cured (eg, by UV curing) to form a hardened coating on the substrate. With respect to a coatable composition, "radiation curable" means that the coatable composition is irradiated with radiation, such as UV radiation or visible light (eg, 180-800 nm), to form a hardened coating. "Substrate" means any surface onto which the coatable compositions of the present invention may be applied, including, but not limited to, vinyl tile (including tile previously coated with a floor sealer or the like), ceramic tile, wood, marble, and the like. It should be understood that "acrylate" herein includes both acrylates and methacrylates. "Monomer" refers to any chemical species (eg, acrylate, methacrylate) having at least one radically polymerizable group. "Tertiary amine alcohol" refers to a tertiary amine that includes alcohol functionality.

Another aspect of the present invention provides a floor finish system comprising the radiation curable coatable composition described above and a primer composition which is coatable on a substrate. In this aspect of the invention, the coatable composition is as previously described. The primer composition comprises an acrylated latex having a solids content in water of about 2-40% by weight. The latex is applied to the substrate and dried prior to application of the coatable composition. A primer is provided on the substrate to enable the coatable composition to bond to the substrate. Furthermore, the presence of a latex primer allows for easy release of the cured coatable composition from the substrate.

Still another aspect of the present invention provides a method of applying a protective coating on a substrate, the method comprising:

(A) applying a radiation curable coatable composition on a substrate, the composition comprising:

(i) a first monomer comprising (a) a polyfunctional isocyanurate having at least three end groups reacted with (b) a hydroxyalkyl acrylate and (c) a tertiary amine alcohol, a : The molar ratio of b:c is about 1:1-2.5:0.5-2, wherein 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) photoinitiators; and

(B) Forming a protective coating on a substrate by subjecting the coatable composition to ultraviolet radiation to harden the composition.

In this aspect of the invention, the first monomer, the second monomer and the photoinitiator are as previously described. In general, the coatable composition preferably comprises at least about 90% solids (eg, less than about 10% solvent). Hardening of the composition in step (B) can be achieved in air at ordinary temperature and humidity (eg, ambient conditions). Although accelerated curing of the coatable composition can be achieved by high-intensity radiation and is generally selected for hardening step (B), it is also possible to cure the coatable composition with low-intensity UV radiation. With a low intensity radiation source providing at least one band of wavelengths less than about 300 nm and a second band between about 300-400 nm, the coatable composition can be hardened relatively quickly (less than 30 seconds) at low UV intensities. Preferably such low-intensity radiation source emits a first wavelength band centered around 254nm and a second wavelength band centered between 350-370nm (such as 365nm), curing the coating (typically about 0.03mm thick) in less than about 30 seconds ). A suitable source of low intensity radiation is one providing a radiation intensity of about 5-15 mW/ ^cm2 . Preferably, the coating is irradiated at a low intensity for a period of up to about 30 seconds.

The aforementioned method also includes: prior to the preceding applying step (A), applying a primer composition on the floor and drying the composition to form a primer coating on the substrate. As discussed above, the preferred primer composition is an acrylated latex, preferably having a solids content between about 2-40% by weight.

Another aspect of the present invention provides a coating derived from the aforementioned radiation-curable coatable composition. The present invention also provides a substrate coated with the above coating.

The present invention also broadly provides a method of applying a protective coating on a substrate, the method comprising:

(a) applying a coatable acrylated latex primer composition to a substrate;

(b) drying the primer composition to form a primer coat of acrylated polymer covering the substrate;

(c) applying a radiation curable coatable composition over the primer coat; and

(d) exposing the composition to ultraviolet radiation to harden the radiation curable coatable composition to form a protective coating covering the substrate.

The details of the invention will be better understood by those skilled in the art from consideration of the detailed description of the preferred embodiments and the disclosure of the claims.

Detailed description of the preferred implementation

Preferred embodiments of the present invention are described below. It should be understood that the preferred embodiments are for illustration only and are not intended to limit the scope of the invention.

The coatable compositions of the present invention are formulated with a first monomer comprising an isocyanurate. A preferred first monomer is derived from the reaction of a multifunctional isocyanate, a hydroxyalkyl acrylate, and a tertiary amino alcohol. The compositions of the present invention also include a second monomer and a photoinitiator.

The components used in the formulation of the coatable composition are described below.

first monomer

In formulating radiation-curable coatable compositions useful as floor finishes, it is desirable that the final product (e.g., final hard coat) be substantially free of visible color, provide a durable hard finish, and be able to recover from application of the The composition is easily removed from the substrate. To this end, it has been found that compositions comprising a class of polyfunctional isocyanurates provide the desired coatings.

The first monomer is preferably obtained from the reaction of a polyfunctional isocyanurate, a (hydroxyalkyl)dialkylamine and a hydroxyalkyl acrylate. In the reaction, about 1 mole of polyfunctional isocyanurate is reacted with about 1-2.5 moles of hydroxyalkyl acrylate and about 0.5-2.0 moles of tertiary amino alcohol. The result of this preparation is that the first monomer comprises (a) a polyfunctional isocyanurate having at least three end groups reacted with (b) a hydroxyalkyl acrylate and (c) a tertiary amino alcohol, a The molar ratio of :b:c is about 1:1-2.5:0.5-2, wherein b+c is at least 3 and not greater than the total number of terminal reactive groups of (a). The terminal reactive groups of polyfunctional isocyanurates include isocyanate groups (-NCO), each of which can react with hydroxyl groups on hydroxyalkyl acrylates and tertiary amines to form carbamic acid bonds (NH -CO-O-). Although the theoretical functionality of the polyfunctional isocyanurate is 3, the actual functionality may be slightly smaller (eg, between 2.5-3.0), which is still within the scope of the present invention.

As a result of the preceding reactions, the first monomers include compounds having the general formula:

R ₁ and R ₂ are H or CH ₃ ;

R ₃ and R ₄ are each an alkyl group (straight chain, branched chain or ring) with 1-12 carbon atoms, or R ₃ and R ₄ together form a divalent cycloalkanediyl group with 2-12 carbon atoms (cycloalkanediyl), oxacycloalkanediyl or azacyclanediyl bridging group; and

Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ and Z ₆ each represent a divalent group with 1-18 carbon atoms, preferably an alkanediyl group with 1-18 carbon atoms (straight chain, branched chain or ring), preferably straight-chain alkanediyl having 1 to 4 carbon atoms.

The polyfunctional isocyanate trimers useful for polyfunctional isocyanurate formulations are preferably low viscosity polyfunctional aliphatic polyisocyanate resins. Preferred polyfunctional isocyanurates are trimers of aliphatic diisocyanates, more preferably trimers derived from hexane diisocyanate (HDI). In formulating the first monomer, the preceding multifunctional isocyanurates were found to be important in formulating clear and essentially colorless coatings by UV curing. Furthermore, compositions based on these polyfunctional isocyanurates cure rapidly (less than 1 minute) in air upon exposure to low-intensity UV light.

Suitable polyfunctional isocyanurates are conveniently synthesized by oligomerization of diisocyanates, such as HDI, to provide the foregoing trimers, as known to those skilled in the art. Suitable HDI-based products derived from isocyanurates are commercially available, for example those available under the tradename DESMODUR N-3300. Additionally, allophanated terpolymers derived from the reaction of HDI with butanol are suitable for use in the present invention, such terpolymers are commercially available as DESMODUR XP 7100 and DESMODUR XP 7040. The aforementioned isocyanate trimers are commercially available from the Industrial Chemical Division of Bayer Corporation, Pittsburgh Pennsylvania. To produce cured coatings with good properties, it is preferred to reduce the allophanate to a minimum amount. In the same way, low viscosity aliphatic isocyanate diluents can be used to achieve the same requirements. To provide a better combination of performance characteristics on polished coatings and lower viscosity of coatable compositions, DESMODUR XP 7100 monomer is the best choice.

The polyfunctional isocyanurates used here provide three different reactive isocyanate groups protruding from the isocyanurate ring. Each isocyanate functional group is capable of reacting with a hydroxyl group on the tertiary amine alcohol and the hydroxyalkyl acrylate to form the first monomer.

Tertiary amino alcohols suitable for use in the present invention include acyclic (hydroxyalkyl) dialkylamines having 3-30 carbon atoms, such as N,N-dimethylaminoethanol, N.N-dimethylaminopropanol, N , N-dimethylaminobutanol, N, N-dimethylaminohexanol, N, N-dimethylaminododecanol, N, N-diethylaminoethanol, N, N-diethyl Aminopropanol, N, N-diethylaminobutanol, N-ethyl-N-methylaminopropanol, N-ethyl-N-hexylaminoethanol, etc.; lipids with 3-30 carbon atoms Cyclo(hydroxyalkyl)dialkylamines; for example, 2-azetidinylethanol, 2-azetidinylethanol, 2-piperidinoethanol, N-methyl-4 -Azacyclohexanol, etc.; polyaminoalcohols with 3-30 carbon atoms, such as N-methylpiperazinoethanol, N-butylpiperazinoethanol, N-methylpiperazinobutyl Alcohol etc. (Hydroxyalkyl)alkylarylamines and (hydroxyalkyl)diarylamines are also useful in the present invention, although less preferred due to the tendency of compositions including arylamines to discolor upon curing. Tertiary amine alcohols, including the preceding examples, can be synthesized according to known methods, or can be purchased from a number of commercial sources, such as Texaco Corp. of Houston, Texas; Ashland Chemical Co. of Columbus, Ohio and Aldrich Chemical Co. of Milwaukee, Wisconsin .

In addition to the preceding tertiary amine alcohol, about 2 moles of hydroxyalkyl acrylate are reacted with about 1 mole of polyfunctional isocyanurate. The hydroxyl group of the hydroxyalkyl acrylate reacts with the isocyanate such that the main reaction product includes pendant acrylate groups on the isocyanurate ring. The double bonds of these acrylic groups provide reactive sites that can form addition bonds with other monomers during the polymerization reaction. Suitable hydroxyalkyl acrylate compounds include any acrylic compound, such as hydroxyalkyl acrylates, N-hydroxyalkylacrylamides, and the like. Preferred are hydroxyalkyl acrylates, especially hydroxyalkyl acrylates comprising C ₁ -C ₄ hydroxyalkyl moieties. A particularly preferred hydroxyalkyl acrylate is 2-hydroxyethyl acrylate, available from Dow Chemical Co. of Midland, Michigan.

second monomer

The preceding first monomer is capable of polymerizing in a reaction with at least one other radiation-curable monomer ("second monomer"). Under the presence of a suitable photoinitiator, the first monomer and the second monomer react to form a highly cross-linked polymer coating, which is suitable for use as a floor finish and the like.

The second monomer can be selected from any photopolymerizable monomer, including mono-, di-, and trifunctional acrylates, as well as higher functionality acrylates and combinations of the foregoing. Preferred second monomers are selected from di- or trifunctional acrylates and combinations thereof. Suitable di- or trifunctional acrylates are commercially available from Sartomer Company, Inc. of West Chester, Pennsylvania. The second monomer is selected to obtain a good combination of uncured composition and cured coating properties. Suitable acrylates for use in the present invention include, but are not limited to: monoacrylates such as tetrahydrofurfuryl acrylate, cyclohexyl acrylate, n-hexyl acrylate, 2-ethoxyethyl acrylate, isodecyl acrylate, 2- -Methoxyethyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, octadecyl acrylate, lauryl acrylate, octyl acrylate, 2-phenoxyethyl acrylate, shrink acrylate Glycerides, isobornyl acrylate, benzyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated nonylphenol acrylate, polypropylene glycol acrylate, etc.; diacrylates such as triethylene glycol diacrylate Ester, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, diethylene glycol diacrylate Alcohol esters, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, propoxylated neopentyl glycol diacrylate, etc.; triacrylic acid Esters such as trimethylolpropane triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, propoxylated Trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, etc.; higher functionality acrylates such as pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate esters, etc.; metal acrylates, such as zinc diacrylate, calcium diacrylate, etc.; acrylated oligomers and polymers, such as polyurethane mono- and multi-acrylates, polyester mono- and multi-acrylates, polyamides Mono- and polyacrylates, polybutadiene mono- and polyacrylates, etc.; and acrylated silicones such as those commercially available under the trade designations "EBECRYL 350" or "EBECRYL 1360" from UCB Radcure of smyrna, Georiga .

The second monomer may comprise materials other than acrylated monomers, preferably those which are readily copolymerizable with acrylate monomers, such as the acrylated first monomers previously described for use in the present invention. Suitable substances include N-vinyl monomers, such as N-vinylformamide, N-vinylpyrrolidone, N-vinylcarbazole, etc.; acrylamide and its derivatives, such as methylolacrylamide; styrene mono Monomers, such as styrene, α-methylstyrene, vinylpyridine, etc.; and other monomers, such as vinyl ether, allyl ether, such as triallyl isocyanurate, allyl acrylate and ether maleate.

Preference is given here to using acrylated substances as second monomers. Preferred are ethoxylated trimethylolpropane triacrylates such as those available from the Sartomer Company under the tradenames "SR 454", "SR 502" and "SR9035", and propoxylated diacrylic acid Esters such as tripropylene glycol diacrylate.

As noted above, the second monomer is added to the reaction mixture of the first monomer and allowed to polymerize to form the durable hard clearcoat of the present invention, as will be described below. In the reaction mixture, the weight percentage of the second monomer is generally in the range of about 5-90%, preferably about 35-70%, more preferably about 45-65%. The first monomer is present in the mixture at a concentration of about 10-90% by weight, preferably about 25-60% by weight, more preferably about 30-50% by weight.

Photoinitiator

As mentioned above, a photoinitiator is added to the composition of the present invention to initiate polymerization. Preferred photoinitiators are free radical initiators for UV curing. When selecting suitable photoinitiators for use in the present invention, particular attention should be paid to high molar absorptivity (e.g. extinction coefficient) at the energy peak of the light source, light color and low coloring tendency after UV irradiation, shelf-life stability , little or pleasant odor, and high photoinitiated polymerization efficiency. In order that the composition of the present invention can be quickly and fully cured, a preferred photoinitiator should have high molar absorptivity (such as greater than 10,000 liter/mole-cm) at one wavelength of the light source, while at the other or second wavelength of the light source The wavelength has low molar absorptivity (eg, less than 10,000 liter/mole-cm). The compositions of the present invention contain the photoinitiator at a preferred concentration such that the absorbance of a 25 micron film at one wavelength (typically 254 nm) is greater than or equal to about 2.5. , to ensure rapid curing on the surface, and the absorbance at longer wavelengths (generally 350-370nm) is about 0.05-0.8, better about 0.4-0.6, to ensure rapid and effective penetration curing.

Photoinitiators useful with the present invention include those known to be useful for UV curing of acrylate polymers. Such photoinitiators include benzophenone and its derivatives; benzoin, α-methylbenzoin, α-phenylbenzoin, α-allylbenzoin, α-benzylbenzoin benzoin ethers such as benzyl dimethyl ketal (commercially available under the trade name "IEGACURE 651" from Ciba-Geigy of Ardsley, New York), benzoin methyl ether, benzoin diethyl ether, benzoin n-butyl ether; acetophenone and its derivatives; such as 2-hydroxy-2-methyl-1-phenyl-1-propanone (available from Ciba-Geigy of Ardsley, New York under the trade name "DAROCUR 1173") ) and 1-hydroxycyclohexylphenylketone (HCPK) (available from Ciba-Geigy Company under the trade name "IEGACURE 184"); 2-methyl-1[4-(methylthio)phenyl] -2-(4-morpholinyl)-1-propanone (available from Ciba-Geigy Company under the trade name "IEGACURE 907"); 2-benzyl-2-(dimethylamino)-1-[ 4-(4-Morpholinyl)phenyl]-1-butanone (commercially available under the trade name "IEGACURE 369" from Ciba-Geigy Company). Other useful photoinitiators include pivaloin ethyl ether, anisoin ethyl ether; anthraquinones such as anthraxanthra, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone Quinone, 2-bromoanthraquinone, 2-nitroanthraquinone, anthraquinone-1-carbaldehyde (carboxaldehyde), anthraquinone-2-thiol, 4-cyclohexylanthraquinone, 1,4-dimethylanthraquinone, 1-methoxyanthraquinone, benzoanthraquinone halomethyl triazine; onium salts, such as diazonium salts, such as phenyldiazonium hexafluorophosphate, etc.; diaryliodonium salts, such as hexafluoroantimonate di Tolyl iodonium, etc.; sulfonium salts, such as triphenylsulfonium tetrafluoroborate, etc.; titanium complexes, such as bis(η ₅ -2,4-cyclopentadien-1-yl) bis[2,6- Difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium (commercially available from Ciba-Geigy Company under the trade name "CGI 784 DC"); uranyl salts such as uranyl nitrate, propane uranyl acid; halomethylnitrobenzenes, such as 4-bromomethylnitrobenzene, etc.; mono- and diacylphosphines, such as available from Ciba-Geigy as "IEGACURE 1700", "IEGACURE 1800", "IEGACURE 1850" and Those purchased under the trade designation "DAROCUR 4265". It is contemplated that other photoinitiators not listed here may also be suitable for use in the present invention. Those skilled in the art will be able to select a suitable photoinitiator.

A preferred photoinitiator useful in the compositions of the present invention is a mixture of about 4 parts by weight of benzophenone (based on the total weight of the composition) and 1 part by weight of N-ethylcarbazole or N-vinylcarbazole. Another preferred photoinitiator is a mixture of about 4 parts by weight benzophenone (based on the total weight of the composition) and 1 part by weight benzoin dimethyl ketal. The concentration of photoinitiator in the compositions of the present invention is preferably about 2-10% by weight, more preferably about 4-7% by weight.

other components

The coatable compositions of the present invention may include additional optional components. For example, small amounts of wetting agents may be included in the coatable compositions to facilitate uniform coating on suitable substrates. Suitable wetting agents include, for example, fluorinating agents such as those available under the tradenames "FLUORAD FC-431" and "FLUORAD FC-171" from Minnesota Mining and Manufacturing Company of St. Paul, Minnesota.

Fillers may be added to the coatable compositions of the present invention to enhance durability. Fillers known to be useful for acrylate clearcoat applications can be used in the present invention. A preferred filler is silica particles modified with 3-mercaptopropyltrimethoxysilane.

Other possible components include defoamers, leveling agents, damage and lubricity additives, degassers, antioxidants, light stabilizers (such as benzotriazole light stabilizers, hydroxybenzophenone light stabilizers, etc.); Brightening agents and other known formulation additives.

Preparation and Use of Coatable Compositions

In preparing the coatable compositions of the present invention, it is preferable to first prepare the first monomer and then mix it with the second monomer, photoinitiator and other components.

In the preparation of the first monomer, polyfunctional isocyanurate and a suitable catalyst, such as dibutyltin dilaurate, are first added to the reactor. A mixture is prepared by adding tertiary amino alcohol and hydroxyalkyl acrylate. A suitable preservative which is not consumed during the reaction, such as butylated hydroxytoluene (BHT), may also be added to the reaction mixture. A mixture of tertiary amino alcohol, hydroxyalkyl acrylate and preservative is added to the reactor (already having the first monomer). The reaction is carried to completion under ambient conditions in air while controlling the temperature of the reaction mixture, preferably below about 40°C, to prevent premature consumption of the preservative. The reaction mixture was then cooled to room temperature. The completion of the reaction is monitored by suitable means, such as by infrared spectrophotometry.

The produced first monomer is mixed with the second monomer, photoinitiator and other optional components in a suitable reactor to provide the coatable composition of the present invention. A particularly preferred coatable composition of the present invention comprises about 42 parts by weight of a first monomer (preferably DESMODUR XP 7100 isocyanurate available from Bayer Corporation), about 48 parts by weight of ethoxylated trihydroxy Methylpropane triacrylate (available from Sartomer Company, Inc. under the trade designation "SR-499"), about 5 parts by weight of tripropylene diacrylate, about 5 parts by weight of a photoinitiator, and about 0.3 parts by weight of a suitable Wetting agent (such as available from Minnesota Mining and Manufacturing Company of St. Paul, Minnesota under the trade designation "FLUORAD FC-171" wetting agent), and about 0.5 parts by weight of acrylated silicone EBECRYL 350, available from UCB Radcure Purchased from Smyrna, Georgia.

Inhibitors may be added for prolonged storage of the compositions of the invention. Suitable inhibitors may be any substance known to inhibit free radical initiated polymerization, including without limitation hindered phenols such as butylated hydroxytoluene (BHT) and its derivatives, hydroquinone and its derivatives such as Methylhydroquinone and the aluminum salt of N-nitrosophenylhydroxylamine are commercially available as "Q-1301" from Wako Chemical USA, Inc. (Richmond, VA). Preferred among them are the aluminum salts of N-nitrosophenylhydroxylamine.

The composition is then spread on a suitable substrate, such as common polyvinyl chloride floor tiles. Once applied to a substrate, exposure of the coatable composition to UV light cures the composition into a hardened protective coating. A person skilled in the art will be able to select a suitable light source. High intensity light sources are generally preferred to allow rapid curing of the coatable composition. However, low intensity UV light is more commonly used when applying the present coatable compositions on installed floors, and the coatable compositions of the present invention are readily curable under low intensity UV light irradiation. Generally, suitable low intensity UV light sources are those that emit at least one wavelength band less than about 300 nm. To allow rapid curing of the applied coating, the light source is preferably also capable of emitting a second wavelength band between about 300-400 nm. It has been found that for a coating about 0.03 mm thick, a UV light source capable of emitting (at the coating surface) at an intensity of about 5-15 mW/ ^cm2 having a wavelength centered around about 254 nm is suitable. Preferably such a low intensity light source also emits a second narrow band centered in the 360-370 nm range, usually around 365 nm, at about the same intensity as above. Under the low intensity UV mentioned above, the compositions of the present invention usually cure in less than 30 seconds, preferably less than 20 seconds. One such light source will be described in the following example.

The general configuration of the light source is considered to be outside the scope of the present invention. Different light sources can be used to cure the compositions of the present invention, such as pulsed xenon flash sources, medium pressure mercury sources, low pressure mercury fluorescent sources and 300 nm fluorescent sources. It is believed that longer wavelength lamps can also be used to initiate polymerization if a suitable photoinitiator is used.

When applying the coatable compositions of the present invention to a suitable substrate, it is preferred to apply the composition in such a manner as to produce a coating thickness of not greater than about 1.3 mm to facilitate curing of the composition within the above time periods. Coatings of this thickness can be obtained by a number of known application techniques, such as roller coating, knife coating, knife coating, curtain coating, spraying, and the like. In applying the foregoing compositions to substrates, suitable substrates include conventional floor tiles, which may or may not be precoated or sealed. When the floor tiles to be coated are vinyl tiles or the like, it is preferable to first treat the substrate with a primer or a sealer before applying the UV-curable composition of the present invention. Primed substrates facilitate subsequent release of the cured coating from tile or other substrates with chemical strippers. To promote adhesion of the coatable composition to the substrate, an acrylate latex primer is preferred. The acrylate latex composition used herein must have at least one free radical polymerizable pendant group on each particle thereof, preferably more than one. The latex is hydrophobic but may contain some hydrophilic groups.

When a primer is used on a substrate, it is desired to provide a film that continuously covers the surface of the substrate, the solids content of the primer is adjusted as necessary to obtain such a film, and at least the required amount of primer is used to obtain a film having the desired adhesion properties. Shield. The solids content of the required primer for wiping (as used) on the coating is generally in the range of about 2-40% by weight, preferably about 2-20% by weight, about 4-15% ( weight) is better. Wetting agents and defoamers can be added to latex emulsions to improve coating properties. The amount of these additives depends on the nature of the substrate and the concentration of the latex emulsion.

A preferred latex emulsion that can be used as a primer is an acrylic emulsion available as "ROSHIELD 3120" from Rohm and Haas Company, Philadelphia, PA. This emulsion was commercially available at a solids content of about 40.5% by weight. A suitable primer was prepared by diluting the concentrated emulsion in a weight ratio of about 9:1 (water:emulsion). A more preferred aqueous primer formulation comprises the preceding ROSHIELD 3120 acrylic latex with a secondary primer polymer, preferably styrene maleic anhydride ammonium (SMA) copolymer (available from Atochem, Inc. of Malvern, Pennsylvania Commercially available under the trade designation "SMA 1000A" with a solids content of 38.5%). Add SMA to the primer as a leveling agent. The weight ratio of acrylated latex to SMA copolymer in the primer is preferably between about 7:1 and about 12:1, more preferably about 10:1. Small amounts of surfactants may also be included in the primer. A particularly preferred primer having a solids content of about 10% by weight comprises about 24.4% by weight of ROSHIELD 3120 acrylated latex, about 73.2% by weight of water, about 2.4% by weight of SMA 1000A copolymer and about 0.02% by weight of a surfactant or wetting agent such as that available under the trade designation "FLUORAD FC-129" from Minnesota Mining and Manufacturing Company of St. Paul, Minnesota.

The primer can be applied to the substrate by any suitable method, eg, rubbing, brushing, spraying, and the like. The latex is typically dried under ambient conditions before the UV curable composition of the present invention is applied thereon and cured. Substrates, such as PVC floor tiles, coated with the above-described acrylated latex primer followed by a UV-curable acrylate (eg, curable composition) can be easily stripped using a benzyl alcohol stripper as described in the Examples below. Therefore, when peeling begins to appear on the surface of the tile, the peeled floor tile presents a good appearance. Correspondingly, unprimed floor tiles coated with the same UV curable acrylate exhibited slower delamination and generally did not delaminate completely (eg on the substrate surface).

In the above aspect of the invention, the primer may comprise a component of a floor finish system comprising the primer and the above-described coatable composition. While primers (with or without the addition of SMA copolymer) including ROSHIELD 3120 Acrylic Latex described above are preferred, other commercially available materials can also be used as primers on certain substrates, such as PVC floor tiles. Some suitable primers include many commercially available floor sealers such as those tradenamed "CORNERSTONE" (Minnesota Mining and Manufacturing Company of St. Paul, Minnesota), "TOPLINE" (Minnesota Mining and Manufacturing Company of St. Paul, Minnesota) and "TECHNIQUE" (S.C. Johnson of Milwaukee, Wisconsin). It is also believed that the foregoing primers, particularly primers comprising ROSHIELD 3120 acrylic latex, may be used in applications other than the field of floor finishes, incorporating any UV polymerizable polymer such as the foregoing coatable composition other polymers) applied to the substrate. Thus, the use of primers provides systems and methods for coating various substrates with UV-curable polymers. In such systems and methods, the resulting coating adheres well to the substrate and is easily released from the substrate with a suitable release agent. When using a non-acrylated latex primer, it is preferred to use a primer with a surface tension of at least 40 dynes/cm.

The cured coatings of the present invention can be released from the applied substrate using a suitable release agent, preferably a pH neutral formulation comprising a solvent, a coupling agent such as a hydrotrope, and water. Dyes, fragrances and thickeners can be added to the stripper composition if desired. Stripper formulations effective for the floor finish compositions of the present invention include those set forth in the Test Methods below.

Example

Material

The components used in the examples are listed below:

DESMODUR N3300 is the trade designation for hexane diisocyanate trimer, available from Bayer Corp.

Purchased from Industrial Chemicals Division.

DESMODUR XP 7100 trade name for a mixture of allophanated hexane diisocyanate trimers, available

Commercially available from Bayer Corp. Industrial Chemicals Division.

DESMODUR XP 7040 Trade name for a mixture of allophanated hexane diisocyanate trimers, available

Commercially available from Bayer Corp. Industrial Chemicals Division.

SR 306 Trade name for Tripropylene Glycol Diacrylate, difunctional acrylate monomer, available

Purchased from Sartomer Co., Inc. of West Chester, PA.

SR 335 Trade designation for lauryl acrylate, monofunctional acrylate monomer available from

Purchased from Sartomer Co., Inc. of West Chester, PA.

SR 454 Trade name for ethoxylated trimethylolpropane triacrylate, a trifunctional propylene

Ester monomer, available from Sartomer Co., Inc. of West Chester, PA

have to.

SR 499 Ethoxylated Trimethylolpropane Triacrylate, Trifunctional Acrylate Monomer

trade designation , available from Sartomer Co., Ine. of West Chester, PA

have to.

DAROCUR 1173 Tradename for 2-Hydroxy-2-methyl-1-phenylpropan-1-one, photoinitiator, available from

Purchased from Ciba-Geigy, Ardsley, New York.

Tradename for DAROCUR 4265 acylphosphine, photoinitiator, available from Ciba-Geigy, Ardsley, New

Purchased in York.

Tradename for IRGACURE 184 1-hydroxycyclohexyl phenyl ketone, photoinitiator, available from Ciba-Geigy,

Purchased from Ardsley, New York.

Trade designation for FLUORAD FC-431 wetting agent available from Minnesota Mining and Manufacturing

Purchased by Company, St. Paul, Minnesota.

Tradename for FLUORAD FC-171 wetting agent, available from Minnesota Mining and Manufacturing

Purchased by Company, St. Paul, Minnesota.

PVC Floor Tiles means standard floor tiles comprising polyvinyl chloride that have been stripped and cleaned to remove factory finish

Road paint.

Sealed PVC floor tiles refer to standard floor tiles comprising polyvinyl chloride that have been stripped and cleaned to remove factory finishes

A floor coat or sealer is then applied.

ROSHIELD 3120 is a trade designation for acrylated emulsion, available from Haas Company, Philadelphia,

    PA was purchased with a solids content of 40.5% (by weight), passed through water at a rate of 9:1 (water:

Emulsion) Dilution Ratio Dilute the concentrate and use it as a primer here.

Tradename for EBECRYL 350 Acrylated Silicone, available from UCB Radcure of Smyrna,

Purchased from Georiga.

TECHNIQUE trade designation for acrylic floor sealer available from S.C. Johnson, Milwaukee,

Purchased from Wisconsin.

TOPLINE trade designation for acrylic floor finishes available from Minnesota Mining and

Purchased from Manufacturing Company, St. Paul, Minnesota.

CORNERSTONE is the trade name for acrylic floor finishes available from Minnesota Mining and

Purchased from Manufacturing Company, St. Paul, Minnesota.

Preparation

The following methods were employed in the preparation of the materials used in the examples.

Preparation of oligomer A

450.0 g (2.30 equivalents) of hexane diisocyanate trimer (DESMODUR N3300) were charged into a dry 5 liter reactor equipped with drying tube, addition funnel, thermometer and mechanical stirring. Four drops of dibutyltin dilaurate were added to the reactor. 68.43 g of 2-(N,N-dimethylamino)ethanol (0.77 equivalent), 178.3 g of 2-hydroxyethyl acrylate (1.54 equivalent) and 0.35 g of methylhydroquinone as a preservative were mixed to prepare a mixture. This mixture was added to the reactor while maintaining the temperature of the contents below 35°C. When the mixture was cooled to room temperature, it was poured into a container and separated. Infrared analysis showed only traces of isocyanate or free alcohol present. The substance is extremely viscous and requires a spatula to dispense.

Preparation of oligomer B

600.0 g (2.93 equivalents) of allophanated hexane diisocyanate trimer (DESMODUR XP 7100) were charged into a dry 5 liter reactor equipped with drying tube, addition funnel, thermometer and mechanical stirring. A mixture was prepared by mixing 87 g of 2-(N,N-dimethylamino)ethanol (0.975 equivalent), 226.7 g of 2-hydroxyethyl acrylate (1.95 equivalent) and 0.45 g of BHT as a preservative. Add 9 drops of dibutyltin dilaurate to the reactor. This mixture was added to the reactor while maintaining the temperature of the mixture below 30°C. When the mixture was cooled to room temperature, it was poured into a container and separated. Infrared analysis showed only traces of isocyanate or free alcohol present and the material was moderately viscous and difficult to pour.

Preparation of oligomer C

642 g (3.018 equivalents) of allophanated hexane diisocyanate trimer (DESMODUR XP 7040) were charged into a dry 1 liter reactor equipped with drying tube, addition funnel, thermometer and mechanical stirring. Add 6 drops of dibutyltin dilaurate to the reactor. A mixture was prepared by mixing 89.7 g of 2-(N,N-dimethylamino)ethanol (1.0 l equivalent), 233.7 g of 2-hydroxyethyl acrylate (2.012 equivalent) and 0.48 g of BHT as a preservative. This mixture was added to the reactor while maintaining the temperature of the contents below 40°C. When the mixture was cooled to room temperature, it was poured into a container and separated. Infrared analysis showed only traces of isocyanate or free alcohol present. The substance is of low viscosity and pours easily.

Preparation of Modified Silica Particles

Preparation of mercapto-functionalized silica. 1176 grams of an aqueous dispersion of colloidal silicon dioxide having a pH 3.2 and a solids content of 34% by weight (commercially available from the Nalco Chemical Company of Napervile, Illinois under the tradename NALCO 1042) was diluted to total solids with distilled water 10%, the total amount is 4000 grams. To this dilution was added 19.6 grams of (3-mercaptopropyl)trimethoxysilane (commercially available from Aldrich Chemical Company, Milwaukee, Wisconsin). The resulting suspension was heated at 80° C. for 18 hours with stirring to give a translucent colorless suspension which was used without purification. A portion of the above suspension (50 grams) was mixed with 45 grams of SR 499 to obtain a slurry. The water was removed under vacuum (aspirator/rotovap) at room temperature to obtain 50 g of a clear liquid.

general method

Curing Method A

UV irradiation was performed using a wheeled cart, capable of operating on 110V electricity, with a face-down mounted panel facing an 18" (45.7cm) fluorescent lamp set, located approximately 1" (2.54cm) from the floor 1.5" ( 3.81cm) in the center. Suspend these lights in front of the wheels so that forward motion over uncured floor coating will not damage the finish. A reflective aluminum sheet is installed behind the lamp so that the radiant energy is directed towards the coating. There are two sets of bulbs on the panel, the first set consists of two 15 watt lamps connected to a 25 watt ballast, located at the front of the panel. These two lamps were one (1) 15 watt germicidal lamp (low pressure mercury lamp, emitting light at about 254nm wavelength) and the other (1) 15 watt blacklight (365nm). The second set consisted of six (6) 15 watt lamps connected to a 15 watt ballast. The second set is on the panel with 2 inches between the two sets of lights. The second set of lights consisted of alternating germicidal and black lights, for a total of six.

All germicidal bulbs are commercially available from General Electric under the trade designation "F15T8". Bulbs for black lights are also commercially available from General Electric under the trade designation "F15T8/BL". The power at the surface of the germicidal bulb, measured at the center of the bulb, is about 11 mW/cm ² for a 25 watt ballast and about 7 mW/cm ² for a 15 watt ballast. The measured power at the center surface of the black light bulb is about 7 mW/cm ² for a 25 watt ballast and about 4.5 mW/cm ² for a 15 watt ballast.

Unless otherwise noted, all samples were cured by 30 seconds of radiation from the above light source.

Curing Method B

A downward facing panel was used with 18 inch (45.7 cm) fluorescent light clusters located approximately 1 inch (2.54 cm) from the floor on 1.5 inch (3.81 cm) centers. A reflective aluminum sheet is mounted behind the lamp to direct the radiant energy towards the coating. This set of lights consists of six germicidal bulbs.

All bulbs are available from General Electric under the trade designation "F1518". The power measured at the center surface of the bulb was 7 mW/cm ² .

Unless otherwise noted, all samples were cured for 30 seconds by irradiation with the above light source.

Coating Method A

When applying the curable composition to a substrate, such as PVC floor tiles or sealed PVC floor tiles, a small amount of the composition, typically about 2-3 grams, is applied to the substrate using a syringe. The composition was then applied by calendering the composition over the desired area of the substrate using a rubber hand roller, spreading the applied composition over the substrate until a fairly uniform coating was obtained over the desired area of the substrate. The composition is then cured. To determine coating weight, the weight of the coated tile is compared to its original weight (eg, before application of the coatable composition).

experiment method

In the following examples, the following test methods were used.

                                                 

4 x 4 inch square samples of material coated for testing were prepared. Use a sample caliper to pinpoint a point on the coating where rubbing will occur and take an initial 20°-60° gloss reading on each side with a Byk-Gardner Micro-Tri-Gloss meter (Byk-Gardner, Silver Spring, MD) (total of four readings). The samples were then mounted on a Taber Standard AbrasionTester (model no. 503, Teledyne Taber, North Tonawanda, NY) with vacuum fittings, 500 gram wheel weight, and CS-10f wheels. The sample was rotated 100 times and the gloss after rubbing was measured as before. Calculate the percent gloss retention for each side and average the results.

              Test Method B (Scratch Hardness)

Scratch hardness was determined using a Byk-Gardner pencil scratch tester (Byk-Gardner, Silver Spring, MD). The assay is repeatable to about ±100 grams. Measurement results generally depend on substrate and film thickness.

             Test Method C (Peel Time)

The coatings of the present invention were tested to determine the time required to peel the radiation-cured coating from the substrate. In the test, the coating was peeled from the substrate using the following formulation: 68.75 parts deionized water, 22.50 parts benzyl alcohol, 5.52 parts n- Octylamine, 3.24 parts glycolic acid, 0.02 parts surfactant ("FLUORAD FC-129", available from Minnesota Mining Manufacturing Company).

Use a dropper to apply the stripper in many places on the cured coating. The stripping time was recorded as the time for 1) the film to bubble in the area fully covered by the stripper; or 2) the stripper completely loosened the coating and the applied stripper was manually wiped off with a paper towel to obtain a stripped clean substrate surface. time needed. A condition of 1 was generally observed for coatings applied on sealed PVC floor tiles and a condition of 2 was generally observed for PVC floor tiles. Peel time is highly sensitive and depends on coating thickness and how well the particular coating is cured. Therefore, care must be taken when comparing peel times for coatings of different thicknesses or degrees of cure.

                      Test Method D (Determination of Gloss)

Gloss measurements were performed using a calibrated Byk-Gardner Micro-Tri-Gloss meter (Byk-Gardner, Silver Spring, MD). Take the reading after cleaning the surface.

               Test Method E (Determination of Color)

Color measurements were made using a calibrated Datacolor International Microflash 200d spectrophotometer (Datacolor International, Charlotte, NC) in mirror mode using a 1.5 cm aperture. All readings are the average of 3 determinations. The CIELAB color coordinates L ^* , a ^* , b ^* and color shift DE used here are well known terms in color determination.

Example

The following non-limiting examples illustrate the preparation, use and comparative advantages of the invention. All parts and percentages are by weight unless otherwise indicated.

Example 1-15

Examples 1-15 were prepared and evaluated according to Test Method A for durability. The results of the analysis indicated that formulations with reduced amounts of SR-306 difunctional acrylate had the best durability. All samples containing 0.3 parts of FC-431 FLUORAD wetting agent were coated on PVC floor tiles. These samples were coated using Coating Method A at 2.5 g/ ^ft2 (26.9 g/ ^m2 ) and cured using Curing Method A. The formulations and abrasion resistance data for these examples are listed in Table 1.

Table 1 Preparation Example part oligomer A copies of SR-499 copies of SR-306 Parts DAROCUR 1173 %20° gloss retention standard deviation 1 50.00 35.00 15.0 5 74.0 4.8 2 30.00 45.00 25.00 5 43.1 8.1 3 40.00 42.50 17.50 5 67.0 2.6 4 40.00 35.00 25.00 5 63.5 3.0 5 35.00 50.00 15.00 5 70.9 3.4 6 40.00 35.00 25.00 5 66.3 3.2 7 40.00 42.50 17.50 5 74.2 1.9 8 50.00 40.00 10.00 5 78.2 1.7 9 45.00 45.00 10.00 5 77.8 1.5 11 40.00 50.00 10.00 5 77.2 1.4 12 50.00 40.00 10.00 5 76.4 3.5 13 30.00 45.00 25.00 5 64.1 3.0 14 30.00 50.00 20.00 5 56.1 3.4 15 45.00 35.00 20.00 5 64.2 2.1

Example 16

A number of samples were prepared according to some of the above data for Examples 1-15. Examples were prepared 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 16 samples. 5 parts photoinitiators such as sDAROCUR 1173 or other photoinitiators including 3 parts benzophenone mixed with 2 parts DAROCUR 1173 or IRGACURE 184 photoinitiators can be used. These compositions were applied according to Application Method A and Curing Method A on sealed PVC floor tiles to which a primer coating of CORNERSTONE floor sealer had been applied. Abrasion resistance, scratch hardness and peel time were determined according to Test Methods A, B and C above. The % gloss retention at 20° for these samples was consistently about 83%. The scratch hardness is about 1200 grams. The peeling time is less than 5 minutes.

Example 17-30

Examples 17-30 were prepared and evaluated according to Test Method A for abrasion resistance. The results of the analysis indicated that formulations with reduced amounts of SR-306 difunctional acrylate had the best durability. All samples containing 0.3 part (FLUORAD FC-431) wetting agent were coated on PVC floor tiles. These samples were coated using Coating Method A at 2.5 g/ ^ft2 (26.9 g/ ^m2 ) and cured using Curing Method A. The compositions and abrasion resistance data for these examples are listed in Table 2.

Table 2 Examples 17-30 Preparation Example part oligomer B copies of SR-499 copies of SR-306 Parts DAROCUR 1173 %20° gloss retention standard deviation 17 60 30 5 5 66.7 0.4 18 60 30 5 5 68.1 1.0 19 45 45 5 5 75.1 8.3 20 45 35 15 5 48.8 6.4 twenty one 45 30 20 5 51.2 4.3 twenty two 41.25 41.25 12.5 5 62.3 1.1 twenty three 45 45 5 5 73.4 2.2 twenty four 45 30 20 5 60.7 1.9 25 30 45 20 5 7.6 5.2 26 30 60 5 5 72.9 2.3 27 37.5 37.5 20 5 56.1 4.1 28 30 52.5 12.5 5 66.2 4.5 29 30 60 5 5 69.0 8.7 30 52.5 30 12.5 5 71.0 3.8

Example 31

Several samples were prepared based on partial results from Examples 17-30. A sample of Example 31 was prepared with 30 parts oligomer B, 65 parts trifunctional acrylate (SR-499), 0.3 parts wetting agent (FLUORAD FC-431 ), and 5 parts photoinitiator. As a photoinitiator, DAROCUR 1173 photoinitiator itself or other photoinitiators including a combination of benzophenone and DAROCUR 1173 photoinitiator, a combination of benzophenone and IRGACURE 184 photoinitiator can be used. These compositions were coated on substrates according to Application Method A and cured according to Curing Method A. Abrasion resistance, scratch hardness and peel time of the cured coatings were determined according to Test Methods A, B and C above.

Using an initiation system of 5 parts DAROCUR photoinitiator and 1 part benzophenone, the abrasion resistance was as high as 82% gloss retention at 20° after 15 seconds of irradiation. When cast onto sealed PVC floor tiles (sealed with a polyvinylidene chloride primed polyester film floor sealer available under the trade designation "THECHNIQUE" from S.C. Johnson, Milwaukee, Wisconsin), These formulations have a scratch hardness of 800-1000 grams. Delamination was observed at a force of 200 grams when a normal floor finish was applied. The peel time from sealed PVC floor tiles (when sealed with a floor finish available from the Minnesota Mining Manufacturing Company under the trade designation "CORNERSTONE") was about 2-3 minutes.

Example 32

Several samples were prepared based on the partial results of Example 16. These samples consisted of 40 parts oligomer C, 45 parts trifunctional acrylate (SR-499), 10 parts difunctional acrylate (SR-306), 5 parts photoinitiator, and 0.3 parts wetting agent (FLUORAD FC-431 ). As photoinitiator, DAROCUR 1173 photoinitiator and other photoinitiators including combination of benzophenone and DAROCUR 1173, combination of benzophenone and IRGACURE 184 photoinitiator can be used. These compositions were coated on substrates according to Application Method A and cured according to Curing Method A. Abrasion resistance, scratch hardness and peel time of the cured coatings were determined according to Test Methods A, B and C above. Abrasion resistance (% gloss retention at 20°) is consistently about 85%. The scratch hardness is about 1300 grams. The peel time from sealed PVC floor tiles (when sealed with a floor finish available from Minnesota Mining Manufacturing Company under the trade designation "CORNERSTONE") was less than 5 minutes.

Example 33-60

Examples 33-60 were prepared and evaluated according to Test Method A for abrasion resistance. All samples contained 0.3 parts of wetting agent (FLUORAD FC-431). The formulations of the examples were coated on PVC floor tiles using coating method A at a dry coating weight of 2.5 g/ft ² (26.9 g/m ² ) and cured using curing method A. The compositions and abrasion resistance data for Examples 33-60 are listed in Table 3. The results of the analysis showed that formulations with reduced amounts of SR-335 monofunctional acrylate had the best durability.

Table 3 Examples 33-60 Preparation Example part oligomer A copies of SR-454 copies of SR-335 Parts DAROCUR 1173 %20° gloss retention %60°gloss retention 33 45.00 35.00 20.00 5 62.50 67.88 34 30.00 20.00 50.00 5 Uncured Uncured 35 30.00 50.00 20.00 5 62.80 37.13 36 35.00 25.00 40.00 5 Uncured Uncured 37 30.00 50.00 20.00 5 29.39 36.47 38 30.00 20.00 50.00 5 Uncured Uncured 39 45.00 35.00 20.00 5 48.56 56.81 40 35.00 40.00 25.00 5 53.81 59.69 41 60.00 20.00 20.00 5 57.43 68.23 42 60.00 20.00 20.00 5 46.32 57.15 43 30.00 35.00 35.00 5 Uncured Uncured 44 50.00 25.00 25.00 5 65.36 76.89 45 45.00 20.00 35.00 5 Uncured Uncured 46 40.00 30.00 30.00 5 Uncured Uncured 47 57.50 30.00 12.50 5 52.90 70.60 48 50.00 30.00 20.00 5 56.90 64.90 49 50.00 50.00 0.00 5 56.80 75.20 50 57.50 42.50 0.00 5 51.20 69.20 51 60.00 38.33 1.67 5 59.50 77.20 52 50.00 30.00 20.00 5 59.60 68.80 53 65.00 35.00 0.00 5 68.30 79.00 54 65.00 30.00 5.00 5 62.70 75.50 55 50.00 50.00 0.00 5 53.40 74.40 56 57.50 36.25 6.25 5 64.40 74.80 57 50.00 40.00 10.00 5 60.80 70.10 58 50.00 40.00 10.00 5 66.30 73.50 59 60.00 31.67 8.33 5 68.20 80.80 60 57.50 36.25 6.25 5 74.20 80.50

Example 61

Several samples were prepared based on partial results from Examples 33-60. These samples included 177 parts oligomer A, 102 parts trifunctional acrylate (SR-454), 21 parts monofunctional acrylate (SR-335), 15 parts photoinitiator (DAROCUR 1173) and 0.3 parts wetting agent ( FLUORAD FC-431). Apply this formulation on PVC floor tiles according to Application Method A and cure according to Curing Method A. The abrasion resistance, scratch hardness and peel time of these samples were determined according to Test Methods A, B and C above. Abrasion resistance is approximately 74% gloss retention at 20°. The scratch hardness is greater than 1700 grams. The peeling time is about 3 minutes.

Example 62

A coatable composition was prepared comprising 60 parts oligomer A, 21 parts trifunctional acrylate (SR-454), 12 parts caprolactone acrylate, 2.4 parts photoinitiator (DAROCUR 1173). Apply a sample approximately 1 mil thick to the PVC floor tile according to Application Method A and cure according to Curing Method B for 20 seconds. According to Test Method C, the peel time of the prepared coating was determined to be about 8 minutes.

Example 63

A coatable composition was prepared comprising 60 parts oligomer A, 20 parts trifunctional acrylate (SR-454), 20 parts caprolactone acrylate, 5 parts photoinitiator (DAROCUR 1173). Using coating method A, the composition was coated on PVC floor tiles and cured according to curing method A. The resulting coatings were tested according to Test Methods A, B and C above. Abrasion resistance is approximately 75% gloss retention at 60°. The scratch hardness is about 500 grams. The peeling time from PVC floor tiles is about 3 minutes.

Examples 64 and 65

Examples 64 and 65 were prepared as listed in Table 4. Example 64 was the same as 65, except that in Preparation Example 65 the functionalized silica was prepared using the preparation method set forth above. Using application method A, the composition was coated on PVC floor tiles and cured according to curing method A to provide a cured coating approximately 0.25mm thick. According to Test Method A, the resulting coatings were tested for abrasion resistance. The gloss retention value at 20° indicates that the coating of Example 65 containing functionalized silica has slightly better abrasion resistance than Example 64.

Table 4 Example 64 and 65 Example composition 20°gloss retention average % standard deviation 64 40 parts oligomer C, 45 parts trifunctional acrylate (SR-499), 10 parts difunctional acrylate (SR-306), 3 parts benzophenone, 2 parts DAROCUR 1173 photoinitiator 83.9 4.5 65 40 parts oligomer C, 45 parts trifunctional acrylate with 10% functionalized silica (SR-499), 10 parts difunctional acrylate (SR-306), 3 parts benzophenone, 2 parts DAROCUR 1173 Photoinitiator 87.9 2.1

Example 66-71

To determine the effect of visible light on the color of cured coatings produced in accordance with the present invention, a premix was prepared. The premix consisted of 30 parts Oligomer C, 65 parts trifunctional acrylate (SR-499), 5 parts photoinitiator shown below, 0.3 parts wetting agent (FLUORAD FC-431). These samples were coated on off-white PVC floor tiles at a coating weight of 2.5 g/ft ² (26.9 g/m ² ) and cured using cure method A except that the cure time was 15 seconds. The cured coating was irradiated with a 6 x 15W Philips F15T8BLB lamp (approximately 5mW/ ^cm2 , 350-370nm) approximately 1 inch away. The sample was then irradiated by a 6 x 15W Philips 15WTLD/03 lamp (wavelength approximately 420nm) approximately 1 inch away. The CIELAB color coordinates L ^* , a ^* and b ^* are reported.

L ^* indicates white, positive a ^* color coordinates determine red, and positive b ^* color coordinates determine yellow. The DE value measures the overall color deviation, and a DE of less than 1-2 generally cannot be perceived by the naked eye. From the data presented in Table 5, it is clear that UV irradiation causes yellowing, which is reversible when irradiated with blue light.

Table 5 Examples 66-71 Example parts premix benzophenone Parts DARO-CUR 1173 Color coordinates after 15 seconds of curing Color coordinates after 45 minutes of 350-370nm light Color coordinates after 45 minutes of 420nm light L ^* a ^* b ^* L ^* a ^* b ^* DE L ^* a ^* b ^* DE 66 9.5 0.0 0.5 87.82 1.03 4.67 86.84 1.17 8.72 4.17 86.91 1.20 5.91 1.55 67 9.5 0.1 0.4 88.25 1.01 4.81 86.92 1.19 8.31 3.75 87.00 1.16 5.61 1.49 68 9.5 0.2 0.3 88.31 1.01 4.74 87.06 1.11 7.19 2.75 86.99 1.14 5.56 1.56 69 9.5 0.3 0.2 88.25 1.00 4.79 87.00 1.12 7.04 2.58 86.94 1.10 5.55 1.52 70 9.5 0.4 0.1 87.61 1.06 5.04 86.98 1.19 7.83 2.86 87.06 1.11 5.66 0.83 71 9.5 0.5 0.0 87.60 1.04 4.91 86.93 1.18 7.81 2.98 87.00 1.09 5.67 0.97

Example 72-80

According to the method for preparing oligomer B, by mixing 42 parts of allophanated HDI terpolymer (DESMODUR XP-7100), 2-hydroxyethyl acrylate and 2-dimethylamino-ethanol (equivalent ratio 3:2: 1) Preparation of oligomers. The oligomer was mixed 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 of wetting agent (FLUORAD FC-171) to provide a UV curable coatable composition. For some embodiments, EBECRYL 350 Acrylated Silicone may be added to the coating composition as a release material. The coatable composition was tested for adhesion to PVC floor tiles and sealed PVC floor tiles. Sealed PVC floor tiles are made by hand-applying a primer or sealer with a mesh to provide a smooth, even coating. The primer is then allowed to air dry at ambient temperature and humidity.

The coatable composition was applied to sealed PVC floor tiles and PVC floor tiles according to Application Method A and UV cured according to Curing Method A with a 10 second irradiation time. After curing, cut from the cured coating and primer (when present) to the tile base with a thin blade knife to form a 1/8 by 1/8 inch (0.32 by 0.32 cm) square grid. Tape ("SCOTCH Rugand Carpet Tape", commercially available from Minnesota Mining Manufacturing Company) was applied to the grid square with a 2.3 kg roller. Grasp one end of the tape by hand and pull at an angle of about 180° so that the back of the tape is overlaid on top of it, peeling the tape from the floor tile. Adhesion was determined by visual inspection of the tile and removed tape to determine the percentage of squares removed from the tile. An adhesion value of 0% means that all of the coating was removed from the tile, while 100% adhesion means that no coating was removed. For sealed PVC tiles, especially those sealed with ROSHILD 3120 Latex, generally all UV-cured coatings will bond to the tile substrate with good adhesion.

The composition of the UV-curable coatings, the primers used and the data of the adhesion tests are listed in Table 6. Unless otherwise noted, the coatings of these examples consisted of 100 parts coatable composition with no added acrylated silicone.

Table 6 Example Primer Adhesion% 72 none 0 73 (100 parts paint + 1 part EBECRYL350 acrylated silicone) none 0 74 TECHNIQUE 10 75 topLINE 0 76 ROSHIELD 3120 100 77 topLINE coated with ROSHIELD3120 90 78 (100 parts paint + 1 part EBECRYL350 acrylated silicone) ROSHIELD 3120 100 79 (100 parts paint + 2 parts EBECRYL350 Acrylated Silicone) ROSHIELD 3120 100 80 (100 parts paint + 3 parts EBECRYL350 acrylated silicone) ROSHIELD 3120 100

Although the invention has been described in detail, it should be understood that modifications and variations can be made to the described embodiments by those skilled in the art without departing from the spirit and scope of the invention as set forth in the following claims .

Claims (43)

1. A monomer useful for the formulation of a radiation-curable coatable composition comprising (a) a polyfunctional isocyanurate having at least three compounds associated with (b) a hydroxyalkyl acrylate The terminal group reacted with (c) tertiary amino alcohol, the molar ratio of a:b:c is 1:1-2.5:0.5-2, wherein b+c is at least 3 and not greater than the terminal reactive group of (a) The total number of monomers has the following general formula:

in: R ₁ and R ₂ are H or CH ₃ ; R ₃ and R ₄ are each straight chain, branched or cycloalkyl having 1-12 carbon atoms, or R ₃ and R ₄ together form a divalent cycloalkanediyl group having 2-12 carbon atoms, oxygen bridging group of heterocycloalkanediyl or azacycloalkanediyl; and Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ and Z ₆ each represent a divalent group having 1 to 18 carbon atoms. 2. The monomer according to claim 1, characterized in that the divalent groups Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ and Z ₆ include straight chains and branched chains with 1-18 carbon atoms or cycloalkanediyl. 3. The monomer according to claim 2, wherein said alkanediyl group is a straight chain alkanediyl group having 1-4 carbon atoms. 4. A radiation curable coatable composition comprising: (a) a first monomer comprising the monomer of claim 1; (b) a second monomer comprising an acrylate material; and (c) Photoinitiators. 5. A coatable composition according to claim 4, characterized in that the first monomer is present in the composition in an amount ranging from 10 to 90% by weight. 6. The coatable composition of claim 4, wherein the acrylate material is selected from the group consisting of monofunctional acrylates, difunctional acrylates, trifunctional acrylates, high-functional acrylates and combinations thereof. 7. The coatable composition as claimed in claim 6, wherein said monofunctional acrylate is selected from tetrahydrofurfuryl acrylate, cyclohexyl acrylate, n-hexyl acrylate, 2-ethoxyethyl acrylate, Isodecyl acrylate, 2-methoxyethyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, octadecyl acrylate, lauryl acrylate, octyl acrylate, 2-phenyl acrylate Oxyethyl acrylate, glycidyl acrylate, isobornyl acrylate, benzyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated nonylphenol acrylate, polypropylene glycol acrylate, and combinations of the above . 8. The coatable composition as claimed in claim 6, wherein said difunctional acrylate is selected from triethylene glycol diacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, diacrylic acid Polyethylene glycol ester, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, diethylene glycol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, Tripropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, propoxylated neopentyl glycol diacrylate, and combinations thereof. 9. The coatable composition as claimed in claim 6, wherein said trifunctional acrylate is selected from trimethylolpropane triacrylate, triacrylic acid tris (2-hydroxyethyl) isocyanuric acid esters, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, and combinations thereof. 10. The coatable composition of claim 6, wherein the highly functional acrylate is selected from the group consisting of pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate; metal acrylates salt, and combinations of the above. 11. Coatable composition according to claim 10, characterized in that the metal acrylates are zinc diacrylate and calcium diacrylate. 12. The coatable composition of claim 4, wherein said acrylate material is selected from the group consisting of acrylated oligomers, acrylated polymers, acrylated silicones, and combinations thereof. 13. The coatable composition of claim 12, wherein the acrylated polymer is selected from the group consisting of polyurethane monoacrylate, polyurethane multiacrylate, polyester monoacrylate , polyester multiacrylate, polyamide monoacrylate, polyamide multiacrylate, polybutadiene monoacrylate, polybutadiene multiacrylate, and combinations thereof. 14. The coatable composition of claim 4, wherein the second monomer is present in the composition in an amount of 5 to 90% by weight. 15. The coatable composition of claim 4, wherein said photoinitiator comprises 2-10% by weight benzophenone. 16. The coatable composition of claim 4, further comprising silica particles modified with 3-mercaptopropyltrimethoxysilane. 17. A coating derived from the coatable composition of claim 4. 18. A floor finish system comprising: The coatable composition of claim 4; and Primer composition. 19. The floor finish system of claim 18, wherein said primer comprises an acrylated latex having a solids content of 2-40% by weight. 20. A method of applying a protective coating on a substrate, the method comprising: (A) applying a radiation curable coatable composition on a substrate, the composition comprising: (i) a first monomer comprising (a) a polyfunctional isocyanurate having at least three end groups reacted with (b) a hydroxyalkyl acrylate and (c) a tertiary amine alcohol, a : The molar ratio of b:c is 1:1-2.5:0.5-2, wherein b+c is at least 3 and not greater than the total number of terminal reactive groups of (a), the first monomer has the following general formula :

R ₁ and R ₂ are H or CH ₃ ; R ₃ and R ₄ are each straight chain, branched or cycloalkyl having 1-12 carbon atoms, or R ₃ and R ₄ together form a divalent cycloalkanediyl group having 2-12 carbon atoms, oxygen bridging group of heterocycloalkanediyl or azacycloalkanediyl; and Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ and Z ₆ each represent a divalent group having 1 to 18 carbon atoms. (ii) a second monomer comprising an acrylate material, including a radiation curable substance, and (iii) photoinitiators; and (B) forming a protective coating on a substrate by subjecting the coatable composition to ultraviolet radiation to harden the composition. 21. The method according to claim 20, characterized in that the method also includes, before step (A), applying a primer composition on the floor, and drying the primer composition to form a primer coating on the substrate. layer. 22. The method of claim 21, wherein said primer composition comprises an acrylated latex having a solids content of 2-40% by weight. 23. The method according to claim 20, characterized in that the method also includes, before step (A), reacting polyfunctional isocyanurate with tertiary amine alcohol and at least one hydroxyalkyl acrylate to obtain the first a single body. 24. Process according to claim 23, characterized in that the polyfunctional isocyanurate is a trimer of hexane diisocyanate or an allophanated trimer derived from the reaction of hexane diisocyanate and butanol. things. 25. The method according to claim 23, wherein said tertiary amino alcohol is selected from the group consisting of acyclic tertiary dialkylamino alcohols with 3-30 carbon atoms, alicyclic tertiary alcohols with 3-30 carbon atoms, Amino alcohols, polyamino alcohols having 3-30 carbon atoms, aromatic amino alcohols, and combinations thereof. 26. The method according to claim 25, wherein said acyclic tertiary dialkylaminoalcohol with 3-30 carbon atoms is selected from N,N-dimethylaminoethanol, N,N-di Methylaminopropanol, N,N-Dimethylaminobutanol, N,N-Dimethylaminohexanol, N,N-Dimethylaminododecanol, N,N-Diethylaminoethanol , N,N-diethylaminopropanol, N,N-diethylaminobutanol, N-ethyl-N-methylaminopropanol, N-ethyl-N-hexylaminoethanol, and the above combination. 27. The method as claimed in claim 25, wherein said alicyclic tertiary amino alcohol with 3-30 carbon atoms is selected from the group consisting of 2-aziridinyl ethanol, 2-azetidinyl ethanol, 2-piperidinoethanol, N-methyl-4-azacyclohexanol, and combinations thereof. 28. The method according to claim 25, wherein the polyaminoalcohol having 3-30 carbon atoms is selected from the group consisting of N-methylpiperazinoethanol, N-butylpiperazinoethanol, N-methylpiperazinoethanol, piperazinobutanol, and combinations thereof. 29. The method of claim 23, wherein said hydroxyalkyl acrylate is 2-hydroxyethyl acrylate. 30. The method of claim 20, wherein the acrylate material is selected from monofunctional acrylate, difunctional acrylate, trifunctional acrylate, high-functional acrylate, and combinations thereof. 31. The method according to claim 30, wherein said monofunctional acrylate is selected from tetrahydrofurfuryl acrylate, cyclohexyl acrylate, n-hexyl acrylate, 2-ethoxyethyl acrylate, isodecyl acrylate , methoxyethyl acrylate, 2-(2-ethoxyethoxy) ethyl acrylate, octadecyl acrylate, lauryl acrylate, octyl acrylate, 2-phenoxyethyl acrylate, Glycidyl acrylate, isobornyl acrylate, benzyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated nonylphenol acrylate, polypropylene glycol acrylate, and combinations thereof. 32. The method according to claim 30, wherein said difunctional acrylate is selected from triethylene glycol diacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate ester, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, diethylene glycol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate esters, ethoxylated bisphenol A diacrylate, propoxylated neopentyl glycol diacrylate, and combinations thereof. 33. The method of claim 30, wherein the trifunctional acrylate is selected from the group consisting of trimethylolpropane triacrylate, triacrylate tris(2-hydroxyethyl)isocyanurate, ethoxy trimethylolpropane triacrylate, pentaerythritol triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, and combinations thereof. 34. The method according to claim 30, wherein the high-functional acrylate is selected from the group consisting of pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate; metal acrylate , and combinations of the above. 35. The method of claim 34, wherein the metal acrylates are zinc diacrylate and calcium diacrylate. 36. The method of claim 20, wherein said acrylate material is selected from the group consisting of acrylated oligomers, acrylated polymers, acrylated silicones, and combinations thereof. 37. The method of claim 36, wherein the acrylated polymer is selected from the group consisting of polyurethane monoacrylate, polyurethane multiacrylate, polyester monoacrylate, polyester polyacrylate Acrylates, polyamide monoacrylates, polyamide multiacrylates, polybutadiene monoacrylates, polybutadiene multiacrylates, and combinations thereof. 38. The method of claim 20, wherein the second monomer is present in the coatable composition in an amount of 5 to 90% by weight. 39. The method of claim 20, wherein the photoinitiator comprises benzophenone in combination with a carbazole derivative, the photoinitiator being present in the composition in an amount of 2-10% by weight. 40. The method of claim 20, wherein hardening of the composition comprises exposing the composition to ultraviolet light for less than 30 seconds. 41. The method according to claim 40, characterized in that said ultraviolet light irradiation includes a first wave band with a wavelength less than 300nm and a second wave band with a wavelength between 300-400nm, and at a ^rate of 5-15mW/cm The intensity of ultraviolet light emitted from the light source. 42. A substrate treated according to the method of claim 20. 43. A method of applying a protective coating on a substrate, the method comprising: (a) applying a coatable acrylated latex primer composition to a substrate; (b) drying the primer composition to form a primer coat of acrylated polymer covering the substrate; (c) applying a radiation-curable coatable composition as claimed in claim 4 on the primer coat; and (d) exposing the composition to ultraviolet radiation to harden the radiation curable coatable composition to form a protective coating covering the substrate.