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EP0929612A1 - Veredelungszusammensetzungen für böden - Google Patents

Veredelungszusammensetzungen für böden

Info

Publication number
EP0929612A1
EP0929612A1 EP96930857A EP96930857A EP0929612A1 EP 0929612 A1 EP0929612 A1 EP 0929612A1 EP 96930857 A EP96930857 A EP 96930857A EP 96930857 A EP96930857 A EP 96930857A EP 0929612 A1 EP0929612 A1 EP 0929612A1
Authority
EP
European Patent Office
Prior art keywords
acrylate
composition
monomer
foregoing
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96930857A
Other languages
English (en)
French (fr)
Inventor
Steven J. Hamrock
Fidelis C. Onwumere
Bradford B. Wright
Michael A. Yandrasits
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP0929612A1 publication Critical patent/EP0929612A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • the present invention relates to a radiation curable coatable composition suitable for use as a floor finish, to a floor finishing system utilizing the composition, to a method for applying a protective coating to a substrate, to substrates coated with the compositions and to a polyfunctional isocyanurate monomer useful in the formulation of the radiation curable coatable compositions.
  • Polymer compositions are used in the formulation of various coating compositions such as floor finishes, for example.
  • Commercially available floor finish compositions typically are aqueous emulsion based polymer compositions comprising one or more organic solvents, plasticizers, coating aids, antifoaming agents, polymer emulsions, waxes and the like. These compositions typically comprise a relatively low solids content (e.g., about 15 - 35%).
  • the polymer composition is applied to a floor surface and then allowed to dry in air, normally at ambient temperature and humidity to form a film that serves as a protective barrier against soil deposited on the floor by pedestrian traffic, for example.
  • photoinitiator refers to any substance or combination of substances that interact with light to generate free radicals capable of inducing free radical polymerization. Photochemical or photoinitiated free radical polymerizations occur when radicals are produced by ultraviolet ("UV") and/or visible light irradiation of a free radical polymerizable reaction system. Energy absorption by one or more compounds in the system results in the formation of excited species, followed by either subsequent decomposition of the excited species into radicals or interaction of the excited species with a second compound to form radicals derived from both the initially excited compound and from the second compound. The exact mechanism for photoinitiation is not always clear and may involve either or both of the aforementioned pathways.
  • 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 in photolithography for producing integrated and printed circuits and in curing dental materials.
  • Many of the known applications involve a combination of photopolymerization and crosslinking with the crosslinking typically achieved by the used of ethylenically polyunsaturated monomers.
  • Acrylate based systems are common as well as those based on unsaturated polyester and styrene.
  • UV curable protective finishes have been applied to vinyl "no wax" flooring during the sheet manufacturing process to provide gloss as well as abrasion resistance. These protective finishes generally cannot be easily stripped from the flooring to which they are applied using conventional stripping methods (e.g., by the application of a chemical stripping composition with a stripping pad or brush). Furthermore, the curing of these finishes is typically carried out using high intensity light. The lamps have high power requirements, large power supplies and generally require ducted venting to remove ozone. Often, these finishes are cured in an inert atmosphere to overcome the deleterious effects of oxygen on the curing process. Because of the above noted power requirements and the like, the use of UV curable polymeric systems in the treatment of flooring has generally been limited to factory scale processes where the expense and additional burdens associated with these systems is more easily justified.
  • the hardened floor finish not alter the color of the floor.
  • the finish should be transparent and substantially free of observable color. This goal is especially desired in the maintenance of floors composed of white floor tiles where an observable color in the hardened finish will more noticeably produce an observable discoloration in the floor.
  • the applied floor finish should also have low odor prior to curing.
  • the invention provides a coatable composition that can be cured quickly in air by exposure to low intensity ultraviolet radiation to provide a durable protective coating for a suitable substrate such as vinyl floor tile, for example.
  • a suitable substrate such as vinyl floor tile, for example.
  • the resulting coating requires little maintenance and can be easily and quickly stripped from the substrate by application of a suitable stripper composition, all as set forth herein.
  • the invention provides a monomer useful in the formulation of radiation curable coatable compositions, comprising (a) polyfiinctional isocyanurate having at least three terminal reactive groups reacted with (b) hydroxyalkyi 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 greater than the total number of terminal reactive groups of (a).
  • a preferred monomer comprises a compound having the general formula:
  • R 3 and R4 may independently be alkyl groups (straight, branched or cyclic) having from 1 to 12 carbon atoms, or R3 and R may together form a divalent cylcoalkanediyl, oxacycloalkanediyl, or azacycloalkanediyl bridging group having from 2 to 12 carbon atoms; and Zi, Z 2 , Z 3 , Z 4 , Z 5 , and Z 6 independently represent divalent groups having from 1 to 18 carbon atoms, preferably alkanediyl groups (straight, branched or cyclic) having from 1 to 18 carbon atoms, most preferably, straight chain alkanediyl groups having from 1 to 4 carbon atoms.
  • the foregoing monomer is formulated into radiation curable coatable compositions as a first monomer by combining it with a second monomer and photoinitiator.
  • the first monomer preferably comprises the reaction product of a trimer of hexane diisocyanate (optionally mixed with an allophanate of hexane d ⁇ socyanate), a hydroxyalkyi acrylate, and a tertiary amine alcohol.
  • the first monomer is typically present within the composition in an amount between about 10 and 80 wt%.
  • the second monomer can be selected from any of a variety of polymerizable monomers.
  • the second monomer is an acrylate, as is further described herein.
  • the second monomer is typically present within the composition in an amount between about 5 and 90 wt%.
  • the composition may further comprise additional polymerizable monomers, including combinations of two or more such monomers.
  • a suitable photoinitiator is included within the composition to facilitate curing by UV radiation. Preferred are those initiators suitable in the formation of clear coatings having a low degree of observable color. Photoinitiator concentrations within the composition may vary depending 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. Certain terms will be understood to have certain meanings, as set forth herein.
  • Ultraviolet radiation and “UV radiation” are used interchangeably to refer to the spectrum of light comprising wavelengths within the range from about 180 nm to 400 nm.
  • Coatable composition means a liquid composition that can be applied to a substrate and thereafter solidified (e.g., by UV curing) to form a hardened coating on the substrate.
  • Rapid curable in 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 (e.g., 180 to 800 nm).
  • Substrate refers to any surface upon which the coatable compositions of the invention are applied and includes without limitation, vinyl floor tiles (including tiles previously coated with floor sealer or the like), ceramic tiles, wood, marble, and the like.
  • acrylate will be understood to include acrylate and methacrylate species.
  • Monomer refers to any chemical species having at least one free radical polymerizable group (e.g., acrylate, methacrylate).
  • Tertiary amine alcohol is meant to indicate a tertiary amine that includes alcohol functionality.
  • the invention provides a floor finishing system, comprising the radiation curable coatable composition described above and a primer composition, the primer composition coatable over a substrate.
  • the coatable composition is as previously described.
  • the primer 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 coatable composition.
  • the primer provides a layer over the substrate to which the coatable composition may bond.
  • the cured coatable composition is readily strippable from the substrate when the latex primer is present.
  • a method for applying a protective coating to a substrate comprising:
  • composition comprising:
  • a first monomer comprising (a) polyfunctional isocyanurate having at least three terminal reactive groups reacted with (b) hydroxyalkyi acrylate and (c) tertiary amine alcohol in a molar ratio of a:b:c of about 1 : 1-2.5:0.5-
  • the first monomer, the second monomer and the photoinitiator are as previously described.
  • the coatable composition is preferably comprises at least about 90% solids (e.g., less than about 10% solvent). Hardening of the composition in step (B) may be achieved in air at prevailing temperature and humidity (e.g., at ambient conditions). Although high intensity radiation achieves faster curing of the coatable composition and is generally preferred in performing the hardening step (B), the coatable compositions can also be cured with low intensity UV radiation.
  • Hardening of the coatable compositions at low UV intensities can be accomplished fairly quickly (e.g., less than 30 seconds) using a low intensity radiation source that provides at least one band of wavelengths less than about 300 nm and a second band between about 300 and 400 nm.
  • a low intensity radiation source emits a first band of wavelengths centered around 254 nm and a second band centered between 350 and 370 nm (e.g., around 365 nm) to cure the coating (typically about 0.03 mm thick) in less than about 30 seconds.
  • a suitable low intensity radiation source is one that provides a radiation intensity between about 5 and 15 mW per square centimeter.
  • 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 foregoing applying step (A), applying a primer composition to the floor and drying the primer composition to form a primer coat over the substrate.
  • a primer composition is an acrylated latex, preferably having a solids content between about 2 and about 40% by weight.
  • the invention provides a coating derived from the foregoing radiation curable coatable composition. In another aspect, the invention provides a substrate coated with the aforementioned coating.
  • the invention broadly provides a method for applying a protective coating to a substrate, comprising:
  • Coatable compositions according to the invention are formulated with a first monomer comprising an isocyanurate.
  • the preferred first monomer is derived from the reaction of a polyfunctional isocyanate, hydroxyalkyi acrylate and tertiary amine alcohol.
  • the compositions of the invention also comprise a second monomer and photoinitiator.
  • the end product e.g., the final hardened coating
  • the end product be substantially free of observable color, provide a hard and durable finish, and be readily removable from the substrate to which the composition has been applied.
  • 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, (hydroxyalkyl)dialkylamine, and a hydroxyalkyi acrylate.
  • polyfunctional isocyanurate is reacted with from about one to about 2.5 moles of the hydroxyalkyi acrylate and with from about 0.5 to about 2.0 moles of the tertiary amine alcohol.
  • the first monomer comprises (a) polyfunctional isocyanurate having about three terminal reactive groups reacted with (b) hydroxyalkyi 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 greater than the total number of terminal reactive groups of (a).
  • the terminal reactive groups of the polyfunctional isocyanurate comprise isocyanate groups (-NCO), each of which is capable of reacting with the hydroxyl groups in both the hydroxyalkyi acrylate and the tertiary amine to form a urethane linkage (- NH-CO-O-) within the reaction product.
  • the theoretical functionality of the polyfunctional isocyanurate is three, it will be appreciated the actual functionality of the polyfunctional isocyanurate may be somewhat less (e.g. between 2.5 and 3.0) while still being within the scope of the present invention.
  • the first monomer may comprise a compound having the general formula:
  • R 3 and R4 may independently be alkyl groups (straight, branched or cyclic) having from 1 to 12 carbon atoms, or R3 and R may together form a divalent cyicoalkanediyl, oxacycloalkanediyl, or azacycloalkanediyl bridging group having from 2 to 12 carbon atoms; and Zi, Z 2 , Z 3 , Z 4 , Zs, and Z ⁇ independently represent divalent groups having from 1 to 18 carbon atoms, preferably alkanediyl groups (straight, branched or cyclic) having from 1 to 18 carbon atoms, most preferably, straight chain alkanediyl groups having from 1 to 4 carbon atoms;
  • the polyfunctional isocyanate trimer useful in the formation of the polyfunctional isocyanurate preferably is a low viscosity polyfunctional aliphatic polyisocyanate resin.
  • the polyfunctional isocyanurate is a trimer of aliphatic d ⁇ socyanate and more preferably is a trimer derived from hexamethylene diisocyanate (HDI).
  • HDI hexamethylene diisocyanate
  • the foregoing polyfunctional isocyanurate is important in the formation of clear and substantially colorless coatings by UV curing.
  • compositions based on these polyfunctional isocyanurates typically cure rapidly (e.g., less than a minute) in air upon exposure to low intensity UV light.
  • Suitable polyfunctional isocyanurate may readily be synthesized by the oligomerization of diisocyanate (e.g., HDI) to provide the foregoing trimer, as is known to those skilled in the art.
  • Suitable products based on HDI derived isocyanurate are commercially available such as those available under the trade designation DESMODUR N-3300.
  • allophanated 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 abovementioned isocyanate trimers are available from the Industrial Chemicals Division of Bayer Corporation, Pittsburgh, Pennsylvania.
  • the amount of allophanate be minimized for better performance of the resulting cured coating.
  • Low viscosity aliphatic isocyanate diluents may be used in a similar manner, subject to the same requirements.
  • the DESMODUR XP 7100 monomer is most preferred.
  • the polyfunctional isocyanurate used herein provides three distinct reactive isocyanate groups extending from the isocyanurate ring. Each of the isocyanate functionalities is capable of reacting with the hydroxyl group on both the tertiary amine alcohol and the hydroxyalkyi acrylate to form the first monomer.
  • Tertiary amine alcohols suitable for use in the invention include acyclic (hydroxyalkyl)dialkylamines having from 3 to 30 carbon atoms such as NN- dimethylaminoethanol, N,N-dimethylaminopropanol, N,N-dimethylaminobutanol, NN-dimethylaminohexanol, NN-dimethylaminododecanol, N,N- diethylaminoethanol, NN-diethylaminopropanol, NN-diethylaminobutanol, N-ethyl-
  • N-methylaminopropanol, N-ethyl-N-hexylaminoethanol, and the like N-methylaminopropanol, N-ethyl-N-hexylaminoethanol, and the like; alicyclic (hydroxyalkyl)dialkylamines having from 3 to 30 carbon atoms such as 2- aziridinylethanol, 2-azetidinylethanol, 2-piperidinoethanol, N-methyl-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)alkylarylamines and (hydroxyalkyl)diarylamines may also be used in the invention, although their use is not preferred due to the tendency of compositions comprising aromatic amines to discolor upon curing.
  • Tertiary amine alcohols including the foregoing examples thereof, may be synthesized according to known methods, or they may be commercially obtained from any of a variety of commercial sources such as Texaco Corp. of Houston, Texas; Ashland Chemical Co. of Columbus, Ohio and Aldrich Chemical Co. of Milwaukee, Wisconsin.
  • hydroxyalkyi acrylate is reacted with about one mole of polyfunctional isocyanurate.
  • the hydroxyl group of the hydroxyalkyi acrylate reacts with isocyanate so that the main reaction product comprises acrylate groups pendant to the isocyanurate ring.
  • the double bonds of these acrylate groups provide reactive sites capable of forming additional bonds with other monomers during polymerization.
  • Suitable hydroxyalkyi acrylate compounds comprise any of a variety of acrylic compounds including hydroxyalkyi acrylates, N-hydroxyalkyl acrylamides, and the like.
  • hydroxyalkyi acrylates especially hydroxyalkyi acrylates comprising a Ci to C 4 hydroxyalkyi moiety.
  • a particularly preferred hydroxyalkyi acrylate is 2-hydroxyethyl acrylate, available from Dow Chemical Co. of Midland, Michigan. SECOND MONOMER
  • the foregoing first monomer may be polymerized in a reaction with at least one additional radiation curable monomer ("second monomer").
  • second monomer additional radiation curable monomer
  • the first monomer and the second monomers react to form a highly crosslinked polymeric coating suitable for use 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.
  • 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 monomer(s) is chosen to achieve a preferred balance of properties in both the uncured composition as well as in the cured coating.
  • Suitable acrylates for use in the invention include, without limitation, monoacrylates such as tetrahydrofurfiiryl acrylate, cyclohexyl acrylate, w-hexyl acrylate, 2-ethoxyethyl acrylate, isodecyl acrylate, 2-methoxyethyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, stearyl 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 the like; diacrylates such as triethylene glycol diacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol di
  • the second monomer may comprise substances other than acrylated monomers, preferably substances that readily copolymerize with acrylate monomers such as the foregoing acrylated first monomer used in the present invention.
  • Suitable materials include N-vinyl monomers such as N-vinylformamide, N- vinylpyrrolidone, N-vinylcarbazole, and the like; acrylamide and derivatives thereof such as methylolacrylamide; styrenic monomers such as styrene, ⁇ -methylstyrene, vinylpyridine, and the like; and other monomers such as vinyl ethers, ally] ethers such as triallyl isocyanurate, ally] 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 Sartomer Company under the trade designations "SR 454", “SR 499”, “SR 502” and “SR 9035” and propoxylated diacrylates such as tripropylene glycol diacrylate.
  • the second monomer(s) is added to a reaction mixture with the first monomer and polymerized to form the hard, durable, clear coatings of the invention, as is further described below.
  • the weight percentage of the second monomer is typically within the range from about 5 to about 90%, preferably from about 35 to about 70 wt% and more preferably from about 45 to about 65 wt%.
  • the first monomer is present within the mixture at a concentration within the range from about 10 to about 90 wt%, preferably from about 25 to about 60 wt%, and more preferably from about 30 to about 50 wt%.
  • photoinitiator is added to the compositions of the invention to initiate the polymerization reaction.
  • Preferred photoinitiators are free radical initiators for ultraviolet curing.
  • special attention is given to the properties of high molar absorptivity (e.g., extinction coefficient) at the power maxima for the light source, low color and low tendency to color after UV exposure, shelf life stability, low or pleasant odor and high efficiency for photoinitiation of polymerization.
  • the photoinitiator will preferably have a high molar absorptivity (e.g., greater than
  • 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 assure a rapid surface cure, while the absorbance at the 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 a rapid and effective through cure.
  • the photoinitiators useful in the invention include those known as useful in the UV cure of acrylate polymers.
  • Such initiators include benzophenone and its derivatives; benzoin, ⁇ -methylbenzoin, ⁇ -phenylbenzoin, ⁇ -allylbenzoin, a- benzylbenzoin; benzoin ethers such as benzil dimethyl ketal ((commercially available under the trade designation "IRGACURE 651" from Ciba-Geigy of Ardsley, New York), benzoin methyl ether, benzoin ethyl ether, benzoin w-butyl ether; acetophenone and its derivatives such as 2-hydroxy-2-methyl-l-phenyl-l-propanone (commercially available under the trade designation "DAROCUR 1173" from Ciba-
  • HCPK 1-hydroxycyclohexyl phenyl ketone
  • IRGACURE 184 also from Ciba-Geigy Corporation
  • 2-methyl- 1 -[4-(methylthio)phenyl]-2-(4-morpholinyl)- 1 - propanone commercially available under the trade designation "IRGACURE 907", also from Ciba-Geigy Corporation
  • 2-benzyl-2-(dimethIamino)-l-[4-(4- morpholinyl)phenyI]-l-butanone commercially available under the trade designation "IRGACURE 369", also from Ciba-Geigy Corporation).
  • photoinitiators include pivaloin ethyl ether, anisoin ethyl ether; anthraquinones such as anthraquinone, 2-methyIanthraquinone, 2-ethyl anthraquinone, 2-f-butyI anthraquinone, 1-chloroanthraquinone, 2-bromoanthraquinone, 2- nitroanthraquinone, anthraquinone- 1-carboxaldehyde, anthraquinone-2-thiol, 4- cyclohexylanthraquinone, 1 ,4-dimethylanthraquinone, 1 -methoxyanthraquinone, benzathraquinonehalomethyl triazines; 'onium salts, for example, diazonium salts such as phenyldiazoniumhexafluorophosphate and the like; diary
  • photoinitiators not listed herein may also be suitable for use in the present invention.
  • the selection of a suitable photoinitiator is well within the skill of those practicing in the field.
  • a preferred photoinitiator used in this composition is a combination of about 4 parts by weight benzophenone (based on the total weight of the composition) and 1 part by weight N-ethylcarbazole or N-vinylcarbazole.
  • Another preferred photoinitiator is a combination of about 4 parts by weight benzophenone (based on the total weight of the composition) and 1 part by weight benzoin dimethyl ketal.
  • the photoinitiator is present in the compositions of the invention at a concentration between about 2 and about 10 wt% and more preferably between about 4 and about 7 wt%.
  • OTHER INGREDIENTS Additional optional components can be included within the coatable compositions of the invention.
  • a wetting agent may be added in minor amounts to the coatable compositions to facilitate uniform coating over 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 the Minnesota Mining and
  • Fillers may be added to the coatable compositions of the invention to modify wear properties. Fillers known to be useful in acrylate clear coat applications may be used in the invention. A preferred filler is one in which silica particles are modified with 3-mercaptopropyltrimethoxysilane.
  • ingredients include defoamers, leveling aids, mar and slip additives, air release additives, antioxidants, light stabilizers such as benzotriazole light stabilizers, hydroxybenzophenone light stabilizers and the like; optical brighteners and other known formulation additives.
  • the first monomer is preferably prepared first and then blended with the second monomer(s), photoinitiator and other ingredients.
  • the polyfunctional isocyanurate is first added to a reaction vessel along with a suitable catalyst such as dibutyltin dilaurate.
  • a suitable catalyst such as dibutyltin dilaurate.
  • a mixture is prepared by the addition of the tertiary amine alcohol and the hydroxyalkyi acrylate.
  • a suitable preservative that will not be consumed during the reaction such as, for example, butylated hydroxytoluene (BHT) may also be added to the reaction mixture.
  • BHT butylated hydroxytoluene
  • the mixture of tertiary amine alcohol, hydroxyalkyi acrylate and preservative are added to the reaction vessel (containing the first monomer).
  • the reaction is allowed to proceed to completion under ambient conditions in air while controlling the temperature of the reaction mixture, preferably at a temperature below about 40°C to prevent the premature consumption of the preservative.
  • the reaction mixture is then allowed to cool to room temperature. Completion of the reaction may be monitored by appropriate means, such as by infrared spectrophotometry.
  • a particularly preferred coatable composition according to the invention is one comprising about 42 parts by weight first monomer (preferably DESMODUR XP 7100 isocyanurate commercially available from Bayer Corporation), about 48 parts by weight of ethoxylated trimethylolpropane triacrylate (commercially available under the trade designation "SR-499" from Sartomer Company, Inc.), about 5 parts by weight of tripropylene diacrylate, about 5 parts by weight photoinitiator and about 0.3 parts by weight of a suitable wetting agent (e.g., FLUORAD FC-171 from Minnesota
  • Suitable inhibitor may be any material known to inhibit free-radically induced polymerization including, but not limited to hindered phenols such as butylated hydroxytoluene (BHT) and its derivatives, hydroquinone and its derivatives such as methylhydroquinone, and N-nitrosophenylhydroxylamine aluminum salt commercially available under the designation "Q-1301" from Wako Chemicals USA, Inc. (Richmond, VA). Of these N-nitrosophenylhydroxylamine aluminum salt is preferred.
  • BHT butylated hydroxytoluene
  • hydroquinone and its derivatives such as methylhydroquinone
  • N-nitrosophenylhydroxylamine aluminum salt commercially available under the designation "Q-1301" from Wako Chemicals USA, Inc. (Richmond, VA). Of these N-nitrosophenylhydroxylamine aluminum salt is preferred.
  • the composition may then be coated onto a suitable substrate such as a conventional polyvinyi chloride floor tile, for example
  • the coatable composition is exposed to UV light to cure the composition to a hardened protective coating.
  • Suitable light sources may be selected by those skilled in the art. In general, high intensity light sources are preferred to achieve a fast cure of the coatable composition. However, in the application of the coatable compositions to installed flooring, low intensity UV light may be more practical, and the coatable compositions of the invention are readily curable by brief exposure to low intensity UV light.
  • a suitable low intensity UV light source is one that emits at least one band of wavelengths less than about 300 nm. To achieve a faster cure of the applied coating, the light source will preferably also emit a second band of wavelengths between about 300 and 400 nm.
  • a UV light source that emits a narrow band of wavelengths centered around 254 nm at an intensity (at the surface of the coating) of approximately 5-15 mW per square centimeter is adequate.
  • a low intensity light source also emits a second narrow band of wavelengths centered in the range 360-370 nm and typically around 365 nm at the same approximate intensity as mentioned.
  • the compositions of the present invention will normally cure in less than 30 seconds, preferably in less than 20 seconds.
  • One such light source is that described below in the Examples.
  • the overall configuration of the light source is outside the scope of the invention.
  • Different light sources may be used to effect curing of the compositions of the invention such as a pulsed xenon flash source, a medium pressure mercury source, a low pressure mercury fluorescent source and a
  • the composition be applied in manner which creates a coating no greater than about 1.3 millimeters in thickness in order to facilitate curing of the composition within the aforementioned time limits. Coatings of this thickness can be achieved by any of a number of known application techniques such as roll coating, squeegeeing, knife coating, curtain coating, spray coating, and the like.
  • suitable substrates include conventional floor tiles which may or may not be previously coated or sealed. When the substrate to be coated is vinyl tile or the like, it is preferred that the substrate is first treated with a primer or sealer prior to the application of the UV curable inventive compositions to that substrate.
  • a primer treatment of the substrate facilitates the ease at which the UV cured coating may subsequently be removed from the tile or other substrate by a chemical stripping formulation, for example.
  • an acrylated latex primer is most preferred.
  • the acrylated latex compositions useful herein must have at least one free-radically polymerizable group pendant from each latex particle, and preferably more than one.
  • the latex is hydrophobic in nature, but may contain some hydrophilic groups.
  • the solids content of the primer required for a wipe on coating (e.g., by hand) will be between about 2 and about 40% by weight, preferably between about 2 and about 20%, and more preferably between about 4 and about 15%.
  • a wetting agent or defoamer may be added to the latex emulsion to improve coating properties. The level of such additives will depend on the nature of the substrate and the concentration of the latex emulsion.
  • One preferred latex emulsion for use as a primer herein is the acrylated emulsion commercially available under the trade designation "ROSFHELD 3120" from Rohm and Haas Company, Philadelphia, PA. This emulsion is available at a solids content of about 40.5% by weight, and a suitable primer can be prepared by dilution of the concentrated emulsion at a dilution weight ratio of up to about 9: 1
  • aqueous primer formulation comprising a blend or the foregoing ROSHIELD 3120 acrylated latex with a second primer polymer, preferably the ammonium salt of a styrene maleic anhydride (SMA) copolymer (commercially available at a solids content of 38.5% under the trade designation "SMA 1000A” from Atochem, Inc. of Malvern, Pennsylvania).
  • SMA styrene maleic anhydride
  • the SMA is added to the primer to act as a leveling aid.
  • the weight ratio of the acrylate to the SMA copolymer in the primer is preferably between about 7: 1 and about 12: 1 and more preferably is about 10:1.
  • a small amount of surfactant may also be included in the primer.
  • a particularly preferred primer having a solids content of about 10 % by weight, comprises about 24.4 wt% of the ROSHIELD 3120 acrylated latex, about 73.2 wt% water, about 2.4 wt % SMA 1000 A copolymer and about 0.02 wt% 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 primer may be applied to the substrate by any suitable method such as wiping, brushing, spraying and the like.
  • the latex is allowed to dry, typically under ambient conditions, and the UV curable compositions of the invention may then be applied thereover and cured, as described herein.
  • Substrates such as PVC tiles, for example, coated with the above acrylated latex primer and then coated with a UV curable acrylate (e.g., a coatable composition) may be readily stripped using a benzyl alcohol stripper such as that described below in the Examples.
  • a benzyl alcohol stripper such as that described below in the Examples.
  • the thus stripped tiles present a very good appearance with stripping appearing to occur at the surface of the tile.
  • the primer can comprise a component of a floor finishing system that includes both the primer as well as the coatable composition described herein.
  • primers comprising the foregoing ROSHIELD 3120 acrylated latex (with or without added SMA copolymer) are preferred, other commercially available materials may also be used as primers on certain substrates such as on PVC composition floor tile.
  • Some suitable primers include various commercial floor sealers such as those available under the trade designations "CORNERSTONE" (Minnesota Mining and Manufacturing Company, St.
  • primers comprising ROSHIELD 3120 acrylated latex
  • the foregoing primer may be used in other applications outside the floor finishing art to apply any of a variety of UV polymerizable polymers (e.g., other than the foregoing coatable compositions) to a substrate.
  • the use of the primer provides a system and a 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 may also be more easily removed from the substrate by suitable stripper compositions.
  • a non-acrylated latex primer it is preferable to use a primer which has a surface tension of at least 40 dynes/cm.
  • the cured coatings of the invention may be stripped from the substrates to which they are applied by the application of a suitable stripper.
  • the stripper is a pH neutral formulation comprising a solvent, coupling agent (e.g., hydrotrope) and water.
  • Dye, fragrance and thickening agent may be added to the stripper composition if desired.
  • An effective stripper formulation for the floor finish compositions of the invention includes those set forth below in the Test Methods.
  • DESMODUR N3300 is the trade designation for a hexane diisocyanate trimer available from Bayer Corp., Industrial Chemicals Division.
  • DESMODUR XP 7100 is the trade designation for an allophanated hexane diisocyanate trimer mixture available from Bayer Corp., Industrial Chemicals Division.
  • DESMODUR XP 7040 is the trade designation for an allophanated hexane d ⁇ socyanate trimer mixture available from Bayer Corp.,
  • SR 306 is the trade designation for tripropylene glycol diacrylate, a difunctional acrylate monomer commercially available from Sartomer Co., Inc. of West
  • SR 335 is the trade designation for lauryl acrylate, a monofunctional acrylate monomer commercially available from Sartomer Co., Inc. of West Chester, PA.
  • SR 54 is the trade designation for ethoxylated trimethylolpropane triacrylate a trifunctional acrylate monomer commercially available from Sartomer Co.
  • SR 499 is the trade designation for ethoxylated trimethylolpropane triacrylate a trifunctional acrylate monomer commercially available from Sartomer Co.
  • DAROCUR 1173 is the trade designation for 2-hydroxy2-methyl-l- phenylpropan-1-one, a photoinitiator commercially ava ⁇ able from Ciba-Geigy, Ardsley, New York.
  • DAROCUR 4265 is the trade designation for an acylphosphine photoinitiator commercially available from Ciba-Geigy,
  • IRGACURE 184 is the trade designation for 1-hydroxycyclohexyl phenyl ketone, a photoinitiator commercially available from
  • FLUORAD FC-431 is the trade designation for a wetting agent available from Minnesota Mining and Manufacturing Company,
  • FLUORAD FC-171 is the trade designation for a wetting agent available from Minnesota Minmg and Manufacturing Company,
  • PVC Tile refers to standard floor tile comprising polyvinyl chloride that has been stripped and cleaned to remove the factory finish.
  • Sealed PVC Tile refers to standard floor tile comprising polyvinyl chloride that has been stripped and cleaned to remove the factory finish and then coated with a floor finish or sealer.
  • ROSHIELD 3120 is the trade designation for an acrylated emulsion commercially available from Rohm and Haas Company, Philadelphia, PA at a solids content of 40.5% by weight, and used herein as a primer by dilution of the concentrate with water at a dilution ratio of 9: 1 (water: emulsion).
  • EBECRYL 350 is the trade designation for acrylated silicones commercially available from UCB Radcure of Smyrna,
  • TECHNIQUE is the trade designation for an acrylic floor sealer commercially available from S.C. Johnson, Milwaukee, Wisconsin.
  • TOPLINE is the trade designation for an acrylic floor finish commercially available from Minnesota Mining and Manufacturing Company, St. Paul, Minnesota,
  • CORNERSTONE is the trade designation for an acrylic floor finish commercially available from Minnesota Mining and Manufacturing Company, St. Paul, Minnesota.
  • a dry one-Uter reaction vessel was fitted with a drying tube, addition funnel, thermometer and mechanical stir and charged with 642 g (3.018 eq.) allophanated hexane d ⁇ socyanate trimer (DESMODUR XP 7040). 6 drops dibutyltin dilaurate were added to the reaction vessel.
  • a mixture was prepared by mixing 89.7 g 2- (NN-dimethylamino)ethanol (1.01 eq.), 233.7 g 2-hydroxyethyl acrylate (2.012 eq.) and 0.48 g BHT as a preservative. This mixture was added to the reaction vessel while maintaining the temperature of the contents below 40 C.
  • UV exposures were made using a wheeled cart capable of running off HO V power having a front mounted downward facing bank of 18 inch (45.7cm) fluorescent Ughts on 1.5 inch (3.81 cm) centers at a distance of approximately 1 inch (2.54 cm) from the floor.
  • the Ughts were cantilevered in front of the cart wheels to allow for forward motion over uncured floor coating without marring the finish.
  • a reflective aluminum sheet was mounted behind the Ughts to boost the radiant energy directed toward the coating.
  • the lamps were in two sets within the bank. The first set consisted of two 15 watt Ughts on a 25 watt ballast in the front of the bank. These two Ughts consisted of one (1) 15 watt germicidal Ught (a low pressure mercury Ught emitting at about 254 nm) and one (1) 15 watt blackUght
  • the second set consisted of six (6) 15 watt Ughts on a 15 watt ballast. The second set was positioned in the bank with a two inch gap between the two light sets.
  • the second Ught set consisted of alternating germicidal and blacklights for a total of six (6) Ughts in the second set. All of the germicidal bulbs were commercially available from General
  • the blackUght bulbs were also available from General Electric under the designation "F15T8/BL”. Power measured at the germicidal bulb surface in the bulb center was about 11 mW/cra 2 for the 25 watt ballast and about 7 mW/cm 2 for the 15 watt baUast. Power measured at the blackUght bulb surface in the bulb center was about 7 mW/cm 2 for the 25 watt ballast and about 4.5 mW/cm 2 for the 15 watt ballast.
  • Curing Procedure B Exposures were made using a downward facing bank of 18" fluorescent Ughts on 1.5 inch centers at a distance of approximately 1 inch from the floor. A reflective aluminum sheet was mounted behind the Ughts to boost the radiant energy director toward the coating. The light set consisted of six germicidal bulbs.
  • Coating Procedure A In applying the coatable compositions to a substrate such as PVC TUe or Sealed PVC Tile, a small volume of the composition, typically about 2-3 grams, was appUed to the substrate using a syringe. The thus appUed composition was then coated over the substrate by using a hand held rubber roller to roll the composition over the desired area of the substrate until a fairly uniform coating was obtained over the desired area of the substrate. The composition was then cured. To determine the coating weight, the weight of the coated tile was compared to the initial tile weight (e.g., before applying the coatable composition).
  • Test Method A (Taber Abrasion Resistance : A 4" x 4" square sample of coated material to be tested was prepared. Using a template to precisely locate a spot on the coating where the abrasion was expected to occur, an initial 20° or 60° gloss reading was obtained for each side (four readings total) using a Byk-Gardner Micro-Tri-Gloss meter (Byk-Gardner,
  • the sample was then mounted on a Taber Standard Abrasion Tester (model no. 503, Teledyne Taber, North Tonawanda, NY) fitted with a vacuum attachment, 500 g wheel weights and CS-1 Of wheels.
  • the sample was subjected to 100 revolutions and the gloss after abrasion was measured as before. The percent gloss retention for each side was calculated, and the results were averaged.
  • Test Method B Scratch Hardness was determined using a Byk-Gardner pencil-type scratch tester (Byk-Gardner, Silver Spring, MD). Measurements were reproducible to about ⁇ 100 g. The results were generally substrate and film thickness dependent.
  • Test Method C Strip Time
  • the following formulation was used to strip coatings from tile substrates: 68.75 parts deionized water, 22.50 parts benzyl alcohol, 5.52 parts n-octylamine, 3.24 parts glycolic acid,
  • the stripper was appUed by a dropper onto a cured coating at numerous locations on the coating.
  • the strip time recorded was the time at which either 1) the film bubbled up over the entire area covered with stripper; or 2) the time required for the stripper to sufficiently loosen the coating so that hand wiping of the applied stripper with a paper towel resulted in a clean stripped substrate surface.
  • Condition 1 was generally observed for coatings applied over Sealed PVC TUe while condition 2 was generally observed for PVC TUe.
  • the strip tune is highly sensitive and will depend on coating thickness as weU as the degree of cure for a particular coating. Consequently, care must be taken in comparing strip time results of coatings having different thicknesses or those that have experienced different degrees of cure.
  • Test Method E 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. AU readings were an average of 3 measurements. CIELAB color coordinates L*, a*, b* and the color shift DE used herein are weU known terms in color measurement.
  • Example 16 samples were made with 40 parts Oligomer A, 45 parts trifunctional acrylate (SR-499), 10 parts difimctional acrylate (SR-306), 0.3 parts wetting agent (FLUORAD FC-431) and photoinitiator. 5 parts of a photoinitiator such as the DAROCUR 1173 material or other photoinitators were all used successfully including 3 parts benzophenone combined with 2 parts of either DAROCUR 1173 photoinitiator or IRGACURE 184 photoinitiator.
  • SR-499 trifunctional acrylate
  • SR-306 10 parts difimctional acrylate
  • FLUORAD FC-431 wetting agent
  • 5 parts of a photoinitiator such as the DAROCUR 1173 material or other photoinitators were all used successfully including 3 parts benzophenone combined with 2 parts of either DAROCUR 1173 photoinitiator or IRGACURE 184 photoinitiator.
  • Examples 17-30 were prepared and evaluated for abrasion resistance according to Test Method A. Analysis of the results indicates that formulations with reduced amounts of the SR-306 difunctional acrylate have the best durabiUty.
  • Example 16 A series of samples were developed based in part on the results of Example 16. These samples comprised 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).
  • the DAROCUR 1173 photoinitator and other photoinitators were aU used successfully including combinations of benzophenone and DAROCUR 1173 photoinitator, and benzophenone and IRGACURE 184 photoinitator.
  • the samples were coated onto a substrate according to Coating Procedure A and cured according to Coating Procedure A.
  • Abrasion Resistance, Scratch Hardness and Strip Time were determined for the cured coatings according to the Test Methods A, B, and C.
  • the abrasion resistance (% 20° Gloss Retention) was consistently 85%, the scratch hardness was 1300 g, and strip tune from Sealed PVC Tile (sealed with a floor sealer commercially available under the trade designation "Cornerstone” from Minnesota Mining and
  • Examples 33-60 were prepared and evaluated for abrasion resistance according to Test Method A.
  • AU samples contained 0.3 parts wetting agent
  • a coatable composition was prepared comprising 60 parts OUgomer A, 21 parts trifunctional acrylate monomer (SR-454), 12 parts caprolactone acrylate, 2.4 parts photoinitiator (DAROCUR 1173). The sample was coated at about 1 mil thickness onto PVC Tile using coating procedure A and cured for 20 seconds under Curing Procedure B. The resulting coating was tested for strip time according to Test Method C, providing a strip time of 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). The composition was coated on PVC Tile using Coating Procedure A and cured using Curing Procedure A. The resulting coatings were tested according to Test Methods A, B and C. The Abrasion resistance was about 75% gloss retention at 60°, scratch hardness was about 500g. The strip time from PVC Tile was about 3 min.
  • Example 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 preparative procedure set forth above.
  • the compositions were coated onto PVC Tile according to Coating Procedure A and cured according to Curing Procedure A to provide a cured coating about 0.25 mm thick.
  • the coatings were tested for abrasion resistance according to Test Method A.
  • the 20° gloss retention values indicated slightly better abrasion resistance for the coating of Example 65 containing the functionalized silica.
  • a premix was prepared.
  • the premix comprised 30 parts OUgomer C, 65 parts trifunctional acrylate (SR-499), 5 parts photoinitiator as indicated below, 0.3 parts wetting agent (FLUORAD FC-431).
  • the samples were coated at 2.5 g/ft 2 (26.9 g/m 2 ) onto off white PVC Tile and cured using Curing Procedure A except that curing times were 15 seconds.
  • the cured coatings were exposed to 6 x 15 W PhiUps F15T8BLB bulbs at a distance of approx. 1 inch (approx. 5 mW/cm 2 , 350-370 nm).
  • the L* indicates whiteness, positive a* coordinates measure redness, positive b* coordinates measure yellowness.
  • DE values measure total color deviation, a DE of less than 1-2 is generally imperceptible to the human eye. Based on the data set forth in Table 5, it is apparent that UV exposure causes yellowing which is reversible upon exposure to blue light.
  • EXAMPLES 72-80 An oligomer was prepared as in the Preparation of Oligomer B by combining 42 parts allophanated 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 trifunctional acrylate (SR-499), 5 parts difunctional acrylate (SR-306), 3 parts benzophenone, 2 parts DAROCUR 4265 photoinitiator and 0.3 parts wetting agent (FLUORAD FC-171) to provide a UV curable coatable composition.
  • SR-499 trifunctional acrylate
  • SR-306 5 parts difunctional acrylate
  • benzophenone 2 parts DAROCUR 4265 photoinitiator
  • wetting agent FLUORAD FC-171
  • EBECRYL 350 acrylated sUicone was added to the coatable composition as a release material.
  • the coatable compositions were tested for adhesion to both PVC Tile and to Sealed PVC TUe.
  • Sealed PVC TUe was prepared by treating with a primer or sealer applied by hand with gauze to provide a smooth even coating. The primer was then allowed to dry in air at ambient temperature and humidity. Coatable composition was then appUed to both Sealed PVC TUe and PVC

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Floor Finish (AREA)
EP96930857A 1996-09-13 1996-09-13 Veredelungszusammensetzungen für böden Withdrawn EP0929612A1 (de)

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BR0017585B1 (pt) 1999-08-25 2012-03-06 piso revestido com um acabamento curado por uv que pode ser coberto com uma composiÇço removedora heterogÊnea.
US6423381B1 (en) 1999-11-12 2002-07-23 Martin Colton Protective, transparent UV curable coating method
CA2407676A1 (en) * 2000-04-28 2001-11-08 Ecolab Inc. Strippable laminate finish
US6593283B2 (en) 2000-04-28 2003-07-15 Ecolab Inc. Antimicrobial composition
WO2001082694A1 (en) 2000-04-28 2001-11-08 Ecolab Inc. Antimicrobial composition
US6544942B1 (en) 2000-04-28 2003-04-08 Ecolab Inc. Phase-separating solvent composition
US6800353B1 (en) * 2000-09-08 2004-10-05 Ecolab Inc. Scratch-resistant strippable finish
US6558795B2 (en) * 2001-04-20 2003-05-06 Ecolab Inc. Strippable coating system
US6822063B2 (en) 2002-08-27 2004-11-23 Ecolab Inc. Highly durable waterborne radiation cured coating
US6861154B2 (en) 2002-09-26 2005-03-01 Ecolab, Inc. Coating wear indicator
US6727309B1 (en) 2002-10-08 2004-04-27 3M Innovative Properties Company Floor finish composition
US7230060B2 (en) 2002-12-19 2007-06-12 Rohm And Haas Company Removable coating compositions
KR100538056B1 (ko) * 2003-02-18 2005-12-20 김석찬 유브이 경화형 박리코팅 올리고머
US7655718B2 (en) 2004-01-12 2010-02-02 Ecolab Inc. Polyurethane coating cure enhancement using zinc carbonate initiators
US7527861B2 (en) 2004-01-12 2009-05-05 Ecolab, Inc. Jobsite-renewable multilayer floor finish with enhanced hardening rate
US8128998B2 (en) 2004-01-12 2012-03-06 Ecolab Usa Inc. Polyurethane coating cure enhancement using ultrafine zinc oxide
WO2005071029A2 (en) * 2004-01-12 2005-08-04 Ecolab Inc. Polyurethane coating system containing zinc initiator
DE102007056477A1 (de) * 2007-11-22 2009-05-28 Kalle Gmbh Druckfarbensystem zum Bedrucken von Nahrungsmittelhüllen auf Polyamidbasis, bedruckte Nahrungsmittelhüllen und Verfahren zu ihrer Herstellung
JP5498247B2 (ja) * 2010-05-12 2014-05-21 旭化成ケミカルズ株式会社 難黄変性厚膜型塗り床材
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EP3099749B1 (de) 2014-01-29 2021-02-24 3M Innovative Properties Company Wässrige oberflächenbeschichtungszusammensetzung und modifizierte partikel

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KR20000036042A (ko) 2000-06-26
KR100475224B1 (ko) 2005-03-10
AU723683B2 (en) 2000-08-31
AU6976396A (en) 1998-04-02
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MX203163B (en) 2001-07-20
WO1998011168A1 (en) 1998-03-19

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