WO2002004539A1 - Radiation curable coating composition comprising an abrasion resistance enhancement agent - Google Patents

Radiation curable coating composition comprising an abrasion resistance enhancement agent Download PDF

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Publication number
WO2002004539A1
WO2002004539A1 PCT/EP2001/007927 EP0107927W WO0204539A1 WO 2002004539 A1 WO2002004539 A1 WO 2002004539A1 EP 0107927 W EP0107927 W EP 0107927W WO 0204539 A1 WO0204539 A1 WO 0204539A1
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WO
WIPO (PCT)
Prior art keywords
radiation curable
compound
abrasion resistance
coating composition
isocyanate
Prior art date
Application number
PCT/EP2001/007927
Other languages
French (fr)
Inventor
Klaas Jan Hendrik Kruithof
Ann Kerstin Birgitta Kjellqvist Lindell
Original Assignee
Akzo Nobel N.V.
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Filing date
Publication date
Application filed by Akzo Nobel N.V. filed Critical Akzo Nobel N.V.
Priority to AU2001269130A priority Critical patent/AU2001269130A1/en
Publication of WO2002004539A1 publication Critical patent/WO2002004539A1/en

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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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation

Definitions

  • the present invention relates to a radiation curable coating composition
  • a radiation curable coating composition comprising an abrasion resistance, scratch resistance and/or indentation resistance enhancement agent.
  • a primary concern in the coating industry is the need to reduce the emission of volatile hydrocarbons into the air.
  • classic heat curing coating compositions a high-viscous film forming resin is mixed with a solvent to aid the manufacture of the coating composition and to facilitate the application of these compositions to substrates.
  • the solvent is driven off by the thermal energy used to effect the curing.
  • a considerable amount of thermal energy is thus used to drive off the solvent.
  • the thermal energy may cause considerable side effects in the coating or on the substrate, in particular when the substrate is heat sensitive.
  • the composition may comprise a crosslinker which reacts with the film forming resin.
  • a further concern in the coating industry is to enhance the abrasion, scratch, and/or indentation resistance of coated substrates, irrespective the way the coating composition was applied to the substrate.
  • an abrasion resistance enhancement compound into the composition, i.e. a compound comprising particles that enhance the abrasion resistance of the composition. It was found that particles that are not chemically bound to the coating matrix can give some enhancement of the abrasion resistance. Surprisingly, it was found that the abrasion, scratch, and/or indentation resistance of a radiation curable coating composition can be enhanced significantly by incorporation of particles that can be chemically bound to the coating matrix, i.e. particles having one or more functional groups that enable the particles to become chemically bound to the coating matrix. In particular it was found that the abrasion, scratch, and/or indentation resistance of a radiation curable coating composition comprising a radiation curable resin can be enhanced by the incorporation of an abrasion resistance enhancement compound having at least one radiation curable functional group.
  • a further improvement was found by using an abrasion resistance enhancement compound having at least two radiation curable functional groups. Without being bound to any specific theory, this further improved abrasion, scratch, and/or indentation resistance seems to relate to the improved incorporation of the particles into the coating matrix by the at least two radiation curable functional groups.
  • a coating composition that contains from 1 to 30 % by weight based on the total weight of the composition of the abrasion resistance enhancement compound. More preferably, the coating composition contains from 1 to 25 % by weight of the abrasion resistance enhancement compound. In a most preferred embodiment, the coating composition contains from 1 to 20 % by weight of the abrasion resistance enhancement compound.
  • a radiation curable coating composition is a coating composition which is cured by using electromagnetic radiation having a wavelength ⁇ ⁇ 500 nm or electron beam radiation.
  • electromagnetic radiation having a wavelength ⁇ ⁇ 500 nm is UV radiation.
  • a radiation curable resin is mixed with vinyl or acrylate capped polyfunctional compounds that are liquid at room temperature, which compounds are prepared from reacting an isocyanate- reactive vinyl or acrylate compound with an isocyanate functional compound obtained by reacting a polyahl, which is an organic substance having a molecular weight of from 60 to 20,000 and containing per molecule at least three isocyanate-reactive functional groups selected from -OH, -SH, -COOH, -NHR, where R is hydrogen, alkyl or epoxy, with a polyisocyanate comprising at least two isocyanate moieties per molecule.
  • a polyahl which is an organic substance having a molecular weight of from 60 to 20,000 and containing per molecule at least three isocyanate-reactive functional groups selected from -OH, -SH, -COOH, -NHR, where R is hydrogen, alkyl or epoxy, with a polyisocyanate comprising at least two isocyanate moieties per molecule
  • the polyahl is a polyoxyalkylene poiyol wherein the oxyalkylene entity comprises oxyethylene, oxypropylene, oxybutylene or mixtures of two or more thereof.
  • R(NCO) k wherein k is 2 or higher and R represents an organic group obtained by removing the isocyanate groups from an organic polyisocyanate having aromatically or (cyclo)aliphatically bound isocyanate groups.
  • diisocyanates are those represented by the above formula wherein k is 2 and R represents a divalent aliphatic hydrocarbon group having 2 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon group having 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group having 7 to 15 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms.
  • organic diisocyanates which are particularly suitable include ethylene diisocyanate, 1 ,3-propylene diisocyanate 1 ,4-tetramethylene diisocyanate, 1 ,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1 ,6- hexamethylene diisocyanate, 2-methyl-1 ,5-diisocyanate pentane, 2-ethyl-1 ,4- diisocyanate butane, 1 ,12-dodecamethylene diisocyanate, cyclohexane-1 ,3- and -1 ,4-diisocyanate, 1-isocyanato-2-isocyanatomethyl cyclopentane, isophorone diisocyanate, bis-(4-isocyanatocyclohexyl)-methane, 2,4'- dicyclohexylmethane diisocyanate, 1 ,3- and 1 ,4-bis(isoocyan
  • Aliphatic polyisocyanates containing 3 or more isocyanate groups such as 4-isocyanatomethyl-1 ,8-octane diisocyanate and aromatic polyisocyanate containing 3 or more isocyanate groups such as 4,4',4"- triphenylmethane triisocyanate, 1 ,3,5-triisocyanate benzene, polyphenyl polymethylene polyisocyanates obtained by phosgenating aniline/formaldehyde condensates, and mixtures thereof may also be used.
  • isocyanate groups such as 4-isocyanatomethyl-1 ,8-octane diisocyanate and aromatic polyisocyanate containing 3 or more isocyanate groups such as 4,4',4"- triphenylmethane triisocyanate, 1 ,3,5-triisocyanate benzene, polyphenyl polymethylene polyisocyanates obtained by phosgenating aniline/formaldehyde condens
  • the isocyanurate trimer of isophorone diisocyanate the reaction product of 3 moles of m-tetramethylxylene diisocyanate with 1 mole of trimethylol propane, the reaction product of 3 moles of toluene diisocyanate with 1 mole of trimethylol propane, toluene diisocyanate, the isocyanurate of hexamethylene diisocyanate, the uretdion of isophorone diisocyanate, the uretdion of hexamethylene diisocyanate, the allophanate of hexamethylene diisocyanate, and mixtures thereof can be used.
  • Isocyanate functional compounds comprising an allophanate structure are prepared by the reaction of the above-mentioned organic polyisocyanates with a mono- or polyalcohol.
  • isocyanate functional compound comprising an allophanate structure are prepared from 1 ,6-hexamethylene diisocyanate and/or isophorone diisocyanate reacted with an alcohol, preferably butanol.
  • Polyisocyanate adducts include the adduct of trimethylol propane and m- tetramethylxylylene diisocyanate and the adduct of trimethylol propane and toluene diisocyanate.
  • the polyisocyanate compound is preferably selected from isomers of toluene diisocyanate, isomers of methylene diphenylisocyanate or mixtures thereof.
  • the isocyanate-reactive vinyl or acrylate capping agent has a vinyl or an acrylate functional group and an isocyanate-reactive functional group such as -OH, -SH, -COOH, -NHR, where R is hydrogen, alkyl or epoxy.
  • examples of such capping agent are 2-hydroxyalkylacrylates or 2- hydroxyalkylmethacrylates where the alkyl substituent has from 1 to 6 carbon atoms, e.g., 2-hydroxyethylmethacrylate.
  • the vinyl or acrylate capped polyfunctional liquid compound is an acrylate capped polyurethane obtained by reacting 2-hydroxyethylmethacrylate with an isocyanate functional compound, said isocyanate-functional compound obtained by reacting a polyoxyalkylene entity comprising oxyethylene, oxypropylene, or mixtures thereof with a diisocyanate.
  • an abrasion resistance enhancement compound by reacting a functionalised abrasion resistant particle with an radiation curable compound having a group reactive with the functional group(s) present on the abrasion resistant particle.
  • an abrasion resistance enhancement compound can be prepared by reacting an hydroxyl-functional abrasion resistant particle with an isocyanate-functional acrylic or vinyl compound.
  • the abrasion resistance enhancement compound can be added to a radiation curable coating composition that as such is capable of curing and film forming without the necessity to add any further components. After addition of the abrasion resistance enhancement compound the whole composition has to be mixed thoroughly to get good film properties.
  • any radiation curable resin or mixtures of resins can be used in the coating composition according to the present invention.
  • These resins are present in an amount of 20 to 99 wt.% of the composition.
  • the resin is present in an amount of 30 to 90 wt.%, more preferred is an amount of 40 to 80 wt.%.
  • Polyesteracrylate resins were found to be very suitable for use in the coating composition according to the present invention.
  • suitable commercially available polyesteracrylate resins are: Crodamer UVP-215, Crodamer UVP-220 (both ex Croda), Genomer 3302, Genomer 3316 (both ex Rahn), Laromer PE 44F (ex BASF), Ebecryl 800, Ebecryl 810 (both ex UCB), Viaktin 5979, Viaktin VTE 5969, and Viaktin 6164 (100%) (all ex
  • Epoxyacrylate resins can also be used in the coating composition according to the present invention.
  • examples of commercially available epoxyacrylate resins are: Crodamer UVE-107 (100%), Crodamer UVE-130 (both ex Croda) Genomer 2254, Genomer 2258, Genomer 2260, Genomer 2263 (all ex Rahn), CN 104 (ex Cray Valley), and Ebecryl 3500 (ex UCB).
  • Polyetheracrylate resins can also be used in the coating composition according to the present invention.
  • Examples of commercially available polyetheracrylate resins are: Genomer 3456 (ex Rahn), Laromer P033F (ex BASF), Viaktin 5968, Viaktin 5978, and Viaktin VTE 6 ⁇ 54 (all ex Vianova).
  • Urethaneacrylate resins can also be used in the coating composition according to the present invention.
  • Examples of commercially available urethaneacrylate resins are: CN 934, CN 976, CN 981 (all ex Cray Valley), Ebecryl 210, Ebecryl 2000, Ebecryl 8800 (all ex UCB), Genomer 4258, Genomer 4652, and Genomer 4675 (all ex Rahn).
  • cycloaliphatic epoxide resins such as cycloaliphatic epoxide resins, (Uvacure 1500, Uvacure 1501 , Uvacure 1502, Uvacure 1530, Uvacure 1531 , Uvacure 1532, Uvacure 1533, Uvacure 1534, Cyracure UVR-6100, Cyracure UVR-6105, Cyracure UVR- 6110, and Cy
  • curable coating composition comprising one or more resins selected from the group consisting of UV curable polyester resins, UV curable polyetheracrylate resins, UV curable epoxyacrylate resins, and UV curable urethaneacrylate resins.
  • UV curable monomers can be added as viscosity reducing agents and reactive oligomers.
  • reactive oligomers are tripropylene glycol diacrylate (TPGDA), hexanediol diacrylate (HDDA), and 2-hydroxyethyl methacrylate (HEMA).
  • the composition can comprise a photoinitiator or a mixture of photo- initiators.
  • suitable photoinitiators that can be used in the radiation curable composition according to the present invention are benzoin, benzoin ethers, benzilketals, , ⁇ -dialkoxyacetophenones, ⁇ - hydroxyalkylphenones, ⁇ -aminoalkylphenones, acylphosphine oxides, benzophenone, thioxanthones, 1 ,2-diketones, and mixtures thereof. It is also possible to use copolymerisable bimolecular photoinitiators or maleimide functional compounds.
  • Co-initiators such as amine based co-initiators can also be present in the radiation curable coating composition.
  • suitable commercially available photoinitiators are: Esacure KIP 100F and Esacure KIP 150 (both ex Lamberti), Genocure BDK and Velsicure BTF (both ex Rahn), Speedcure EDB, Speedcure ITX, Speedcure BKL, and Speedcure DETX (all ex Lambson), Cyracure UVI-6990, Cyracure UVI-6974, Cyracure UVI-6976, Cyracure UVI-6992 (all ex Union Carbide), and CGI-901 , Darocur 184, Darocur 500, Darocur 1000, and Darocur 1173 (all ex Ciba Chemicals).
  • the presence of a photoinitiator is not necessary.
  • a photoinitiator when electron beam radiation is used to cure the composition, it is not necessary to add a photoinitiator.
  • UV radiation when used, in general a photoinitiator is added to get a coating with good film properties.
  • the total amount of photoinitiator in the composition is not critical, it should be sufficient to achieve acceptable curing of the coating when it is irradiated. However, the amount should not be so large that it affects the properties of the cured composition in a negative way.
  • the composition should comprise between 0 and 10 wt.% of photoinitiator, calculated on the total weight of the composition.
  • the composition can also contain one or more fillers or additives.
  • Fillers can be any fillers known to those skilled in the art, e.g., barium sulphate, calcium sulphate, calcium carbonate, silicas or silicates (such as talc, feldspar, and china clay).
  • Additives such as stabilisers, antioxidants, levelling agents, anti- settling agents, matting agents, rheol ⁇ gy modifiers, surface-active agents, amine synergists, waxes, or adhesion promoters can also be added.
  • the coating composition according to the present invention comprises 0 to 50 wt.% of fillers and/or additives, calculated on the total weight of the coating composition.
  • the composition according to the present invention can also contain one or more pigments. Pigments known to those skilled in the art can be used in the radiation curable composition according to the present invention. However, care should be taken that the pigment does not show a too high absorption of the radiation used to cure the composition.
  • the composition according to the present invention comprises 0 to 40 wt.% of pigment, calculated on the total weight of the coating composition.
  • the coating compositions according to the present invention are particularly suited to be used as a radiation curable coating for wooden, wood-like and/or cellulose containing substrate, for example solid wood, veneer of wood, impregnated paper or reconstituted wood substrates, but they can also be used for the coating of metal or plastic substrates.
  • Reconstituted wood substrates are substrates produced from wood particles, fibers, flakes or chips, such as, a hardboard, a medium density fiberboard, an oriented strand board also known as wafer board, a flake board, a chipboard and a particleboard.
  • a reconstituted wood substrate is typically fabricated under heat and pressure from particles, fibers, flakes or chips.
  • a reconstituted wood substrate is normally produced by treating particles, flakes, chips or fibers with a binder and then arranging these treated particles, flakes, chips or fibers in the form of a mat under dry or wet conditions. The mat is then compressed into a dense substrate, typically in a sheet form, by the application of heat and pressure.
  • the binder binds particles, flakes, chips or fibers and enhances the structural strength and integrity of the reconstituted wood substrate and its water resistance.
  • the reconstituted wood substrate if desired, may be molded into desired shape or provided with a textured surface, such as, wood grain texture.
  • Typical examples of reconstituted wood substrates are hardboard, Medium Density Fiberboard (MDF), High Density Fiberboard (HDF), and chipboard.
  • the coating compositions according to the present invention are particularly suited for parquet flooring, both as a base coat, mid coat or top coat.
  • the coating compositions according to the present invention are particularly suited to be used as an enhancer of the abrasion resistance, scratch resistance, and/or indentation resistance of wooden, wood-like and/or cellulose containing substrate.
  • the present invention further relates to a process for the preparation of wooden, wood-like and/or cellulose containing substrate with enhanced abrasion resistance, scratch resistance, and/or indentation resistance.
  • the substrate is coated with a radiation curable base coat, a radiation curable mid coat and/or a radiation curable top coat whereby at least one of the applied coating layers comprises an abrasion resistance enhancement compound having at least one radiation curable functional groups, i.e. a coating composition as described above.
  • the coating composition comprises a vinyl or acrylate capped polyfunctional liquid compound.
  • the present invention further also relates to a coated wooden, wood-like and/or cellulose containing substrate with enhanced abrasion resistance, scratch resistance, or indentation resistance.
  • This substrate is coated with a radiation curable base coat, a radiation curable mid coat and/or a radiation curable top coat whereby at least one of the applied coating layers comprises a abrasion resistance enhancement compound having at least one radiation curable functional groups, i.e. a coating composition as described above.
  • Preference is given to a coated wooden, wood-like and/or cellulose containing substrate wherein the substrate is coated with a radiation curable base coat, a radiation curable mid coat and/or a radiation curable top coat whereby at least one of the applied coating layers comprises a vinyl or acrylate capped polyfunctional liquid compound.
  • a UV curable base coat used for parquet flooring was prepared comprising (parts by weight denotes parts by weight):
  • This base coat was thoroughly mixed with different types of abrasion resistance enhancement compounds and applied to wooden flooring substrates.
  • the coated substrates were placed on a belt and passed under a 80W/cm 2 Hg lamp. The speed of the belt was adjusted to get a fully cured lacquer after one passage under the lamp.
  • the abrasion resistance of the coated substrates was measured using the falling sand method according to
  • PLC-1 A 6-functional acrylate capped urethane compound obtained by reacting a polyoxyalkylene poiyol wherein the oxyalkylene entity comprises only oxypropylene with a diisocyanate and 2- hydroxyethylmethacrylate.
  • PLC-2 A 3-functional acrylate capped urethane compound obtained by reacting a polyoxyalkylene poiyol wherein the oxyalkylene entity comprises only oxypropylene with a diisocyanate and 2- hydroxyethylmethacrylate.
  • PLC-3 A 6-functional acrylate capped urethane compound obtained by reacting a polyoxyalkylene poiyol wherein the oxyalkylene entity comprises 60 mol.% of oxyethylene and 40 mol.% of oxypropylene with a diisocyanate and 2-hydroxyethylmethacrylate.
  • PLC-4 A 3-functional acrylate capped urethane compound obtained by reacting a polyoxyalkylene poiyol wherein the oxyalkylene entity comprises 40 mol.% of oxyethylene and 60 mol.% of oxypropylene with a diisocyanate and 2-hydroxyethylmethacrylate.
  • a UV curable mid coat used for parquet flooring comprising: 63,9 parts by weight of a mixture of polyesteracrylate resins; 30,0 parts by weight of a urethaneacrylate resin; 3,1 parts by weight of a mixture of photoinitiators; and 3,0 parts by weight of a mixture of additives.
  • This mid coat was thoroughly mixed with one of the above-mentioned abrasion resistance enhancement compounds and applied to wooden flooring substrates.
  • the coated substrates were placed on a belt and passed under a 80W/cm 2 Hg lamp. The speed of the belt was adjusted to get a fully cured lacquer after one passage under the lamp.
  • the abrasion resistance of the coated substrates was measured using the falling sand method according to Swedish Industrial Standard SIS 923509/Provisional European Norm PREN 175.333.08 using CS-39. The results of the tests are presented in Table 2
  • Example 3 A UV curable top coat used for parquet flooring was prepared comprising:
  • Example 4 Using the base coat of Examplel , the mid coat of Example 2 and the top coat of example 3, parquet coating systems were tested for the wear through resistance of the coating layer. To one or more of the coating components, one of the above-mentioned abrasion resistance enhancement compounds was added. First, the base coat was applied to a substrate by a roller coater. After curing of the coating using a 80W/cm 2 Hg lamp a mid coat layer was applied. This layer was also cured using a 80W/cm 2 Hg lamp and a top coat was applied on top of the mid coat. This top-coat layer was also cured using a 80W/cm 2 Hg lamp. The abrasion resistance to 50% wear through was measured in accordance with Swedish Industrial Standard SIS 923509/Provisional European Norm PR EN 175.333.08 using CS-39. The results of the tests are presented in Table 4
  • a solvent free UV curable base coat used for parquet flooring was prepared comprising: 86,5 parts by weight of a polyesteracrylate resin;
  • This base coat was thoroughly mixed with 9,6 parts by weight of an abrasion resistance enhancement compound similar to the PLC-4 mentioned above.
  • the mixture was heated to 60°C and applied to a flooring panel at 60 g/m 2 using a heated roller coater.
  • the coated substrate was placed on a belt and passed under a 80W/cm 2 Hg lamp. The speed of the belt was adjusted to get a fully cured lacquer after one passage under the lamp.
  • the top coat of Example 3 was applied on top of the cured based coat at 12 g/m 2 .
  • the top coat was also cured by passing the substrate under a 80W/cm 2 Hg lamp.
  • the abrasion resistance to 50% wear through was measured in accordance with Swedish Industrial Standard SIS 923509/Provisional European Norm PREN 175.333.08 using CS-39. For this coated flooring panel an abrasion resistance of 9500 cycles to 50% wear through was found.
  • a UV curable coating composition that can used as furniture lacquer was prepared comprising: epoxy diacrylate resin; and 3 parts by weight of a mixture of photoinitiators.
  • This composition was thoroughly mixed with increasing amounts of an abrasion resistance enhancement compound similar to the PLC-4 mentioned above.
  • the amount of PLC and the amount of epoxy diacrylate resin together made out 97 parts by weight of the mixtures.
  • These coating compositions were applied to wooden furniture panels. The coated substrates were placed on a belt and passed under a 80W/cm Hg lamp.
  • the pendulum hardness was measured in accordance with Swedish
  • a UV curable coating composition that can be used as a UV-sealer coat was prepared comprising: - 62,1 parts by weight of a polyester acrylate;

Abstract

The invention relates to a radiation curable coating composition comprising a radiation curable resin and an abrasion resistance enhancement compound having at least one radiation curable functional groups. The invention further relates to a process for coating a wooden, wood-like and/or cellulose containing substrate and to a wooden, wood-like and/or cellulose containing substrate with enhanced resistance, scratch resistance, and/or indentation resistance.

Description

RADIATION CURABLE COATING COMPOSITION COMPRISING AN ABRASION RESISTANCE ENHANCEMENT AGENT
The present invention relates to a radiation curable coating composition comprising an abrasion resistance, scratch resistance and/or indentation resistance enhancement agent.
A primary concern in the coating industry is the need to reduce the emission of volatile hydrocarbons into the air. In classic heat curing coating compositions a high-viscous film forming resin is mixed with a solvent to aid the manufacture of the coating composition and to facilitate the application of these compositions to substrates. During curing of the coating the solvent is driven off by the thermal energy used to effect the curing. A considerable amount of thermal energy is thus used to drive off the solvent. However, the thermal energy may cause considerable side effects in the coating or on the substrate, in particular when the substrate is heat sensitive.
To solve this problem, it was suggested to use a radiation sensitive reactive solvent to reduce the viscosity of the film forming resin. Upon radiation, these reactive solvents react with each other or with the film forming resin and a coating of good quality can be obtained. Optionally, the composition may comprise a crosslinker which reacts with the film forming resin.
A further concern in the coating industry is to enhance the abrasion, scratch, and/or indentation resistance of coated substrates, irrespective the way the coating composition was applied to the substrate.
For both solvent borne and radiation curable coating compositions it was contemplated to incorporate an abrasion resistance enhancement compound into the composition, i.e. a compound comprising particles that enhance the abrasion resistance of the composition. It was found that particles that are not chemically bound to the coating matrix can give some enhancement of the abrasion resistance. Surprisingly, it was found that the abrasion, scratch, and/or indentation resistance of a radiation curable coating composition can be enhanced significantly by incorporation of particles that can be chemically bound to the coating matrix, i.e. particles having one or more functional groups that enable the particles to become chemically bound to the coating matrix. In particular it was found that the abrasion, scratch, and/or indentation resistance of a radiation curable coating composition comprising a radiation curable resin can be enhanced by the incorporation of an abrasion resistance enhancement compound having at least one radiation curable functional group.
A further improvement was found by using an abrasion resistance enhancement compound having at least two radiation curable functional groups. Without being bound to any specific theory, this further improved abrasion, scratch, and/or indentation resistance seems to relate to the improved incorporation of the particles into the coating matrix by the at least two radiation curable functional groups.
It was found that above a certain level of the abrasion resistance enhancement compound in the coating composition a decrease is observed in the film properties of the cured coating film such as hardness, adhesion and chemical resistance. Additionally an increase of yellowing and scratch sensitivity is observed. Therefore, to obtain a cured film with good film properties and a good abrasion, scratch, and/or indentation resistance preference is given to a coating composition that contains from 1 to 30 % by weight based on the total weight of the composition of the abrasion resistance enhancement compound. More preferably, the coating composition contains from 1 to 25 % by weight of the abrasion resistance enhancement compound. In a most preferred embodiment, the coating composition contains from 1 to 20 % by weight of the abrasion resistance enhancement compound. Within the framework of the present invention, a radiation curable coating composition is a coating composition which is cured by using electromagnetic radiation having a wavelength λ < 500 nm or electron beam radiation. An example of electromagnetic radiation having a wavelength λ < 500 nm is UV radiation.
In a preferred embodiment of the radiation curable coating composition according to the present invention a radiation curable resin is mixed with vinyl or acrylate capped polyfunctional compounds that are liquid at room temperature, which compounds are prepared from reacting an isocyanate- reactive vinyl or acrylate compound with an isocyanate functional compound obtained by reacting a polyahl, which is an organic substance having a molecular weight of from 60 to 20,000 and containing per molecule at least three isocyanate-reactive functional groups selected from -OH, -SH, -COOH, -NHR, where R is hydrogen, alkyl or epoxy, with a polyisocyanate comprising at least two isocyanate moieties per molecule.
Good results are obtained when the polyahl is a polyoxyalkylene poiyol wherein the oxyalkylene entity comprises oxyethylene, oxypropylene, oxybutylene or mixtures of two or more thereof. By reacting a polyoxyalkylene poiyol with a polyisocyanate a compound comprising urethane linkages is obtained.
Examples of polyisocyanates that can be used in the preparation of the vinyl or acrylate capped polyfunctional compounds include organic polyisocyanates represented by the formula
R(NCO)k wherein k is 2 or higher and R represents an organic group obtained by removing the isocyanate groups from an organic polyisocyanate having aromatically or (cyclo)aliphatically bound isocyanate groups. Examples of diisocyanates are those represented by the above formula wherein k is 2 and R represents a divalent aliphatic hydrocarbon group having 2 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon group having 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group having 7 to 15 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms. Examples of the organic diisocyanates which are particularly suitable include ethylene diisocyanate, 1 ,3-propylene diisocyanate 1 ,4-tetramethylene diisocyanate, 1 ,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1 ,6- hexamethylene diisocyanate, 2-methyl-1 ,5-diisocyanate pentane, 2-ethyl-1 ,4- diisocyanate butane, 1 ,12-dodecamethylene diisocyanate, cyclohexane-1 ,3- and -1 ,4-diisocyanate, 1-isocyanato-2-isocyanatomethyl cyclopentane, isophorone diisocyanate, bis-(4-isocyanatocyclohexyl)-methane, 2,4'- dicyclohexylmethane diisocyanate, 1 ,3- and 1 ,4-bis(isocyanatomethyl)- cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, 1 -methyl-2,4- diisocyanato cyclohexane, 1 -isocyanato-1 -methyI-4(3)-isocyanatomethyl cyclohexane, xylene diisocyanate, 1-methyl-2,4-diisocyanato benzene, α,α,α' ,α' -tetramethyl-1 ,3- and -1 ,4-xylylene diisocyanate, 2,4- and 2,6- hexahydrotoluylene diisocyanate, 1 ,3- and 1 ,4-phenylene diisocyanate, 2,4- and 2,6-toluylene diisocyanate, 2,4- and 4,4'-diphenylmethane diisocyanate, 1 ,5-diisocyanato naphthalene, norbornane diisocyanate, and mixtures thereof. Aliphatic polyisocyanates containing 3 or more isocyanate groups such as 4-isocyanatomethyl-1 ,8-octane diisocyanate and aromatic polyisocyanate containing 3 or more isocyanate groups such as 4,4',4"- triphenylmethane triisocyanate, 1 ,3,5-triisocyanate benzene, polyphenyl polymethylene polyisocyanates obtained by phosgenating aniline/formaldehyde condensates, and mixtures thereof may also be used. Also the isocyanurate trimer of isophorone diisocyanate, the reaction product of 3 moles of m-tetramethylxylene diisocyanate with 1 mole of trimethylol propane, the reaction product of 3 moles of toluene diisocyanate with 1 mole of trimethylol propane, toluene diisocyanate, the isocyanurate of hexamethylene diisocyanate, the uretdion of isophorone diisocyanate, the uretdion of hexamethylene diisocyanate, the allophanate of hexamethylene diisocyanate, and mixtures thereof can be used. Isocyanate functional compounds comprising an allophanate structure are prepared by the reaction of the above-mentioned organic polyisocyanates with a mono- or polyalcohol. Preferably, isocyanate functional compound comprising an allophanate structure are prepared from 1 ,6-hexamethylene diisocyanate and/or isophorone diisocyanate reacted with an alcohol, preferably butanol.
Polyisocyanate adducts include the adduct of trimethylol propane and m- tetramethylxylylene diisocyanate and the adduct of trimethylol propane and toluene diisocyanate. The polyisocyanate compound is preferably selected from isomers of toluene diisocyanate, isomers of methylene diphenylisocyanate or mixtures thereof.
The isocyanate-reactive vinyl or acrylate capping agent has a vinyl or an acrylate functional group and an isocyanate-reactive functional group such as -OH, -SH, -COOH, -NHR, where R is hydrogen, alkyl or epoxy. Examples of such capping agent are 2-hydroxyalkylacrylates or 2- hydroxyalkylmethacrylates where the alkyl substituent has from 1 to 6 carbon atoms, e.g., 2-hydroxyethylmethacrylate. Best results were found for a radiation curable coating compositions wherein the vinyl or acrylate capped polyfunctional liquid compound is an acrylate capped polyurethane obtained by reacting 2-hydroxyethylmethacrylate with an isocyanate functional compound, said isocyanate-functional compound obtained by reacting a polyoxyalkylene entity comprising oxyethylene, oxypropylene, or mixtures thereof with a diisocyanate.
More and detailed information on the preparation of polyurethanes that can be used as a starting material for the radiation curable polyfunctional liquid compound having urethane linkages that can be used in the coating composition according to the present invention can be found in WO 91/14726, WO 96/34904, WO 98/06770, WO98/20060, WO 98/37113, and WO 99/16800. Commercially available products that can be used as radiation curable polyfunctional liquid compound having urethane linkages are UV curable Vorastartm compounds (ex. Dow Chemical Company).
It was found that the use of a vinyl or acrylate capped polyfunctional liquid compound that is substantially free of isocyanate functional groups gives the optimum in abrasion, scratch, and/or indentation resistance properties.
Further, it is also possible to prepare an abrasion resistance enhancement compound by reacting a functionalised abrasion resistant particle with an radiation curable compound having a group reactive with the functional group(s) present on the abrasion resistant particle. For example, an abrasion resistance enhancement compound can be prepared by reacting an hydroxyl-functional abrasion resistant particle with an isocyanate-functional acrylic or vinyl compound.
As indicated above, the abrasion resistance enhancement compound can be added to a radiation curable coating composition that as such is capable of curing and film forming without the necessity to add any further components. After addition of the abrasion resistance enhancement compound the whole composition has to be mixed thoroughly to get good film properties.
In principle any radiation curable resin or mixtures of resins can be used in the coating composition according to the present invention. These resins are present in an amount of 20 to 99 wt.% of the composition. Preferably, the resin is present in an amount of 30 to 90 wt.%, more preferred is an amount of 40 to 80 wt.%.
Polyesteracrylate resins were found to be very suitable for use in the coating composition according to the present invention. Examples of suitable commercially available polyesteracrylate resins are: Crodamer UVP-215, Crodamer UVP-220 (both ex Croda), Genomer 3302, Genomer 3316 (both ex Rahn), Laromer PE 44F (ex BASF), Ebecryl 800, Ebecryl 810 (both ex UCB), Viaktin 5979, Viaktin VTE 5969, and Viaktin 6164 (100%) (all ex
Vianova).
Epoxyacrylate resins can also be used in the coating composition according to the present invention. Examples of commercially available epoxyacrylate resins are: Crodamer UVE-107 (100%), Crodamer UVE-130 (both ex Croda) Genomer 2254, Genomer 2258, Genomer 2260, Genomer 2263 (all ex Rahn), CN 104 (ex Cray Valley), and Ebecryl 3500 (ex UCB). Polyetheracrylate resins can also be used in the coating composition according to the present invention. Examples of commercially available polyetheracrylate resins are: Genomer 3456 (ex Rahn), Laromer P033F (ex BASF), Viaktin 5968, Viaktin 5978, and Viaktin VTE 6Ϊ54 (all ex Vianova). Urethaneacrylate resins can also be used in the coating composition according to the present invention. Examples of commercially available urethaneacrylate resins are: CN 934, CN 976, CN 981 (all ex Cray Valley), Ebecryl 210, Ebecryl 2000, Ebecryl 8800 (all ex UCB), Genomer 4258, Genomer 4652, and Genomer 4675 (all ex Rahn).
Another example of radiation curable resins that can be used in the coating composition according to the present invention are cationic UV curable resins, such as cycloaliphatic epoxide resins, (Uvacure 1500, Uvacure 1501 , Uvacure 1502, Uvacure 1530, Uvacure 1531 , Uvacure 1532, Uvacure 1533, Uvacure 1534, Cyracure UVR-6100, Cyracure UVR-6105, Cyracure UVR- 6110, and Cyracure UVR-6128, (all ex. UCB Chemicals), or SarCat K126 (ex. Sartomer), acrylate modified cycloaliphatic epoxides, caprolactone- based resins (SR 495 (=caprolactone acrylate ex. Sartomer), Tone 0201 (=caprolactone triol), Tone 0301 , Tone 0305, Tone 0310, (all caprolactone triol ex. Union Carbide), aliphatic urethane divinyl ether, aromatic vinyl ether oligomer, bis-maleimide, diglycidyl ether of bisphenol A or neopentyl glycol, hydroxy-functional acrylic monomer, hydroxy-functional epoxide resin, epoxidised linseed-oil, epoxidised polybutadiene, glycidyl ester or partially acrylated bisphenol A epoxy resin. Other radiation curable compounds that are suitable to be used in the coating composition according to the present invention are, e.g., vinyl ether- containing compounds, unsaturated polyester resins, acrylated polyetherpolyol compounds, (meth)acrylated epoxidised oils, (meth)acrylated hyperbranched polyesters, silicon acrylates, maleimide functional compounds, unsaturated imide resins, compounds suitable for photo- induced cationic curing, or mixtures thereof.
In view of the overall properties of the cured coating film, preference is given to a curable coating composition comprising one or more resins selected from the group consisting of UV curable polyester resins, UV curable polyetheracrylate resins, UV curable epoxyacrylate resins, and UV curable urethaneacrylate resins.
To obtain a suitable application viscosity of the coatings, well-known UV curable monomers can be added as viscosity reducing agents and reactive oligomers. Examples of these reactive oligomers are tripropylene glycol diacrylate (TPGDA), hexanediol diacrylate (HDDA), and 2-hydroxyethyl methacrylate (HEMA).
Further, the composition can comprise a photoinitiator or a mixture of photo- initiators. Examples of suitable photoinitiators that can be used in the radiation curable composition according to the present invention are benzoin, benzoin ethers, benzilketals, ,α-dialkoxyacetophenones, α- hydroxyalkylphenones, α-aminoalkylphenones, acylphosphine oxides, benzophenone, thioxanthones, 1 ,2-diketones, and mixtures thereof. It is also possible to use copolymerisable bimolecular photoinitiators or maleimide functional compounds. Co-initiators such as amine based co-initiators can also be present in the radiation curable coating composition. Examples of suitable commercially available photoinitiators are: Esacure KIP 100F and Esacure KIP 150 (both ex Lamberti), Genocure BDK and Velsicure BTF (both ex Rahn), Speedcure EDB, Speedcure ITX, Speedcure BKL, and Speedcure DETX (all ex Lambson), Cyracure UVI-6990, Cyracure UVI-6974, Cyracure UVI-6976, Cyracure UVI-6992 (all ex Union Carbide), and CGI-901 , Darocur 184, Darocur 500, Darocur 1000, and Darocur 1173 (all ex Ciba Chemicals).
However, the presence of a photoinitiator is not necessary. In general, when electron beam radiation is used to cure the composition, it is not necessary to add a photoinitiator. When UV radiation is used, in general a photoinitiator is added to get a coating with good film properties. Although the total amount of photoinitiator in the composition is not critical, it should be sufficient to achieve acceptable curing of the coating when it is irradiated. However, the amount should not be so large that it affects the properties of the cured composition in a negative way. In general, the composition should comprise between 0 and 10 wt.% of photoinitiator, calculated on the total weight of the composition.
The composition can also contain one or more fillers or additives. Fillers can be any fillers known to those skilled in the art, e.g., barium sulphate, calcium sulphate, calcium carbonate, silicas or silicates (such as talc, feldspar, and china clay). Additives such as stabilisers, antioxidants, levelling agents, anti- settling agents, matting agents, rheolόgy modifiers, surface-active agents, amine synergists, waxes, or adhesion promoters can also be added. In general, the coating composition according to the present invention comprises 0 to 50 wt.% of fillers and/or additives, calculated on the total weight of the coating composition.
The composition according to the present invention can also contain one or more pigments. Pigments known to those skilled in the art can be used in the radiation curable composition according to the present invention. However, care should be taken that the pigment does not show a too high absorption of the radiation used to cure the composition. In general, the composition according to the present invention comprises 0 to 40 wt.% of pigment, calculated on the total weight of the coating composition. The coating compositions according to the present invention are particularly suited to be used as a radiation curable coating for wooden, wood-like and/or cellulose containing substrate, for example solid wood, veneer of wood, impregnated paper or reconstituted wood substrates, but they can also be used for the coating of metal or plastic substrates.
Reconstituted wood substrates are substrates produced from wood particles, fibers, flakes or chips, such as, a hardboard, a medium density fiberboard, an oriented strand board also known as wafer board, a flake board, a chipboard and a particleboard. Such a reconstituted wood substrate is typically fabricated under heat and pressure from particles, fibers, flakes or chips. A reconstituted wood substrate is normally produced by treating particles, flakes, chips or fibers with a binder and then arranging these treated particles, flakes, chips or fibers in the form of a mat under dry or wet conditions. The mat is then compressed into a dense substrate, typically in a sheet form, by the application of heat and pressure. The binder binds particles, flakes, chips or fibers and enhances the structural strength and integrity of the reconstituted wood substrate and its water resistance. The reconstituted wood substrate, if desired, may be molded into desired shape or provided with a textured surface, such as, wood grain texture. Typical examples of reconstituted wood substrates are hardboard, Medium Density Fiberboard (MDF), High Density Fiberboard (HDF), and chipboard. The coating compositions according to the present invention are particularly suited for parquet flooring, both as a base coat, mid coat or top coat.
The coating compositions according to the present invention are particularly suited to be used as an enhancer of the abrasion resistance, scratch resistance, and/or indentation resistance of wooden, wood-like and/or cellulose containing substrate. The present invention further relates to a process for the preparation of wooden, wood-like and/or cellulose containing substrate with enhanced abrasion resistance, scratch resistance, and/or indentation resistance. In this process the substrate is coated with a radiation curable base coat, a radiation curable mid coat and/or a radiation curable top coat whereby at least one of the applied coating layers comprises an abrasion resistance enhancement compound having at least one radiation curable functional groups, i.e. a coating composition as described above. Preference is given to a process wherein the coating composition comprises a vinyl or acrylate capped polyfunctional liquid compound.
The present invention further also relates to a coated wooden, wood-like and/or cellulose containing substrate with enhanced abrasion resistance, scratch resistance, or indentation resistance. This substrate is coated with a radiation curable base coat, a radiation curable mid coat and/or a radiation curable top coat whereby at least one of the applied coating layers comprises a abrasion resistance enhancement compound having at least one radiation curable functional groups, i.e. a coating composition as described above. Preference is given to a coated wooden, wood-like and/or cellulose containing substrate wherein the substrate is coated with a radiation curable base coat, a radiation curable mid coat and/or a radiation curable top coat whereby at least one of the applied coating layers comprises a vinyl or acrylate capped polyfunctional liquid compound.
The invention will be elucidated with reference to the following examples. These are intended to illustrate the invention but are not to be construed as limiting in any manner the scope thereof. Examples
Example 1
A UV curable base coat used for parquet flooring was prepared comprising (parts by weight denotes parts by weight):
16,8 parts by weight of a polyesteracrylic resin;
26,5 parts by weight of a mixture of unsaturated polyester resins;
25,8 parts by weight of fillers;
4,1 parts by weight of a mixture of photoinitiators; 17,1 parts by weight of a reactive diluent; and
9,7 parts by weight of a mixture of additives.
This base coat was thoroughly mixed with different types of abrasion resistance enhancement compounds and applied to wooden flooring substrates. The coated substrates were placed on a belt and passed under a 80W/cm2 Hg lamp. The speed of the belt was adjusted to get a fully cured lacquer after one passage under the lamp. The abrasion resistance of the coated substrates was measured using the falling sand method according to
Swedish Industrial Standard SIS 923509/Provisional European Norm PREN
175.333.08 using CS-39.
The following abrasion resistance enhancement compounds were prepared: PLC-1 : A 6-functional acrylate capped urethane compound obtained by reacting a polyoxyalkylene poiyol wherein the oxyalkylene entity comprises only oxypropylene with a diisocyanate and 2- hydroxyethylmethacrylate.
PLC-2 A 3-functional acrylate capped urethane compound obtained by reacting a polyoxyalkylene poiyol wherein the oxyalkylene entity comprises only oxypropylene with a diisocyanate and 2- hydroxyethylmethacrylate. PLC-3 A 6-functional acrylate capped urethane compound obtained by reacting a polyoxyalkylene poiyol wherein the oxyalkylene entity comprises 60 mol.% of oxyethylene and 40 mol.% of oxypropylene with a diisocyanate and 2-hydroxyethylmethacrylate. PLC-4 A 3-functional acrylate capped urethane compound obtained by reacting a polyoxyalkylene poiyol wherein the oxyalkylene entity comprises 40 mol.% of oxyethylene and 60 mol.% of oxypropylene with a diisocyanate and 2-hydroxyethylmethacrylate.
The results of the tests are presented in Table 1.
Table 1
Figure imgf000014_0001
Example 2
A UV curable mid coat used for parquet flooring was prepared comprising: 63,9 parts by weight of a mixture of polyesteracrylate resins; 30,0 parts by weight of a urethaneacrylate resin; 3,1 parts by weight of a mixture of photoinitiators; and 3,0 parts by weight of a mixture of additives. This mid coat was thoroughly mixed with one of the above-mentioned abrasion resistance enhancement compounds and applied to wooden flooring substrates. The coated substrates were placed on a belt and passed under a 80W/cm2 Hg lamp. The speed of the belt was adjusted to get a fully cured lacquer after one passage under the lamp. The abrasion resistance of the coated substrates was measured using the falling sand method according to Swedish Industrial Standard SIS 923509/Provisional European Norm PREN 175.333.08 using CS-39. The results of the tests are presented in Table 2
Table 2
Figure imgf000015_0001
Example 3 A UV curable top coat used for parquet flooring was prepared comprising:
3,4 parts by weight of a polyesteracrylate resin;
35,0 parts by weight of an urethaneacrylate resin;
47,0 parts by weight of a reactive diluent;
6,0 parts by weight of a mixture of photoinitiators; and 8,6 parts by weight of a mixture of additives and fillers. This top coat was thoroughly mixed with one of the above-mentioned abrasion resistance enhancement compounds and applied to wooden flooring substrates. The coated substrates were placed on a belt and passed under a 80W/cm2 Hg lamp. The speed of the belt was adjusted to get a fully cured lacquer after one passage under the lamp. The abrasion resistance of the coated substrates was measured using the falling sand method according to Swedish Industrial Standard SIS 923509/Provisional European Norm PREN 175.333.08 using CS-39. The results of the tests are presented in Table 3
Table 3
Figure imgf000016_0001
Example 4 Using the base coat of Examplel , the mid coat of Example 2 and the top coat of example 3, parquet coating systems were tested for the wear through resistance of the coating layer. To one or more of the coating components, one of the above-mentioned abrasion resistance enhancement compounds was added. First, the base coat was applied to a substrate by a roller coater. After curing of the coating using a 80W/cm2 Hg lamp a mid coat layer was applied. This layer was also cured using a 80W/cm2 Hg lamp and a top coat was applied on top of the mid coat. This top-coat layer was also cured using a 80W/cm2 Hg lamp. The abrasion resistance to 50% wear through was measured in accordance with Swedish Industrial Standard SIS 923509/Provisional European Norm PREN 175.333.08 using CS-39. The results of the tests are presented in Table 4
Table 4
Figure imgf000017_0001
Example 5
A solvent free UV curable base coat used for parquet flooring was prepared comprising: 86,5 parts by weight of a polyesteracrylate resin; and
3,8 parts by weight of a mixture of photoinitiators.
This base coat was thoroughly mixed with 9,6 parts by weight of an abrasion resistance enhancement compound similar to the PLC-4 mentioned above. The mixture was heated to 60°C and applied to a flooring panel at 60 g/m2 using a heated roller coater. The coated substrate was placed on a belt and passed under a 80W/cm2 Hg lamp. The speed of the belt was adjusted to get a fully cured lacquer after one passage under the lamp. The top coat of Example 3 was applied on top of the cured based coat at 12 g/m2. The top coat was also cured by passing the substrate under a 80W/cm2 Hg lamp. The abrasion resistance to 50% wear through was measured in accordance with Swedish Industrial Standard SIS 923509/Provisional European Norm PREN 175.333.08 using CS-39. For this coated flooring panel an abrasion resistance of 9500 cycles to 50% wear through was found.
Example 6
A UV curable coating composition that can used as furniture lacquer was prepared comprising: epoxy diacrylate resin; and 3 parts by weight of a mixture of photoinitiators.
This composition was thoroughly mixed with increasing amounts of an abrasion resistance enhancement compound similar to the PLC-4 mentioned above. The amount of PLC and the amount of epoxy diacrylate resin together made out 97 parts by weight of the mixtures. These coating compositions were applied to wooden furniture panels. The coated substrates were placed on a belt and passed under a 80W/cm Hg lamp.
The pendulum hardness was measured in accordance with Swedish
Standard SS 184186.
The results of the tests are presented in Table 5. Table 5
Figure imgf000019_0001
In a second series, 75 parts by weight of the coating compositions were thoroughly mixed with 25 parts by weight of aluminium oxide. The results of the tests are presented in Table 6.
Table 6
Figure imgf000019_0002
Example 7
A UV curable coating composition that can be used as a UV-sealer coat was prepared comprising: - 62,1 parts by weight of a polyester acrylate;
- 3,6 parts by weight of an urethane acrylate;
- 8,7 parts by weight of a photoinitiator;
- 9,4 parts by weight of fillers, and
- 16,2 parts by weight of reactive diluents and additives; This composition was thoroughly mixed with 0-50 parts by weight of of an abrasion resistance enhancement compound similar to the PLC-4 mentioned above. The amount of PLC and the amount of polyester acrylate resin together made out 62,1 parts by weight of the mixtures. The coating compositions were applied to wooden substrates. The coated substrates were placed on a belt and passed under a 80W/cm2 Hg lamp. Several properties of the cured coating compositions were measured, viz. the Pendulum hardness according to Swedish Standard no SS 184186, the abrasion resistance in accordance to Swedish Industrial Standard SIS 923509/Provisional European Norm PREN 175.333.08 using CS-39, and Chemical Resistance to ethanol according Provisional European Norm PREN 175.333.16. The results of the tests are presented in Table 7.
Table 7
Figure imgf000021_0001

Claims

Claims
1. Radiation curable coating composition comprising a radiation curable resin and an abrasion resistance enhancement compound having at least one radiation curable functional group, characterised in that it comprises from 1 to 30 % by weight based on the total weight of the composition of the abrasion resistance enhancement compound having at least one radiation curable functional group.
2. Radiation curable coating composition according to claim 1 , characterised in that it comprises from 1 to 25 % by weight based on the total weight of the composition of the abrasion resistance enhancement compound having at least one radiation curable functional group.
3. Radiation curable coating composition according to claim 1 or 2, characterised in that the abrasion resistance enhancement compound is a vinyl or acrylate capped polyfunctional liquid compound obtainable by reacting an isocyanate-reactive vinyl or acrylate compound with an isocyanate functional compound, wherein said isocyanate functional compound is obtainable by reacting an organic substance having a molecular weight of from 60 to 20;000 and containing per molecule at least three isocyanate-reactive functional groups selected from -OH, - SH, -COOH, -NHR, where R is hydrogen, alkyl or epoxy, with a polyisocyanate comprising at least two isocyanate moieties per molecule.
4. Radiation curable coating composition according to claim 3, characterised in that the vinyl or acrylate capped polyfunctional liquid compound is substantially free of isocyanate functional groups.
5. Radiation curable coating composition according to any one of the preceding claims, characterised in that the composition comprises one or more resins selected from the group consisting of UV curable polyester resins, UV curable polyetheracrylate resins, UV curable epoxyacrylate resins, and UV curable urethaneacrylate resins.
6. Radiation curable coating composition according to claim 3 or 4, characterised in that the vinyl or acrylate capped polyfunctional liquid compound is an acrylate capped polyurethane obtained by reacting 2- hydroxyethylmethacrylate with an isocyanate functional compound, said isocyanate-functional compound obtained by reacting a polyoxyalkylene entity comprising oxyethylene, oxypropylene, or mixtures thereof with a diisocyanate.
7. Process for the preparation of a wooden, wood-like and/or cellulose containing substrate with enhanced abrasion resistance, scratch resistance, and/or indentation resistance wherein the substrate is coated with a radiation curable base coat, a radiation curable mid coat and/or a radiation curable top coat whereby at least one of the applied coating layers comprises from 1 to 30 % of an abrasion resistance enhancement compound having at least one radiation curable functional group.
8. Wooden, wood-like and/or cellulose containing substrate with enhanced abrasion resistance, scratch resistance, and/or indentation resistance wherein the substrate is coated with a radiation curable base coat, a radiation curable mid coat and/or a radiation curable top coat whereby at least one of the applied coating layers comprises from 1 to 30 % of an abrasion resistance enhancement compound having at least one radiation curable functional group.
9. Use of a radiation curable coating composition according to any one of claims 1 to 6 as a base coat, mid coat or top coat for parquet flooring.
PCT/EP2001/007927 2000-07-11 2001-07-10 Radiation curable coating composition comprising an abrasion resistance enhancement agent WO2002004539A1 (en)

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