Enhanced abrasion resistance radiation curable coating for substrates

Abstract

An abrasion resistant, radiation or heat curable dual composition is applied to a polymer substrate, such as an opthamlic lens. An abrasion enhancement layer is deposited on a surface of the substrate. The abrasion enhancement layer has a modulus of M.sub.1 and a Shore A value of 50 or less. A top coating is deposited on the abrasion enhancement layer. It has a modulus of M.sub.2 that is greater than M.sub.1. The top coating has an abrasion resistance Bayer Haze Gain ratio of 1.0 or greater.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates generally to radiation or heat curable coating compositions for a variety of articles, particularly plastic ophthalmic lenses, and more particularly to dual coated ophthalmic lenses with high abrasion and scratch resistance.

2. Description of the Related Art

Plastic materials have found increased usage for the construction of a variety of substrates, including but not limited to ophthalmic lenses for eyeglasses, cameras, and optical instruments, due to their light weight, ease of fabrication and relatively low cost. Common lens forming materials include CR-39 (diethyleneglycol bisallyl carbonate) available from PPG Industries, bisphenol A polycarbonate (PC), and poly(methylmethacrylate) (PMMA).

Plastic lens materials have traditionally possessed inferior resistance to scratching, commonly evaluated by rubbing the surface with steel wool; and inferior resistance to abrasion, usually measured by shaking the lens surface under a bed of sand in the Bayer Abrasion Test. The cumulative effect of scratching and abrading the lens surface is to increase the haze in the lens and ultimately to produce a substantially translucent lens incapable of providing a coherent image. Consequently, plastic lens surfaces have required treatment to provide a scratch and/or abrasion resistant layer on the lens surface to increase the field durability of the lens, and retard the development of haze.

With current lens coating formulations, there is a trade off in the desired properties of scratch resistance and abrasion resistance. One is usually sacrificed for the other.

There is a need for a coating formulation for a plastic substrate that does not sacrifice the scratch resistance or the abrasion resistance for the other. It would be desirable to provide a dual coating for a plastic substrate that provides the substrate with scratch and abrasion resistance characteristics that are substantially similar to glass.

SUMMARY

Accordingly, it is an object of the invention to provide a dual layer coating composition for a plastic substrate that increases abrasion resistance of a coating associated with the substrate while maintaining its scratch resistance.

A further object of the invention is to provide a plastic substrate with an abrasion enhancement coating between the substrate, and a second coating with the abrasion enhancement coating that increases the abrasion resistance of the top coating layer without reducing the second coating's scratch resistance.

Yet another object of the invention is to provide a plastic lens with a dual layer coating composition, with a top coat having increased abrasion resistance while maintaining its scratch resistance.

Another object of the invention is to provide a dual layer coating for a plastic substrate which provides the substrate with substantially the same abrasion and scratch resistance characteristics of a glass substrate.

These and other objects of the invention are obtained for an abrasion resistant, dual coating composition for a substrate. An abrasion enhancement coating is applied to a surface of a substrate. A top coating layer is then applied to the abrasion enhancement coating. The top coating layer has a certain scratch resistance value. The abrasion enhancement coating increases the abrasion resistance value of the top coating layer without sacrificing the top coating layer's scratch resistance value, and provides adhesion between the substrate and the top coating layer. The abrasion enhancement coating has a Young's modulus of M.sub.1 and a Shore A value of 50 or less. The top coating layer has a Young's modulous of M.sub.2 that is greater than M.sub.1 and an abrasion resistance Bayer haze gain ratio of 1.0 or greater.

The substrate can be a made of a polymer. For purposes of this disclosure the polymer substrate can include any type of optically clear and colorless materials, clear colored materials, plastics filled with glass or minerals, wood and metal surfaces.

In one embodiment, the abrasion enhancement coating is made of thirty to ninety-five parts of a flexible acrylated oligomer or acrylated oligomer/acrylate monomer blend resin; and five to seventy parts of a monovinyl functional reactive diluent. The top coating layer is made of twenty to seventy parts of alkane polyols, wherein the alkane polyols contain up to about forty eight carbon atoms and average at least three O-�acryloyl(polyalkylene oxide)! chains, wherein each of the polyalkylene oxide chains comprise from one to twenty alkylene oxide groups; and fifteen to seventy five parts of a polyacrylated urethane, wherein the urethane oligomer has a molecular weight of about 2500 or less and an average of at least two acrylate groups.

In another embodiment, the abrasion enhancement coating is made of thirty to eighty parts of a flexible acrylated oligomer or acrylated oligomer/acrylate monomer blend resin; and twenty to seventy parts of a monovinyl functional reactive diluent. The top coating layer is made of twenty to seventy parts of alkane polyols, wherein the alkane polyols contain up to about forty eight carbon atoms and average at least three O-�acryloyl(polyalkylene oxide)! chains, wherein each of the polyalkylene oxide chains comprise from one to twenty alkylene oxide groups; and fifteen to seventy five parts of a polyacrylated urethane, wherein the urethane oligomer has a molecular weight of about 2500 or less and an average of at least two acrylate groups.

In yet another embodiment of the invention the abrasion enhancement coating is made of thirty to eighty parts of a flexible acrylated oligomer or acrylated oligomer/acrylate monomer blend resin; twenty to seventy parts of a monovinyl functional reaction diluent; optionally, five to thirty parts of polyacryloylated alkane polyols, wherein the alkane polyols contain up to about twenty four carbon atoms and an average of at least two O-acryloyl groups; optionally five to thirty parts of alkane polyols, wherein the alkane polyols contain up to about forty eight carbon atoms and average at least three O-�acryloyl(polyalkylene oxide)! chains, wherein each of the polyalkylene oxide chains comprise from one to twenty alkylene oxide groups; optionally, fifteen to seventy five parts of a polyacrylated urethane, wherein the urethane oligomer has a molecular weight of about 2500 or less and an average of at least two acrylate groups; and optionally, one tenth to fifteen parts of a non-vinyl functional plasticizer.

In a further embodiment, the top coating layer is made of twenty to seventy parts of alkane polyols, wherein the alkane polyols contain up to about forty eight carbon atoms and average at least three O-�acryloyl(polyalkylene oxide)! chains, wherein each of the polyalkylene oxide chains comprise from one to twenty alkylene oxide groups; fifteen to seventy five parts of a polyacrylated urethane, wherein the urethane oligomer has a molecular weight of about 2500 or less and an average of at least two acrylate groups; optionally, twenty to seventy parts of polyacryloylated alkane polyols, wherein the alkane polyols contain up to twenty four carbon atoms and an average of at least three O-acryloyl groups; and optionally, one to twenty five parts of a mono vinyl functional reactive diluent.

The compositions of the invention can include a photoinitiator, a surfactant, a flow control agent, and a stabilizer.

DESCRIPTION OF THE DRAWINGS

FIG. 1 is cross-sectional view of a substrate with an abrasion enhancement coating and a top coating layer.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Referring now to FIG. 1 a substrate 10, which can be made of a polymer, is first coated with a compliant abrasion enhancement layer 12, followed by a scratch and abrasion resistant top layer 14. Substrate 10 can be a lens, including but not limited to lenses useful as eyeglasses, camera lens components, scientific and medical instrumentation, automotive and aerospace light transmitting components, and the like. Layers 12 and 14 are applied in the liquid state, and then cured by exposure to ultraviolet actinic radiation or by the application of heat to obtain the desired final composite layer properties. It will be appreciated that layers 12 and 14 are applied in the liquid states, with viscosities of about 5 to 5,000 centipoise Tables I and II list different suitable abrasion enhancement coatings 12 and top coatings 14 respectively.

Inclusion of layer 12, with a lower modulus than layer 14, enhances the scratch and abrasion resistance of top coating layer 14. Top coating layer 14 can be tintable. The scratch and abrasion resistance properties of top coating layer 14 can approximate those of glass as illustrated in Table III. Table III is a listing of the abrasion resistance Bayer Haze Gain ratio, scratch resistance (steel wool percent of Haze Gain) and cross-hatch tape peel adhesion for a variety of different dual layer coatings.

Table IV lists different hardness characteristics of abrasion enhancing layer. Table V lists different hardness characteristics of top coating layer 14. Abrasion enhancement layer 12 has a number of desirable properties:

1. It adheres well to both the substrate, e.g., the lens, and top coating 14, and provides a substantial durable bond. 2. Abrasion enhancement layer 12 is compliant to top coating layer 14 and is a "soft" material relative to the harder top coating layer 14. The general physical characteristics of abrasion enhancement layer 12 are those of a compliant material. A degree of cross-linking is desirable for the performance of the abrasion enhancement layer 12, including resistance to creep. 3. Abrasion enhancement layer 12 can be solvent-borne, but is preferably a 100% solids system that can be applied as a liquid, such as by spray or spin TABLE I__________________________________________________________________________EXAMPLE COMPOSITIONS FOR ABRASION ENHANCING LAYERCOMPOSITION OF ABRASION ENHANCING LAYER FORMULATION, IN PERCENT BYWEIGHT A2 DSM A3 A4 AE1 AOA1 RD1 RD2 RD3 RD5 RD6 A1 3471 SR SR SR SR SR SR SR RD4 SR Eb UA1 UA2 P1 Eb767 1-135 9008 9013 344 9035 285 256 395 H8061 493 BCEA H6008 H6210 DOP__________________________________________________________________________AEL01 50 50AEL02 50 25 25AEL03 55 45AEL04 50 25 25AEL05 50 25 25AEL08 60 40AEL09 80 20AEL10 75 15 10AEL11 50 20 30AEL12 40 60AEL13 45 55AEL19 65 35AEL20 70 30AEL21 50 10 40AEL22 70 10 20AEL23 10 80 5 5AEL24 38.8 38.8 22.4AEL25 3 97AEL26 3 50 47AEL27 40 3 57AEL28 40 3 27 30AEL29 50 10 40AEL30 50 5 45AEL31 100AEL32 60 10 30AEL33 50 10 40AEL34 10 50 40AEL35 5 35 60AEL36 40 10 10 40AEL37 20 40 40AEL38 20 40 5 20 15AEL39 10 50 5 20 15AEL40 20 45 5 20 10AEL41 20 50 5 25AEL42 40 20 5 35AEL43 40 10 5 20 25AEL44 50 5 20 25AEL45 50 10 20 20AEL46 35 35 30AEL47 40 20 40AEL48 50 20 5 25AEL49 50 10 5 35AEL50 30 30 5 35AEL51 30 40 5 25AEL52 50 5 35 10AEL53 45 15 5 35AEL54 45 10 5 40AEL55 55 25 20AEL56 45 25 30AEL57 50 40 10AEL58 50 35 15AEL59 40 25 35AEL60 50 10 40__________________________________________________________________________Prefix Class of CompositionA FLEXIBLE OLIGOMER OR OLIGOMER/MONOMER BLENDAE ACRYLATE ESTERAOA ALKOXYL ACRYLATERD REACTIVE DILUENTUA URETHANE ACRYLATEP PLASTICIZERNumeric suffixes designate distinct species of the class of compositiondesignated by prefix.LEGEND FOR TABLE IComponent Supplier Composition__________________________________________________________________________A = flexible oligomer componentAT = Eb 767 UCB Chemicals Corp., Radcure Business 60% polyurethane acrylate, 38% 2000 Lake Park Dr., Smyrna, GA 30080 isobornylacrylate, 2% TMPTAA2 = DSM 3471-1-135 DSM Desotech, Inc., 1122 St. Charles polyacrylate ester coating resin Elgin, IL 60120A3 = SR 9008 Sartomer Company, Inc., Oakland Corporate alkoxylated trifunctional acrylate 502 Thomas Jones Way, Exton, PA 19341 ester resin (Sartomer)A4 = SR 9013 (Sartomer) mono functional acrylate ester resinAE = acrylic ester componentAE1 = SR 344 (Sartomer) poly(ethylene glycol) diacrylate ester, 400 MWAOA = alkoxylated acrylic ester componentAOA1 = SR 9035 (Sartomer) 15 moles ethoxylated trimethylolpropane triacrylate esterRD - reactive diluent componentRD1 = SR 285 (Sartomer) tetrahydrofurfuryl acrylateRD2 = SR 256 (Sartomer) 2-(2-ethoxyethoxy)ethyl acrylateRD3 = SR 395 (Sartomer) iso dodecyl acrylateRD4 = H 8061 Henkel Corporation, Coating Chemicals polyester polyacrylate ester resin 300 Brookside Ave., Ambler, PA 19003-3491 (Henkel)RD5 = SR 493 (Sartomer) tridecyl methacrylateRD6 = BCEA (Radcure) .beta.-carboxyethyl acrylateUA = urethane acrylate componentUA1 = H 6008 (Henkel) polyurethane acrylate resinUA2 = H 6210 (Henkel) aliphatic polyurethane polyacrylateP = plasticizer componentP1 = DOP Eastman Chemical Company dioctyl phthalate Kingsport, TN 37662__________________________________________________________________________ TABLE II__________________________________________________________________________EXAMPLE COMPOSITIONS FOR TOPCOATSCOMPOSITION OF TOPCOAT FORMULATION, IN PERCENT BY WEIGHT UA1 UA2 UA3 AE1 AE2 AOA1 AOA2 AOA3 AOA4 AOA5 RD1 RD2 RD3 Eb 220 Eb 6602 H 6210 SR 9041 SR 454 SR 9035 SR 415 SR 499 SR 502 SR 9008 SR 497 SR SR__________________________________________________________________________ 285TC 01 50 25 25TC 02 50 25 25TC 03 30 30 15 25TC 03A 28.5 5 28.5 14.2 23.8TC 03B 27 10 27 13.5 22.5TC 03C 28.5 28.5 14.2 23.8 5TC 03D 27 27 13.5 22.5 10TC 04 30 30 15 25TC 05 15 15 50 20TC 06 15 15 45 25TC 07 30 50 20TC 08 30 45 25TC 09 35 45 20TC 11 45 55TC 12 50 50TC 13 50 50TC 14 60 40TC 15 60 15 25TC 16 60 40TC 17 65 35TC 18 56.5 43.5TC 19 30 30 40TC 20 30 25 20 25TC 21 25 25 25 25TC 22 30 30 40TC 23 70 20 10TC 24 40 15 35 10TC 25 45 15 25 15TC 26 50 30 20TC 27 55 45TC 28 40 35 25TC 29 30 25 25 20TC 30 40 60TC 31 30 30 40TC 32 40 55 5TC 33 75 25TC 34 30 25 30 15TC 35 30 30 40TC 36 30 25 35 10TC 37 30 25 45TC 38 30 35 25 10TC 39 30 35 25 10TC 40 30 30 25 15TC 41 20 60 20TC 42 45 25 30TC 43 30 30 20 20TC 44 30 30 15 25TC 45 30 30 30 10__________________________________________________________________________Prefix Class of CompositionUA URETHANE ACRYLATEAE ACRYLATE ESTERAOA ALKOXYL ACRYLATERD REACTIVE DILUENTNumeric suffixes designate distinct species of the class of compositiondesignated by prefix.LEGEND FOR TABLE IIComponent Supplier Composition__________________________________________________________________________A = flexible oligomer componentA = Eb 767 UCB Chemicals Corp., Radcure Business 60% polyurethane acrylate, 38% 2000 Lake Park Dr., Smyrna, GA 30080 Isobornylacrylate, 2% TMPTAA2 = DSM 3471-1-135 DSM Desotech, Inc., 1122 St. Charles polyacrylate ester coating resin Elgin, IL 60120A3 = SR 9008 Sartomer Company, Inc., Oaklands Corporate alkoxylated trifunctional acrylate ester resin 502 Thomas Jones Way, Exton, PA 19341A4 = SR 9013 (Sartomer) monofunctional acrylate ester resinAE = acrylic ester componentAE1 = SR 9041 (Sartomer) pentaacrylate esterAE2 = SR 454 (Sartomer) 3 moles ethoxylated trimethylolpropane triacrylate esterAOA = alkoxylated acrylic ester componentAOA1 = SR 9035 (Sartomer) 15 moles ethoxylated trimethylolpropane triacrylate esterAOA2 = SR 415 (Sartomer) 20 moles ethoxylated trimethylolpropane triacrylate esterAOA3 = SR 499 (Sartomer) 6 moles ethoxylated trimethylolpropane triacrylate esterAOA4 = SR 502 (Sartomer) 9 moles ethoxylated trimethylolpropane triacrylate esterAOA5 = SR 285 (Sartomer) alkoxylated trifunctional acrylate ester resinRD - reactive diluent componentRD1 = SR 497 (Sartomer) N-vinylformamideRD2 = SR 256 (Sartomer) 2-(2-ethoxyethoxy)ethyl acrylateRD3 = SR 285 (Sartomer) Tetrahydrofurfuryl acrylateUA = urethane acrylate componentUA1 = Eb 220 (Radcure) aromatic polyurethane polyacrylate (6)UA2 = Eb 6602 (Radcure) aromatic polyurethane polyacrylate (3)UA3 = H 6210 Henkel Corporation, Coating Chemicals aliphatic polyurethane polyacrylate 300 Brookside Ave., Ambler, PA 19003-3491__________________________________________________________________________ TABLE III__________________________________________________________________________EFFECT of ABRASION ENHANCING LAYER on ABRASION and SCRATCHRESISTANCE of TOPCOATS Abrasion Scratch Resistance Resistance Cross-Hatch AEL TC Bayer Haze Steel Wool Tape PeelSubstrate Reference # Reference # Gain Ratio % Haze Gain Adhesion__________________________________________________________________________Polycarbonate None TC 45 1.53 0 PASS" AEL12 TC 45 1.67 PASS" AEL52 TC 45 1.72 0.02 PASS" AEL54 TC 45 1.75 0 PASS" AEL53 TC 45 1.75 0.02 PASS" AEL37 TC 45 1.78 PASS" AEL47 TC 45 1.8 PASS" AEL60 TC 45 1.95 0 PASS" AEL57 TC 45 1.98 0 PASS" AEL56 TC 45 1.99 0.5 PASS" AEL61 TC 45 2.20 FAIL" AEL62 TC 45 2.60 FAIL" AEL63 -- CRAZEDCR-39 None TC 11 1.6 1.4 PASS" AEL03 TC 11 2.1 1.5 PASS" AEL01 TC 11 2.3 0.9 PASSPolycarbonate None TC 03 1.4 0 PASS" AEL03 TC 03 2 0 PASS" AEL24 TC 03 2.3 0 PASSCR-39 AEL03 TC 14 1.8 FAIL" AEL03 TC 23 1.8 0.1 PASS" AEL03 TC 13 2.1 0.8 PASS" AEL03 TC 11 2.5 1.3 PASS" AEL03 TC 20 2.2 0.1 PASSPolycarbonate AEL31 TC 30 1.98 2.2 PASS" AEL31 TC 03 2.09 FAIL" AEL31 TC 32 2.8 8.3 PASSCR-39 None None 1 53 --Polycarbonate None None <0.2 >60 --Crown Glass None None 3 0 --__________________________________________________________________________ TABLE IV______________________________________HARDNESS CHARACTERISTICS ofABRASION ENHANCING LAYER (AEL)AEL Shore A Shore DReference # Durometer Durometer______________________________________AEL01 9.0AEL03 7.0 <0.5AEL09 42.0 9.0AEL12 11.0AEL22 57.0 19.0AEL24 43.0 8.5AEL31 51.5 16.0AEL37 35.0 7.0AEL41 51.5 18.0AEL47 24.0AEL52 24.5AEL53 36.5AEL54 30.0AEL56 33.0 8.0AEL57 8.0AEL60 32.5 <0.5AEL63 52.5 16.0______________________________________ TABLE V______________________________________HARDNESS CHARACTERISTICS OF TOPCOAT LAYERS Topcoat Shore D Reference # Durometer______________________________________ TC03 91 TC11 80 TC17 90 TC18 89 TC24 92 TC25 90 TC26 95 TC27 89 TC45 91 TC46 82______________________________________ coating techniques, and is convertible to its desired final physical state by exposure to an energy source, preferably ultraviolet actinic radiation, although thermal curing to the desired final physical state is possible. Free radical based curing regimens are preferred, but cationic or catalyzed curing systems can be used. 4. Abrasion enhancement layer 12 is resistant to environmental degradation, including but not limited to exposure to temperature, humidity or sunlight, and is also durable. The operational temperature range is at least 20 degrees C. to 50 degrees C.

Without being bound by any specific explanation for the observed benefit effects of abrasion enhancement layer 12, it is believed that abrasion enhancement layer 12 allows the deformation of top coating layer 14 when it is contacted by rough objects. This deformation allows the transfer of the frictional and impact energy from top coating 14 to abrasion enhancement layer 12 where it can be absorbed and dissipated. Top coating layer 14, which is innately more brittle than abrasion enhancement layer 12, does not reach the critical tensional and compressional threshold where cracks can form that scatter light, and give a hazy appearance. While the steel wool resistance of a coating is believed to be mostly related to the hardness of the coating, the Bayer abrasion resistance is believed to be more related to the ability of a coating to endure impact without chipping or cracking. Additionally, in the prior art, a single coating layer is tightly bonded directly to the lens surface and a considerable internal stress remains in the coating after curing, particularly in the x and y directions. With the present invention, abrasion enhancement layer 12 is bonded to the substrate; the residual stress in top coating layer 14 from that curing process is greatly reduced or eliminated altogether, and top coating layer 14 becomes more notch insensitive relative to the traditional single coating layer approach.

Substrate 10 has abrasion enhancement layer 12 deposited on a surface of the substrate. Abrasion enhancement layer 12 has a Young's modulus of M.sub.1 and a Shore A value of 50 or less. Top coating layer 14 is deposited on abrasion enhancement layer 12. Top coating layer 14 has a Young's modulous of M.sub.2 that is greater than M.sub.1 and an abrasion resistance Bayer haze gain ratio of 1.0 or greater. Top coating layer 14 has a Shore D value of 50 or higher, and a steel wool % haze gain of 10 or lower. The thicknesses of abrasion enhancement layer 12 and top coating layer 14 can vary and be independent. Preferable thicknesses are 2-50 microns, more preferably 5-20 microns for each layer. In one embodiment, layers 12 and 14 are about 15 microns or less.

Abrasion enhancement layer 12 can have the following composition:

I. Thirty to ninety five parts of a flexible acrylated oligomer or acrylated oligomer/acrylate monomer blend resin (A); II. Five to seventy parts of a mono vinyl functional reactive diluent (RD); and III. Optionally, five to thirty parts of alkane polyols, wherein the alkane polyols contain up to about twenty four carbons atoms and an average of at least two O-acryloyl groups (AE); IV. Optionally, five to thirty parts of alkane polyols, wherein the alkane polyols contain up to about forty eight carbon atoms and average at least three O-�acryloyl(polyalkylene oxide)! chains; wherein each of the polyalkylene oxide chains comprise from one to twenty alkylene oxide groups (AOA); V. Optionally, fifteen to seventy five parts of polyacrylated urethane, wherein the urethane oligomer has a molecular weight of about 2500 or less and an average of at least two acrylate groups (UA); and VI. Optionally, one tenth to fifteen parts of a non-vinyl functional plasticizer (P), such that the cured abrasion enhancing layer is softer than the cured top coat layer

This composition can also contain a photoinitiating amount of a photoinitiator, typical one tenth to about ten parts, as well as optional surfactants and stabilizers.

Additionally, abrasion enhancement layer 12 can have the following composition:

I. Thirty to eighty parts of a flexible acrylated oligomer or acrylated oligomer/acrylate monomer blend resin (A); and II. Twenty to seventy parts of a mono vinyl functional reactive diluent (RD). a

Top coating layer 14 can have the following composition:

I. Twenty to seventy parts of alkane polyols, wherein the alkane polyols contain up to about forty eight carbon atoms and average at least three O-�acryloyl(polyalkylene oxide)! chains; where in each of the polyalkylene oxide chains comprise from one to twenty alkylene oxide groups (AOA); II. Fifteen to seventy five parts of a polyacrylated urethane, wherein the urethane oligomer has a molecular weight of about 2500 or less and average of at least two acrylate groups (UA); III. Optionally, twenty to seventy parts of polyacryloylated alkane polyols, wherein the alkane polyols contain up to twenty four carbon atoms and an average of at least three O-acryloyl groups (AE); IV. Optionally, one to twenty five parts of a mono vinyl functional reactive diluent (RD).

This dual composition can also contain a photoinitiating amount of photoinitiator, typically one tenth to about ten parts, as well as optional surfactants and stabilizers.

Another class of a scratch and abrasion-resistant, radiation curable or heat curable coating composition used in accordance with the present invention comprises:

I. Ten to fifty parts of polyacryloylated alkane polyols, wherein the alkane polyols contain up to about twenty four carbon atoms and an average of at least three O-acryloyl groups (AE); II. Twenty to eighty parts of alkane polyols, wherein the alkane polyols contain up to about forty eight carbon atoms and average at least three O-�acryloyl(polyalkylene oxide)! chains; wherein each of the polyalkylene oxide chains comprise from one to twenty alkylene oxide groups (AOA);

This composition will also contain a photoinitiating amount of a photoinitiator, typically one tenth to about ten parts, as well as optional surfactants and stabilizers.

COMMERCIAL EXAMPLES OF COMPOSITION COMPONENTS

"A" (FLEXIBLE ACRYLATED OLIGOMER OR OLIGOMER/MONOMER BLEND RESIN MATERIAL,) EXAMPLES

Examples of suitable flexible oligomer or oligomer/monomer blend materials are Sartomer CN 300, Sartomer9008, Sartomer 9013; Radcure Ebecryl 3600, Ebecryl 3703, Ebecryl 270, Ebecryl 4830, Ebecryl 4834, Ebecryl 4881, Ebecryl 4883, Ebecryl 8402, Ebecryl 525, Ebecryl 585, Ebecryl 745, Ebecryl 754, Ebecryl 767, Ebecryl 1755; Henkel Photomer 6230; DSM Desotech 3471-1-135.

"RD" (REACTIVE DILUENTS) EXAMPLES

Examples of suitable mono vinyl functional reactive diluents are Sartomer SR 203, SR 232, SR 244, SR 256, SR 285, SR 339, SR 395, SR 440, SR 493, SR 497, SR 506; Radcure IBOA, Radcure ODA, Radcure B-CEA; Henkel Photomer 4039, Photomer 4812, Photomer 4816, Photomer 4822, Photomer 8061 and Photomer 8127.

"AE" (ACRYLATE ESTER) EXAMPLES FOR ABRASION ENHANCEMENT LAYER 12:

Examples of suitable two functional acrylated aliphatic polyol esters are Sartomer SR 205, SR 209, SR 210, SR 230, SR 231, SR 252, SR 259, SR 268, SR 272, SR 306, SR 344, SR 9003, SR 9209; Radcure TRPGDA, Radcure HDODA; Henkel Photomer 4050, Photomer 4065, Photomer 4061, Photomer 4126, Photomer 4127, Photomer 4160, Photomer 4193, and Photomer 4204. Examples of three or greater functional acrylated aliphatic polyol ester are Sartomer SR 350, SR 351, SR 444, SR 295, SR 335, SR 399, SR 9041; Radcure DPHPA, Radcure PETA K,. Radcure TMPTA; Henkel Photomer 4006, Photomer 4335, and Photomer 4399.

A general chemical structure may be written: (Polyol)--(O--CO--CH.dbd.CH.sub.2).sub.n, where n.gtoreq.2 "AOA" EXAMPLES

Examples of alkoxylated acrylates are Sartomer SR 415, SR 454, SR 492, SR 499, SR 502, SR 9008, SR 9035; Radcure OTA-480, Radcure TMPTEOA, Radcure Ebecryl 53; Henkel Photomer 4072, Photomer 4094, Photomer 4095, Photomer 4149, Photomer 4155, Photomer 4158, and Photomer 4355.

A general chemical structure may be written: (Polyol)--((--O--(CH--R).sub.s --).sub.m --O--CO--CH.dbd.CH.sub.2).sub.p where p.gtoreq.3 m=1-20 s=1-6 R is H or lower alkyl, preferable H or methyl "UA" (ACRYLATED URETHANE) EXAMPLES

Examples of urethane acrylates are Sartomer CN 953, CN 961, CN 963, CN 964, CN 970, CN 971, CN 972, CN 975, CN 980; Radcure Ebecryl 8804, Ebecryl 220, Ebecryl 6602, Henkel Photomer 6210, Photomer 6008, Photomer 6010.

"P" (PLASTICIZER) EXAMPLES

Examples of plasticizers are the aliphatic or arakyl esters of aromatic acids, diacids, and triacids, (such as benzoic, phthalic, isophthalic, terephthalic, and trimellitic acids) such as dioctyl phthalate (DOP) and dibenzyl phthalate; the aliphatic or aralkyl esters of aliphatic acids (such as adiptic, azelaic, glutaric, and citric acids) such as dioctyl adipate; and phosphate esters.

"AE" (ACRYLATE ESTER) EXAMPLES FOR TOP OATING LAYER 14

Examples of acrylated aliphatic polyol ester which average three or greater acrylic functionality are Sartomer SR 350, SR 351, SR 454, SR 295, SR 355, SR 399, SR 9041; Radcure DPHPA, Radcure PETA K, Radcure TMPTA; Henkel Photomer 4006, Photomer 4355, and 4399.

A general chemical structure may be written: (Polyol)--(O--CO--CH.dbd.CH.sub.2).sub.n, where n.gtoreq.3

TEST METHOD DESCRIPTION

BAYER ABRASION RESISTANCE

A Bayer Sand Abrasion Tester is used for the determination of surface abrasion resistance. The sample, dual coated with abrasion enhancing layer and top coat, along with a control sample of CR-39 is cleaned with mild soapy water, rinse with water, then air dried. The light transmission of the both at 550 nm is determined using a Fisher UV-VIS Spectrophotometer (reference ASTMD 1003-61 "Standard Test Method for Measuring Haze and Luminous Transmittance of Transparent Plastics"). The cleaned sample is mounted to cover one of the holes in the underside of the testing pan. The control sample of uncoated CR-39 is place under the other hole, then 1.0 kilograms of new sand, which has been sieved to retain the portion passing a #7 but held by a #14 sieve, is placed in the pan. The sand filled pan is shaken over a 4 inch stroke at a rate of sieve, is placed in the pan. The sand filled pan is shaken over a 4 inch stroke at a rate of 150 cycles per minute for a total of 300 cycles. Both sample and control are cleaned with mild soapy water, rinsed with water, then air dried. The light transmission of the both at 550 nm is determined. The percent haze gain due to abrading the sample surfaces with sand is calculated; the Bayer Haze Gain Ratio is determined by dividing the measured haze gain for the CR-39 control by that of the sample under evaluation. By definition, the Bayer Haze Gain Ratio for CR-39 is 1.0.

SCRATCH RESISTANCE

An Eberbach 6000 Steel Wool Abrasion Tester is used for the determination of surface scratch resistance. A piece of 000 steel wool (Pro's Best, International Steel Wool Co.) is mounted over the end of a one inch by one inch mandrel with the steel wool strands aligned in the direction of motion. The sample, dual coated with abrasion enhancing layer and top coat layer, is cleaned with mild soapy water, rinsed with water, then air dried. The light transmission of the sample at 550 nm is determined using a Fisher UV-VIS Spectrophotometer (reference ASTMD 1003-61 "Standard Test Method for Measuring Haze and Luminous Transmittance of Transparent Plastics"). The cleaned sample is mounted onto the testing stage, then the mandrel set in place and weighted with 32 pounds. Twenty complete cycles back and forth across the sample are applied at a rate of 100 cycles per minute. The sample is re-cleaned with mild soapy water, rinsed with water, then air dried and the light transmission of the sample at 550 nm is determined. The percent hazed gain due to scratching the sample surface with steel wool is calculated by comparison with the value before testing and reported.

CROSS-HATCH TAPE PEEL ADHESION TEST

A sample plastic substrate is coated and cured with the abrasion enhancing layer and topcoat layer under evaluation. A cross-hatched grid of twenty five squares 2 mm on a side is scored through both layers down to the substrate using a razor knife. One end of a three inch by three fourths inch piece of Scotch Tape.RTM. (3M Co.) is placed over the grid and pressed to bond uniformly to the topcoat surface. The tape is then peeled off the surface with a rapid hand motion. If no more than one square of the grid is found to have debonded from the substrate an adhered to the tape, the sample configuration is deemed to have passed the adhesion test. If no more than on square debonds, the sample is deemed to have failed the adhesion test. Reference is made to test ASTM D-3359.

HARDNESS EVALUATION OF CURED AEL AND TOPCOAT COMPOSITIONS

The relative hardness of cured AEL and topcoat compositions on the Shore A and/or Shore D scales was determined using a durometer. The neat resin sample was poured into a 1".times.1".times.1/8" mold cavity formed by a PVC gasket held between two quartz plates. The sample was cured using a Fusion System H Bulb with an exposure time of about 8-12 seconds. Cured samples were removed from the mold, allowed to cool to ambient temperature, then the hardness on the Shore A or D scale determined with the respective Shore Durometer. There is some overlap in the scales, but the A scale can assess the hardness of softer samples, while the D scale is used for relatively harder samples.

DESCRIPTION OF EXAMPLE SAMPLE PREPARATION

SPIN COATING AND UV CURING

A substrate sample, about 3 inches in diameter and 1/8 inch thick, is mounted on the spin table of the spin coating apparatus. While spinning at about 150 rpm, the sample surface is washed with ispropyl alcohol, then the speed increased to 2000-3000 rpm and held until sample surface is dry, about 30-60 seconds. While spinning at about 150 rpm, the abrasion enhancing layer (AEL) is applied with a pipette to the substrate surface, working from the center to the edge of the sample, to form a uniform coating layer. The spin speed is then increased to the range 1000-6000 rpm and held for 15-90 seconds until the desired layer thickness is achieved, generally in the range of 1-50 microns. The wet coated substrate is placed in an enclosed chamber with a quartz window, nitrogen purged through the cavity, then the chamber with sample is passed on a conveyor belt under a Fusion systems UV Lamp to cure the abrasion enhancing layer. Total irradiation time for AEL is 1-10 seconds. The coated sample is returned to the spin table, then the topcoat is applied by pipette across the slowly spinning AEL sample surface. The spin speed is then increased to the range 1000-6000 rpm and held for 15-90 seconds until the desired layer thickness is achieved, generally in the range of 1-50 microns. The wet coated AEL/substrate is placed in the chamber with a quartz window, nitrogen purged through the cavity, then the chamber passed on a conveyor belt under a Fusion Systems UC Lamp to cure the topcoat layer. Total irradiation time for the top coat layer is 1-10 seconds.

Claims

1. An abrasion resistant article, comprising:

a plastic substrate;

an abrasion enhancement layer deposited on a surface of the plastic substrate which adheres to the surface of the plastic substrate, the abrasion enhancement layer including an acrylated oligomer or acrylated oligomer/acrylate monomer blend resin; and

a top coating layer deposited on the abrasion enhancement layer, the top coating layer including polyacrylated urethane the top coating layer having an abrasion resistance Bayer haze gain ratio of 1.0 or greater and a greater hardness than the abrasion enhancement layer.

2. The abrasion resistant article of claim 1, wherein the top coating layer has a Shore D value of between about 80 and about 95.

3. The abrasion resistant article of claim 1, wherein the top coating layer has a steel wool percent haze gain of 10 or less.

4. The abrasion resistant article of claim 1, wherein the abrasion enhancement layer and the top coating layer each have a thickness of 50 microns or less.

5. The abrasion resistant article of claim 1, wherein the abrasion enhancement layer and the top coating layer each have a thickness of 20 microns or less.

6. The abrasion resistant article of claim 1, wherein the abrasion enhancement layer and the top coating layer each have a thickness of 15 microns or less.

7. The abrasion resistant article of claim 1, wherein the abrasion enhancement layer increases an abrasion resistance of the top coating layer without substantially reducing a scratch resistance of the top coating layer.

8. The abrasion resistant article of claim 1 wherein the plastic substrate is selected from the group consisting of polycarbonate, diethylene glycol bis allyl polycarbonate and polymethylmethyacrylate.

9. An abrasion resistant article, comprising:

a plastic substrate;

an abrasion enhancement layer deposited on a surface of the plastic substrate, the abrasion enhancement layer including thirty to ninety five percent by weight of a acrylated oligomer or acrylated oligomer/acrylate monomer blend resin and five to seventy percent by weight of a monovinyl functional reaction diluent; and

a top coating layer deposited on the abrasion enhancement layer including twenty to seventy percent by weight of alkane polyols, wherein the alkane polyols contain up to about forty eight carbon atoms and average at least three O-�acryloyl(polyalkylene oxide)! chains, wherein each of the polyalkylene oxide chains comprise from one to twenty alkylene oxide groups, and fifteen to seventy five percent by weight of a polyacrylated urethane, wherein the urethane oligomer has a molecular weight of about 2500 or less and an average of at least two acrylate groups.

10. The abrasion resistant article of claim 9, wherein the abrasion enhancement layer includes thirty to eighty percent by weight of a acrylated oligomer or acrylated oligomer/acrylate monomer blend resin and twenty to seventy percent by weight of a monovinyl functional reaction diluent.

11. The abrasion resistant article of claim 9, wherein the abrasion enhancing layer further includes a photoinitiating amount of a photoinitiator responsive to ultraviolet radiation.

12. The abrasion resistant article of claim 9, wherein the top coat layer further includes a photoinitiating amount of a photoinitiator responsive to ultraviolet radiation.

13. The abrasion resistant article of claim 9, wherein the abrasion enhancing layer further includes a surfactant and a stabilizer.

14. The abrasion resistant article of claim 9, wherein the top coat layer further includes a surfactant and a stabilizer.

15. The abrasion resistant article of claim 9, wherein the abrasion enhancing layer further includes a polyol compound or mixture of the formula

(Polyol)--(O--CO--CH.dbd.CH.sub.2).sub.n,

wherein n is on average greater than or equal to 2.

16. The abrasion resistant article of claim 9, wherein the alkane polyols is selected from compounds having the general formula

(Polyol)--((--O--(CH--R).sub.s --).sub.m --O--CO--CH.dbd.CH.sub.2).sub.p

where, p is on average greater than or equal to 3, m is between 1 and 20, s is between 1 and 6, and R is H or alkyl.

17. The composition of claim 16, wherein R is H or methyl.

18. The abrasion resistant article of claim 9, wherein the abrasion enhancing layer further includes a polyacrylated urethane selected from compounds having the general formula

(Polyol)--(O--CO--CH.dbd.CH.sub.2).sub.n

wherein n is on average greater or equal to 3.

19. An abrasion resistant article, comprising:

a plastic substrate;

an abrasion enhancement layer deposited on a surface of the plastic substrate, the abrasion enhancement layer including

five to seventy percent by weight of a monovinyl functional reaction diluent, five to thirty percent by weight of polyacryloylated alkane polyols, wherein the alkane polyols contain up to about twenty four carbon atoms and an average of at least two O-acryloyl groups,

five to thirty percent by weight of alkane polyols, where the alkane polyols contain up to about forty eight carbon atoms and average at least three O-�acryloyl(polyalkylene oxide)! chains, wherein each of the polyalkylene oxide chains comprise from one to twenty alkylene oxide groups,

fifteen to seventy five percent by weight of a polyacrylated urethane, wherein the urethane oligomer has a molecular weight of about 2500 or less and an average of at least two acrylate groups, and

one tenth to fifteen percent by weight of a non-vinyl functional plasticizer such that the cured abrasion enhancing layer is softer than the cured topcoat layer; and a top coating layer deposited on the abrasion enhancement layer including

twenty to seventy percent by weight of alkane polyols, wherein the alkane polyols contain up to about forty eight carbon atoms and average at least three O-�acryloyl(polyalkylene oxide)! chains, wherein each of the polyalkylene oxide chains comprise from one to twenty alkylene oxide groups,

fifteen to seventy five percent by weight of a polyacrylated urethane, wherein the urethane oligomer has a molecular weight of about 2500 or less and an average of at least two acrylate groups

twenty to seventy percent by weight of polyacryloylated alkane polyols, wherein the alkane polyols contain up to twenty four carbon atoms and an average of at least three O-acryloyl groups, and

one to twenty five percent by weight of a mono vinyl functional reactive diluent.

20. The abrasion resistant article of claim 19, wherein the abrasion enhancing layer includes thirty to ninety five percent by weight of a acrylated oligomer or acrylated oligomer/acrylate monomer blend resin, and five to seventy percent by weight of a monovinyl functional reaction diluent.

21. The abrasion resistant article of claim 19, wherein the abrasion enhancing layer further includes a surfactant and a stabilizer.

22. The abrasion resistant article of claim 19, wherein the top coat layer further includes a surfactant and a stabilizer.

23. The abrasion resistant article of claim 19, wherein the polyol of the abrasion enhancing layer is a compound or mixture of the formula

(Polyol)--(O--CO--CH.dbd.CH.sub.2).sub.n,

wherein n is on average greater than or equal to 2.

24. The abrasion resistant article of claim 19, wherein the alkane polyols is selected from compounds having the general formula

(Polyol)--((--O--(CH--R).sub.s --).sub.m --O--CO--CH.dbd.CH.sub.2).sub.p

where, p is on average greater than or equal to 3, m is between 1 and 20, s is between 1 and 6, and R is H or alkyl.

25. The composition of claim 24, wherein R is H or methyl.

26. The abrasion resistant article of claim 9, wherein the abrasion enhancing layer further includes a polyacrylated urethane selected from compounds having the general formula

(Polyol)--(O--CO--CH.dbd.CH.sub.2).sub.n

wherein n is on average greater or equal to 3.