AU2013203003B2

AU2013203003B2 - Coatings for optical elements

Info

Publication number: AU2013203003B2
Application number: AU2013203003A
Authority: AU
Inventors: David Robert Diggins
Original assignee: Carl Zeiss Vision Australia Holdings Ltd
Current assignee: Carl Zeiss Vision Australia Holdings Ltd
Priority date: 2005-12-21
Filing date: 2013-04-08
Publication date: 2014-10-02
Anticipated expiration: 2026-12-21
Also published as: AU2013203003A1

Abstract

The invention provides an abrasion resistant coating composition for an optical element. The composition includes a polymerisable epoxy monomer having an average of at least two epoxy groups in the monomer molecule. The composition is capable of forming an abrasion resistant coating on an optical element after ionic polymerisation. The coating composition may also include an ionically polymerisable alkene monomer having an average of at least two polymerisable double bonds in the molecule.

Description

- 1 COATINGS FOR OPTICAL ELEMENTS The present application is a divisional application from Australian patent application number 2006326864, which claims priority from Australian Provisional Patent 5 Application No. 2005907161 filed on 21 December 2005, the contents of which is to be taken as incorporated herein by this reference. Field of the Invention 10 The present invention relates to compositions for use in forming coatings on optical elements, to coated optical elements, and to methods of coating optical elements. Background of the Invention 15 Optical elements, including ophthalmic lenses, sunglass lenses and other optical lenses, are commonly manufactured from plastic materials having good optical properties. However, plastic optical elements frequently lack optimal physical properties. As a consequence, it is common practice to coat plastic optical elements with coatings to improve one or more of the physical properties of the optical element. 20 To coat an optical element with an organic coating, a polymerisable coating composition is typically coated onto outer surfaces of the optical element and the composition is then cured to form the coating. Alternatively, optical elements can be coated using an in-mould coating process that involves coating an inner mould 25 surface with a polymerisable coating composition prior to casting or moulding an optical element. One common type of coating is an abrasion resistant or "hard" coat that is more resistant to abrasion than the plastic material from which the optical element is 30 formed. We have previously developed an abrasion resistant coating composition that is particularly useful for coating thermoplastic optical elements. C:\pof\ord\Document3.docx -2 The coating composition contains a relatively rigid multifunctional monomer and a relatively flexible difunctional monomer which are capable of co-reacting to form an abrasion resistant coating on the optical element. An advantage of this coating over the prior art at the time was its ability to be UV cured and to have excellent abrasion 5 resistance and coatability with anti-reflection (AR) coatings. Common thermoplastic materials that are used in the manufacture of optical elements, such as the polycarbonate of bisphenol A or a polyamide, can be coated with this abrasion resistant coating composition. However, we have found adhesion of this composition to thermoset materials, such as CR-39TM, FinaliteTM (a registered trademark of Sola International 10 Inc.), Spectralite T M (a registered trademark of Sola International Inc.), and high index polythiourethane systems is not optimal. The present invention aims to provide a method of coating an optical element and a coating composition that is UV curable and can be used for forming abrasion resistant 15 coatings on optical elements manufactured from both thermoset and thermoplastic materials. A reference herein to a patent document or other matter which is given as prior art is not to be taken as an admission that that document or matter was known or that the 20 information it contains was part of the common general knowledge. Summary of the Invention The present invention provides an abrasion resistant coating composition for an optical 25 element, the composition including: a polymerisable epoxy monomer having an average of at least two epoxy groups in the monomer molecule selected from the group consisting of ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl 30 ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 hexane diol diglycidyl ether, glycerine diglycidyl ether, pentaerythritol diglycidyl ether, bisphenol A diglycidyl ether (BPADGE), bisphenol-F diglycidyl ether, and their extended chain analogs, 1,4-butanediol diglycidyl ether, diglycidyl ethers of tetrabromo-bisphenol-A, epoxy based ethers of 4,4'-biphenylene, trimethylol propane triglycidyl ether, 35 pentaerythritol triglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, -3 diglycerol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexamethylene glycol diglycidyl ether, neopenthyl glycol diglycidyl ether, alicyclic hydrogenated bisphenol A diglycidyl ether, hydrogenated diglycidyl isophthalic acid ester, 3,4-epoxy cyclohexyl 5 methyl-3,4-epoxy cyclohexane carboxylate, bis(3,4-epoxy cyclohexyl)adipate; diglycidyl hydantoin, diglycidyl oxyalkyl hydantoin; aromatic bisphenol A diglycidyl ether, bisphenol A diglycidyl ether initial condensate, diphenylmethane diglycidyl ether, diglycidyl terephthalic acid ester, diglycidyl isophthalic acid ester, diglycidyl aniline, triglycidyl isocyanurate, triglycidyl cyanurate, triglycidyl hydantoin; aromatic triglycidyl para- or 10 meta-aminophenol, tetraglycidyl benzyl ethane, sorbitol tetraglycidyl ether, tetraglycidyl diaminophenyl methane, tetraglycidyl bisaminomethyl cyclohexane, phenol novolac epoxy resin, and cresol novolac epoxy resin; a (meth)acrylate monomer polymerisable with a cationic photoinitiator, the (meth)acrylate monomer having an average of at least two polymerisable double bonds 15 in the molecule; a hardness enhancer, which is a colloidal metal oxide; and a cationic photoinitiator; wherein the composition is capable of forming an abrasion resistant coating on an optical element after ionic polymerisation. 20 The present invention also provides an optical element having an abrasion resistant coating on a surface thereof, the abrasion resistant coating having been formed by polymerising the above abrasion resistant coating composition. 25 The present invention further provides a method of forming an abrasion resistant coating on a surface of an optical element, the method including: - providing an optical element having a surface to be coated; - coating a surface of the optical element with the above abrasion resistant coating composition; and 30 - polymerising the coating composition to form the abrasion resistant coating on the surface of the optical element. The present invention also provides a method of forming an abrasion resistant coating on a surface of an optical element, the method including: -4 - coating a surface of a mould section used to manufacture the optical element with the above abrasion resistant coating composition: - at least partially polymerising the coating composition; - assembling a mould containing the mould section; 5 - filling the mould with a cross-linkable polymeric casting composition; and - polymerising the casting composition so as to form the optical element with the abrasion resistant coating on a surface. We have found that the use of an epoxy monomer in an abrasion resistant coating 10 composition allows for the formation of an organic abrasion resistant coating on both thermoset and thermoplastic materials. Prior to the - A - development of the present invention there had been difficulties in forming UV curable abrasion resistant coatings having a desired level of abrasion resistance on thermoset optical elements. In general, coatings that have been applied to thermoset materials in the past have been thermally 15 cured. The few UV cured coatings that have been applied to thermoset materials have been found to have very poor abrasion resistance. We have found that an organic abrasion resistant coating can be formed on thermoset optical elements by including a polymerisabie epoxy monomer in the coating 20 composition. We have found that epoxy monomers can assist with adhesion of the coating to the optical element without significantly affecting the abrasion resistance of the coating. Therefore, we are able to form hard coats that have levels of abrasion resistance that are comparable to traditional polyacrylate hard coats. 25 The optical element may be a lens such as an ophthalmic lens, a camera lens, an instrument lens, or any other optically transparent material such as a domestic, commercial or residential window sheet or window, motor vehicle windscreen or window, transparent display panel and the like. In an embodiment of the invention, the optical element is an ophthalmic lens. 30 The optical element may be formed from any one of a variety of plastics. For example, the optical element may be formed from a thermoset or themoplastic material used for optical or ophthalmic lenses, such as CR-39TM, multi-functional (meth)acrylates, polyurethanes, polythiourethanes, polythioepoxides, polythioesters, polycarbonate, 35 episulfide polymers, and polyamide.

-5 The coating composition may be polymerised using a UV curing step. In this embodiment, the coating composition contains a cationic photoinitiator which may be a UV-activated cationic photoinitiator. 5 The coating composition also includes a hardness enhancer which is a metal oxide, such as colloidal silica. In an embodiment of the invention the hardness enhancer is (meth)acrylated or epoxylated colloidal silica. Detailed Description of the Invention 10 The present invention was developed as a result of a need for a UV curable abrasion resistant coating composition that could be coated directly onto a thermoset or thermoplastic plastic optical element and would provide a desired degree of abrasion resistance. 15 Coatings that can be photopolymerised, especially UV curable coatings, have significant process advantages over conventional thermally cured coatings. UV curing significantly reduces the time to process lenses and therefore reduces the time to meet a customer's requirements. Thermally cured coatings require a relatively long time to cure and 20 therefore the coating can become contaminated with airborne particulates. The limited time required for UV curing reduces the opportunity for optical elements to be contaminated with airborne particulates. Also, thermally cured resins generally have limited shelf life and pot life. 25 We have previously developed a UV curable abrasion resistant coating composition containing a relatively rigid multifunctional crosslinking monomer and a relatively flexible difunctional monomer (see published International patent application W02003/05201 1). An advantage of this prior art coating composition is that it can be used to form an abrasion resistant coating on plastic optical elements without the need for an 30 intermediate or primer layer to assist with adhesion of the abrasion resistant coating to the optical element. In practice, the prior art coating composition is particularly useful for coating thermoplastic optical elements, such as those formed from the polycarbonate of 35 bisphenol A or a polyamide. It is thought that the presence of a solvent in the coating -6 composition assists in adhesion of the abrasion resistant coating layer to thermoplastic substrates. However, this solvent assisted adhesion is not effective for thermoset materials. 5 We have discovered that a coating composition containing an epoxy monomer and another polymerisable (meth)acrylate monomer, can be used to form an abrasion resistant coating layer on thermoset materials. Without being bound by theory, we think that the epoxy groups of the epoxy monomer are able to react with free hydroxyl groups on the surface of the thermoset material to form covalent bonds to thereby assist with 10 the adhesion of the abrasion resistant coating to the surface. The optical element may be any optically transparent material that requires an abrasion resistant coating layer. In an embodiment of the invention, the optical element is an ophthalmic lens. The optical element can be a thermoset polymer such as a polymer of 15 diethylene glycol bis(allyl carbonate) (e.g. CR-39

TM

, a trade mark of PPG Industries, Inc), a polyacrylate copolymer (e.g. Spectralite T M , a trade mark of Sola International Inc.), a thiolene polymer (e.g. Finalite

TM

, a trade mark of Sola International Inc.), a urethane polymer (e.g. Trivex

TM

, a trade mark of PPG), a thiourethane polymer (e.g. high index MR series of materials from Mitsui Chemicals) or a thioepoxy polymer (e.g a high index 20 resin from Mitsubishi Gas). Whilst the coating composition of the present invention may be particularly suited to forming an abrasion resistant coating on thermoset materials, we have found that it can also be used on thermoplastic materials and, therefore, the optical element could alternatively be a thermoplastic material such as the polycarbonate polymer of bisphenol A or a polyamide. 25 The abrasion resistance of a coating layer can be measured using standard ophthalmic industry tests. We have found that the levels of Bayer abrasion resistance that can be achieved with the coating of the present invention are WO 2007/070976 PCT/AU2006/001986 -7 good. Furthermore, the levels of steel wool abrasion resistance that can be achieved are excellent. In this context, we use a star rating to rank abrasion resistance. This star rating is based on a ratio of haze developed for an uncoated CR-39TM lens to that developed for a sample under evaluation when 5 subjected to an abrasion test. The star rating based on haze ratios is as specified below. Steel Wool Abrasion Resistance 10 <0.5 no stars 0.5-1.0 * 1.0-1.5 ** 1.5-2.5 *** 2.5-10 15 >10 Bayer Abrasion Resistance <0.5 no stars 20 0.5-1.0 * 1.0-1.5 ** 1.5-2.5 *** 2.5-5 >5 25 An abrasion resistant coating is considered to be good if, using the standard ophthalmic industry tests, it has a rating of 3 stars, very good if it has a rating of 4 stars and excellent if it has a rating of 5 stars in the standard steel wool or Bayer abrasion tests. For comparative purposes, uncoated CR-39TM has a 30 Bayer abrasion resistance and steel wool abrasion resistance rating of 2 stars. Uncoated polycarbonate has a Bayer abrasion resistance and steel wool abrasion resistance rating of 0 stars.

WO 2007/070976 PCT/AU2006/001986 The present invention provides a method of forming an abrasion resistant coating on an optical element. The method includes a step of coating the optical element with a coating composition. This may involve applying the 5 coating composition to a preformed optical element or it may involve applying the coating during the formation of the optical element, such as in an in-mould coating process. Any of the techniques that are used for that purpose in the art can be used to 10 coat the optical element, including dip coating, spin coating, flow coating, spray coating and in-mould coating. Spin coating is the preferred method of applying the coating to both thermoset and thermoplastic materials. The coating can also be applied to thermoset materials such as CR-39TM, SpectraliteTM or Finalite TM by in-mould coating. 15 Depending on the use of the optical element, all or part of any of the surface(s) of the element may be coated. For example, ophthalmic lenses have front and back surfaces that are susceptible to abrasion and therefore it may be preferred that both surfaces are coated. Alternatively, with a semifinished ophthalmic 20 lens the front surface may need to be coated with a conventional coating and the other surface may be coated with a coating composition of the present invention after that surface has been generated to the appropriate surface power. Alternatively, a coating composition of the present invention may be applied to the front surface and the other surface may be coated with either a 25 coating composition of the present invention or a conventional coating after that surface has been generated to the appropriate surface power. Optical lenses for use in an optical instrument may only have one lens surface exposed and therefore it may only be necessary to coat the exposed surface. The abrasion resistant coating composition of the present invention includes a 30 polymerisable epoxy monomer having an average of at least two epoxy groups in the monomer molecule wherein the composition is capable of forming an -9 abrasion resistant coating on an optical element after polymerization. The coating composition also includes a (meth)acrylate monomer having an average of at least two polymerisable double bonds in the molecule. 5 As a general principal, in order to achieve an abrasion resistant coating, it is ideal to use monomers that form a highly crosslinked network when polymerised. Therefore, the epoxy monomer is preferably a polymerisable monomer having two epoxy groups and more preferably three or more epoxy groups. As used herein, the term epoxy group refers to a group of formula 10 0

R

1

R

2 C - CR 3

R

4 . Epoxy monomers that can be used include, but are not limited to difunctional, trifunctional 15 and other multi-functional epoxy monomers. The epoxy monomer may also contain other functional groups. For example, the epoxy monomer may be a silane having two or more epoxy groups per molecule. Specific examples of polymerisable epoxy monomers include ethylene glycol diglycidyl 20 ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 hexanediol diglycidyl ether, glycerine diglycidyl ether, pentaerythritol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol triglycidyl ether, glycerol triglycidyl 25 ether, diglycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, bisphenol-A diglycidyl ether (BPADGE), bisphenol-F diglycidyl ether, and their extended chain analogs, 1,4-butanediol diglycidyl ether, diglycidyl ethers of tetrabromo-bisphenol-A, epoxy based ethers of 4,4' biphenylene, such as 4, 4'-diglycidyloxybiphenyl, and so on. 30 WO 2007/070976 PCT/AU2006/001986 - 10 Specific examples of polymerisable epoxy monomers having an average of two epoxy groups in the molecule include aliphatic polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexamethylene glycol diglycidyl ether, neopenthyl glycol diglycidyl 5 ether, glycerin diglycidyl ether; pentaerythritol diglycidyl ether, alicyclic hydrogenated bisphenol A diglycidyl ether, hydrogenated diglycidyl isophthalic acid ester, 3,4-epoxy cyclohexyl methyl-3,4-epoxy cyclohexane carboxylate, bis(3,4-epoxy cyclohexyl)adipate; diglycidyl hydantoin, diglycidyl oxyalkyl hydantoin; aromatic bisphenol A diglycidyl ether, bisphenol A diglycidyl ether 10 initial condensate, diphenylmethane diglycidyl ether, diglycidyl terephthalic acid ester, diglycidyl isophthalic acid ester, and diglycidyl aniline. Specific examples of polymerisable epoxy monomers having an average of three epoxy groups in the molecule include aliphatic trimethylol propane 15 triglycidyl ether, pentaerythritol triglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, triglycidyl isocyanurate, triglycidyl cyanurate, triglycidyl hydantoin; and aromatic triglycidyl para- or meta-aminophenol. Specific examples of polymerisable epoxy monomers having an average of four 20 epoxy groups in the molecule include diglycerol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, tetraglycidyl benzyl ethane, sorbitol tetraglycidyl ether, tetraglycidyl diaminophenyl methane, and tetraglycidyl bisaminomethyl cyclohexane. 25 Specific examples of polymerisable epoxy monomers having an average of two to several epoxy groups include phenol novolac epoxy resin, and cresol novolac epoxy resin. Epoxy monomers that have the highest crosslink densities when polymerised 30 may be particularly suitable. As a general rule, the higher the crosslink density, the higher the abrasion resistance. With this criterion, low molecular weight epoxy monomers with high functionality are preferred. With the above list the -11 trifunctional and tetrafunctional epoxy monomers are suitable. Examples of such monomers include trimethylol propane triglycidyl ether, pentaerythritol triglycidyl ether, glycerol triglycidyl ether, triglycidyl isocyanurate, triglycidyl cyanurate, triglycidyl hydantoin, pentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, and tetraglycidyl 5 benzyl ethane. The above listed epoxy monomers may be used alone or combined to make epoxy mixtures for use in the compositions described herein. 10 The (meth)acrylate monomer having an average of at least two polymerisable double bonds in the molecule that is used with the epoxy monomer can be an acrylate and/or a methacryiates The monomer is copolymerisable with the epoxy molecule when subjected to photoinitiation, and is of high crosslink density when polymerised. The (meth)acrylate monomer may be cationically polymerisable. 15 The (meth)acrylate monomer having an average of at least two polymerisable double bonds in the molecule is an organic molecule having a carbon based backbone with two or more polymerisable double bonds. Due to the variety of high crosslinking (meth)acrylate monomers commercially available, such criteria are readily satisfied with 20 (meth)acrylate monomers. Any reference to the term (meth)acrylate in this specification is intended to include reference to acrylate and/or methacrylate. The (meth)acrylate monomer may contain three or more double bonds and a relatively rigid backbone. Most suitably rigid backbones include those that contain ring moieties such as 5, 6 and 7 membered aromatic or aliphatic cyclic or heterocyclic rings. The (meth)acrylate group may 25 be bonded to the backbone either directly or indirectly. Additionally, other functional groups may be incorporated within a single monomer molecule.

- 12 By way of example, suitable (meth)acrylate monomers may be selected from the list consisting of pentaerythritol tetraacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, trimethylol propyl triacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, 2,2,4,4,6,6-hexahydro-2,2, 4,4,6, 6-hexakis(2-((2-methyl-1 -oxo-2 5 propenyl)oxy)ethoxy)-1 ,3,5,2,4,6-triazatriphosphorine, U6HA (a hexafunctional urethane (meth)acrylate), U4HA (a tetrafunctional urethane (meth)acrylate), tricyclodecane dimethanol diacrylate and tris(2-hydroxyethyl)isocyanurate diacrylate. The (meth)acrylate monomer may be selected from one or more of the group consisting of: pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate. The 10 (meth)acrylate monomer may also be a mixture of any two or more of the listed monomers. The ratio of epoxy monomer to (meth)acrylate monomer in the composition can be varied depending on the desired performance of the hard coat. The amount of epoxy monomer in 15 the composition will affect the degree of adhesion of the abrasion resistant coating to a thermoset substrate. Additionally, the ratio of epoxy monomer to (meth)acrylate monomer can be adjusted so that the composition, and ultimately the abrasion resistant coating formed, includes additives such as hardness enhancers. The ratios of epoxy monomer to (meth)acrylate monomer that can be used will depend on the specific monomers used and 20 are able to be determined empirically. By way of non-limiting example, we have found that a ratio of epoxy monomer and ionically polymerisable alkene monomer of about 2:3 (w/w) yields an abrasion resistant coating when the epoxy monomer is trimethylol propane triglycidyl ether and the (meth)acrylate monomer is pentaerythritol tetraacrylate. The minimum amount of epoxy monomer required to achieve satisfactory adhesion is 10% 25 w/w monomer. However, at these low levels of epoxy monomer, the ability to cure, and therefore the abrasion resistance, is compromised. Alternatively, from a theoretical perspective, satisfactory resins could be formulated at 100% w/w -13 epoxy monomer concentrations. However, in practice, epoxy monomers of sufficient crosslink density are not readily available and therefore commercially viable resin formulations require an amount of a high crosslinking (meth)acrylate monomer. 5 The composition may also include a solvent. If a thermoplastic material is to be coated, the composition preferably contains a solvent that is sufficiently aggressive to partially dissolve the thermoplastic but not so aggressive as to cause haze. This balance in aggressiveness is most easily achieved by using a mixture of an aggressive solvent, such as a ketone solvent (eg. methyl isobutyl ketone) an ester solvent (eg ethyl acetate), or an 10 ether solvent, and a non-aggressive solvent, such as a lower alcohol (eg. isopropyl alcohol). The term 'aggressive solvent' is intended to mean a solvent that affects the polymer network of an adjoining polymer layer or substrate, whilst the term 'non aggressive solvent' is intended to mean a solvent to which an adjoining polymer layer or substrate is substantially inert. The use of one or more aggressive solvents in the coating 15 composition assists adhesion of the abrasion resistant coating layer to the thermoplastic substrate, such as the polycarbonate of bisphenol A or a polyamide, as the solvent disrupts the thermoplastic polymer network at the abrasion resistant coating-substrate interface to allow the intermingling of polymer chains from the abrasion resistant coating layer and the polycarbonate substrate. In general, some of the solvent evaporates prior to 20 polymerisation but it is also necessary to remove substantially all of the solvent from the composition prior to polymerisation. The solvent removal can be facilitated by heating or time. In the case of a thermoset material, the choice of solvent is not critical. As mentioned 25 previously, it is thought that adhesion is achieved by epoxy groups of the coating reacting with the hydroxyl groups or other reactive functional groups on the surface of the substrate. The composition also includes a hardness enhancer which is a metal oxide. More 30 specifically, the incorporation of metal oxide sols into the coating composition is beneficial - 14 for abrasion resistance. The metal oxide sol generally incorporated is colloidal silica. If high index systems are required other high refractive index metal oxides such as titanium dioxide, zirconium dioxide, antimony oxide, and so on can be utilised. In order to disperse and copolymerise these metal oxides into an organic matrix the metal oxide sols may 5 need to be functionalised with a polymerisable functional group. The functionality facilitates dispersion of the colloidal silica and subsequent copolymerisation of the silica with the monomers present in the resin. Non-limiting examples of suitable silica include (meth)acrylated and epoxylated colloidal silica. A specific means to functionalise colloidal silica is to graft methacryloxy propyl trimethoxy silane or glycidoxy propyl trimethoxy silane 10 onto the surface of the silica. (Meth)acrylated or epoxylated colloidal silicas are generally dispersed in polymerisable monomers. A common dispersant monomer for commercial acrylated colloidal silica preparations is hexane diol diacrylate. In order to minimise the presence of a low 15 crosslinking monomer in the coating composition it is preferable to use a dispersant monomer that is the high crosslinking monomer that is used in the formulation. The amount of (meth)acrylated or epoxylated colloidal silica that is present in the composition may vary between 0% and about 50% (w/w solids) however, the amount used will depend on the amount of high cross linking monomer that is present in the composition. 20 The colloidal silica can be made in accordance with the procedures described in United States patents 4,348,462 and 5,614,321 , both of which are incorporated herein solely for the purpose of providing procedures for preparing colloidal silica. Alternatively, commercial (meth)acrylated silicas are available under the product name of FSD 100 25 (available from General Electric) or as the product series Highlink (available from Clariant). The composition also contains a cationic photoinitiator. Ionic initiation is required for polymerisation of epoxy monomers. Any of the many compounds known to initiate 30 polymerization by a cationic mechanism may be used. Compounds known to initiate -15 polymerisation by a cationic mechanism include, for example, diaryliodonium salts, triarylsulfonium salts, diaryliodosonium salts, dialkylphenylsulfonium salts, dialkyl(hydroxydialkylphenyl)sulfonium salts and ferrocenium salts. Such salts may be modified by the attachment of alkyl, alkoxy, siloxy and the like groups. Particularly useful 5 initiators include (4-n-decyloxyphenyl) phenyliodonium hexafluoroantimonate (IOC10), (4 n-decyloxyphenyl)diphenylsulfonium hexafluoroantimonate (SOC10) and S-methyl-S-n dodecylphenacylsulfonium hexafluoroantimonate (DPS-Ci C12). The amount of polymerisation initiator used and the conditions of polymerisation will be readily determined by those skilled in the art, or can easily be determined empirically. Typically, 10 the polymerisation initiator is employed in concentrations ranging from 0.01 to 10% w/w of solids. The coating composition may also contain flow agents. Flow agents are typically based on a polydimethylsiloxane or a fluoropolymer backbone. Suitable flow agents that are based 15 on a polydimethylsiloxane backbone can be sourced from companies such as Tego Chemie Service or Byk-Chemie. Specific suitable flow agents with a polydimethylsiloxane backbone include Byk 371 and Byk 300 from Byk-Chemie. Suitable flow agents based on a fluoropolymer backbone can be sourced from Daikin or 3M. Specific suitable flow agents with a fluoropolymer backbone include FC-431 from 3M and NS-1606 from Daikin. 20 The thickness of the coating can be controlled by adjusting the amount of solids in the composition and the parameters of the particular coating process that is used. For example, if the coating is applied by spin coating, the thickness of the coating will depend on the spin speed. Similarly, if the coating is applied by dip coating, the thickness will 25 depend on the pull up speed. Preferably, the level of solids in the composition is about 50% by weight. The coating composition may also contain other additives such as stabilisers, antioxidants, flexibilisers, reinforcing fillers, surfactants, flow agents, levelling agents, - 16 refractive index modifiers (e.g. titanium dioxide, zirconium dioxide, antimony dioxide) and antistatic agents. The method of the present invention also includes a step of polymerising the coating 5 composition to form the abrasion resistant coating. The composition may be cured using a UV curing step. In an embodiment of the invention, the composition is cured by UV initiated cationic polymerisation. Cationic polymerisation enables epoxy groups of the epoxy monomer to react with free hydroxyl or other functional groups on the surface of the thermoset material. The use of catonic photoinitiators also enables the polymerisation of 10 the photocationically polymerisable (meth)acrylate monomer without oxygen inhibition. The composition of the present invention can also be used in an in-mould coating process. In mould coating processes are known in the art - for example see published International patent application WO 01/21375, which is incorporated herein by reference 15 solely for the purpose of exemplifying in-mould coating processes. An in-mould coating process involves applying the coating composition to a surface of a mould section that is part of a mould used to cast the optical element. The composition is then partially cured by UV initiated cationic photopolymerisation. In order to prevent epoxy 20 groups from reacting with the mould surface, it is necessary to prevent the silanol groups of a glass mould surface reacting with the epoxide. This is achieved by capping the silanol groups with an inert material. Following partial polymerisation of the abrasion resistant coating composition mould 25 pieces are fitted together to form a mould cavity that is coated with the abrasion resistant coating composition in a partially polymerised form. Thermosetting monomer is then poured into the mould and the plastic is cured in the usual way. The moulded article is finally removed from the mould to provide the coated article. This then provides an in mould coating process for forming an optical element that has a good level of abrasion 30 resistance.

-17 It will be appreciated from the foregoing discussion that the coating composition is suitable for coating directly onto a surface of a pre-formed optical element. However, the optical element may contain further coating layers in addition to the abrasion resistant coating 5 layer to form a multi-layer coating on the optical element. For example, the abrasion resistant coating layer may be coated over a second abrasion resistant coating on the surface of the optical element. Further, multi-layer coatings, such as a multi-layer coating that forms, for instance, an anti-reflection (AR) stack, may be coated over the abrasion resistant coating layer of the invention. 10 The present invention also provides an optical element, such as an ophthalmic lens, having an abrasion resistant coating on a surface thereof, the abrasion resistant coating having been formed by polymerising an abrasion resistant coating composition as described previously. 15 Description of Embodiments of the Invention Several examples will now be provided in order to illustrate embodiments of the present invention. However, it is to be understood that the following description is not to limit the 20 generality of the above description. The following composition was used in a spin coating process for lenses manufactured from a variety of plastics. 25 WO 2007/070976 PCT/AU2006/001986 - 18 Example 1 - Coating Composition A coating composition having the following components was prepared as outlined below: 5 Component Weight (g) % Pentaerythritol 5.9g 40% (w/w of tetraacrylate monomer) Trimethylol propane 23.8g 60% (w/w of triglycidyl ether monomer) Acrylated colloidal 22.6g 15% (w/w of solids) silica Isopropyl alcohol 20.3g 50% (w/w of solvent) Methyl isobutyl ketone 25.0g .50% (w/w of solvent) Triarylsulfonium 2.5g 5% (w/w of solids) hexafluorophoshonate Byk 371 0.3g 0.60% (w/w of solids) Solids content 50% (w/w) The acrylated colloidal silica was supplied as a concentrate in pentaerythritol tetraacrylate. On analysis the chemical breakdown of the concentrate was as 10 follows: Silica Content 43.0% Solids content of silica 77.3% Isopropanol 21.0% 15 Water 1.70% To a 200ml beaker was added 5.9g of pentaerythritol tetraacrylate, 23.8g of trimethylol propane triglycidyl ether, 22.6g of acrylated colloidal silica, 20.3g of WO 2007/070976 PCT/AU2006/001986 -19 isopropyl alcohol, 25.Og of methyl isobutyl ketone, 0.3g of Byk 371 and 2.5g of triarylsulfonium hexafluorophoshonate. The beaker was covered with aluminium foil to prevent stray UV initiating polymerisation. 5 Example 2 - Coating of Lenses Lenses were spin coated with the coating composition of Example 1 by dispensing 3ml of resin at the centre of a lens spinning at 500 rpm. Lenses were spun for a period of 10 seconds after the dispensing of resin. This 10 ensured a coating thickness of approximately 6ptm. Prior to curing, coated lenses were exposed to infrared heat from ceramic heaters to remove solvent. The coated lenses were then irradiated with UV light from a d-lamp from Fusion Systems with a maximum intensity of 12 Wcm 2 15 (as measured in the UVA region of the spectrum), for 24 seconds, corresponding to a final dose of 1.0 Jcm 2 (as measured in the UVA region of the spectrum). The prepared lenses were then tested using the standard industry abrasion 20 tests described earlier. Lens tested were those having a hard coat only, and those having a hard coat and an anti-reflection (AR) coat that was applied using standard procedures. Example 2.1 - CR-39 Lens 25 Hard Coat Only Primary Adhesion Pass 3 Hour Boil Pass 30 Outdoor Weathering Pass Steel Wool WO 2007/070976 PCT/AU2006/001986 -20 Bayer Abrasion *** AR Coated over Hard Coat 5 Primary Adhesion Pass Salt Water Boil Pass Outdoor Weathering Pass 10 Steel Wool Bayer Abrasion **** Example 2.2 - Polycarbonate lens 15 Hard Coat Only Primary Adhesion Pass 3 Hour Boil Pass Outdoor Weathering Pass 20 Steel Wool Bayer Abrasion *** AR Coated over Hard Coat 25 Primary Adhesion Pass Salt Water Boil Pass Outdoor Weathering Pass 30 Steel Wool Bayer Abrasion

****

WO 2007/070976 PCT/AU2006/001986 -21 Example 2.3 - Spectralite TM (Polyacrvlate) Hard Coat Only 5 Primary Adhesion Pass 3 Hour Boil Pass Outdoor Weathering Pass Steel Wool 10 Bayer Abrasion AR Coated over Hard Coat (polycarbonate) Primary Adhesion Pass 15 Salt Water Boil Pass Outdoor Weathering Pass Steel Wool Bayer Abrasion **** 20 Example 2.4 - Finalite (Thiolene) Hard Coat Only 25 Primary Adhesion Pass 3 Hour Boil Pass Outdoor Weathering Pass Steel Wool **** 30 Bayer Abrasion *** WO 2007/070976 PCT/AU2006/001986 -22 AR Coated over Hard Coat Primary Adhesion Pass Salt Water Boil Pass 5 Outdoor Weathering Pass Steel Wool Bayer Abrasion **** 10 Example 2.5 - MR7 (Thiourethane) Hard Coat Only Primary Adhesion Pass 15 3 Hour Boil Pass Outdoor Weathering Pass Steel Wool **** Bayer Abrasion *** 20 AR Coated over Hard Coat Primary Adhesion Pass Salt Water Boil Pass 25 Outdoor Weathering Pass Steel Wool Bayer Abrasion **** 30 WO 2007/070976 PCT/AU2006/001986 -23 Finally, it will be appreciated that there may be other variations and modifications made to the embodiments described herein that are also within the scope of the present invention.

Claims

1. An abrasion resistant coating composition for an optical element, the composition including: 5 a polymerisable epoxy monomer having an average of at least two epoxy groups in the monomer molecule selected from the group consisting of ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 hexane diol 10 diglycidyl ether, glycerine diglycidyl ether, pentaerythritol diglycidyl ether, bisphenol-A diglycidyl ether (BPADGE), bisphenol-F diglycidyl ether, and their extended chain analogs, 1,4-butanediol diglycidyl ether, diglycidyl ethers of tetrabromo-bispheno-A, epoxy based ethers of 4,4'-biphenylene, trimethylol propane triglycidyl ether, pentaerythritol triglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, diglycerol tetraglycidyl ether, 15 pentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexamethylene glycol diglycidyl ether, neopenthyl glycol diglycidyl ether, alicyclic hydrogenated bisphenol A diglycidyl ether, hydrogenated diglycidyl isophthalic acid ester, 3,4-epoxy cyclohexyl methyl-3,4-epoxy cyclohexane carboxylate, bis(3,4-epoxy cyclohexyl)adipate; diglycidyl hydantoin, diglycidyl oxyalkyl hydantoin; aromatic bisphenol A 20 diglycidyl ether, bisphenol A diglycidyl ether initial condensate, diphenylmethane diglycidyl ether, diglycidyl terephthalic acid ester, diglycidyl isophthalic acid ester, diglycidyl aniline, triglycidyl isocyanurate, triglycidyl cyanurate, triglycidyl hydantoin; aromatic triglycidyl para- or meta-aminophenol, tetraglycidyl benzyl ethane, sorbitol tetraglycidyl ether, tetraglycidyl diaminophenyl methane, tetraglycidyl bisaminomethyl cyclohexane, phenol novolac epoxy 25 resin, and cresol novolac epoxy resin; a (meth)acrylate monomer polymerisable with a cationic photoinitiator, the (meth)acrylate monomer having an average of at least two polymerisable double bonds in the molecule; a hardness enhancer, which is a colloidal metal oxide; and 30 a cationic photoinitiator; wherein the composition is capable of forming an abrasion resistant coating on an optical element after ionic polymerisation.

2. An abrasion resistant coating composition according to claim 1, wherein the epoxy 35 monomer is selected from one or more of the group consisting of: ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol Cfilename> -25 diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 hexane diol diglycidyl ether, glycerine diglycidyl ether, pentaerythritol diglycidyl ether, bisphenol-A diglycidyl ether (BPADGE), bisphenol-F diglycidyl ether, and their extended chain analogs, 5 1,4-butanediol diglycidyl ether, diglycidyl ethers of tetrabromo-bisphenol-A, and epoxy based ethers of 4,4'-biphenylene.

3. An abrasion resistant coating composition according to claim 1, wherein the epoxy monomer has an average of at least three epoxy groups per molecule. 10

4. An abrasion resistant coating composition according to claim 3, wherein the epoxy monomer is selected from one or more of the group consisting of: trimethylol propane triglycidyl ether, pentaerythritol triglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, and di pentaerythritol 15 tetraglycidyl ether.

5. An abrasion resistant coating composition according to any one of claims 1 to 4, wherein the (meth)acrylate monomer has an average of at least three polymerisable double bonds in the molecule. 20

6. An abrasion resistant coating composition according to claim 5, wherein the (meth)acrylate monomer has an average of at least four polymerisable double bonds in the molecule. 25

7. An abrasion resistant coating composition according to claim 6, wherein the (meth)acrylate monomer is selected from one or more of the group consisting of: pentaerythritol tetraacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, trimethylol propyl triacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, 2,2,4,4,6,6 hexahydro-2,2,4,4,6,6-hexakis(2-((2-methyl-1 -oxo-2-propenyl)oxy)ethoxy)- 1, 3,5,2,4,6 30 triazatriphosphorine, U6HA (hexafunctional urethane (meth)acrylate), U4HA (tetrafunctional urethane (meth)acrylate), tricyclodecane dimethanol diacrylate, and tris(2-hydroxyethyl) isocyanurate diacrylate.

8. An abrasion resistant coating composition according to any one of claims 1 to 7, 35 wherein the ionically polymerisable alkene monomer is pentaerythritol tetraacrylate. <Filename> -26

9. An abrasion resistant coating composition according to any one of claims 1 to 8, wherein the colloidal metal oxide is functionalised with a polymerisable group.

10. An abrasion resistant coating composition according to any one of claims 1 to 9, 5 wherein the hardness enhancer is (meth)acrylated colloidal silica or epoxylated colloidal silica.

11. An abrasion resistant coating composition according to any one of claims 1 to 10, further including a solvent. 10

12. An abrasion resistant coating composition according to claim 11, wherein the solvent is a mixture of: (a) one or more of solvents selected from the group consisting of: a ketone solvent, an ester solvent, and an ether solvent; and 15 (b) a lower alcohol.

13. An optical element having an abrasion resistant coating on a surface thereof, the abrasion resistant coating having been formed by polymerising an abrasion resistant coating composition according to any one of claims 1 to 12. ?0

14. An optical element according to claim 13, wherein the optical element is formed from a thermoset polymer selected from one or more of the group consisting of: a polymer of diethylene glycol bis(allyl carbonate), an acrylate polymer, a thiolene polymer, a urethane polymer, a thiourethane polymer, and a thioepoxide polymer. 25

15. An optical element according to claim 13, wherein the optical element is formed from a thermoplastic polymer selected from one or more of the group consisting of: a polycarbonate polymer of bisphenol A, and a polyamide. 30

16. An optical element according to any one of claims 13 to 15, wherein when an uncoated diethylene glycol bis(allyl carbonate) lens and the optical element are subjected to a Bayer abrasion test, a ratio of haze developed for the uncoated lens to haze developed for the optical element is 1.5 - 2.5 or greater. 35

17. An optical element according to any one of claims 13 to 16, wherein when an uncoated diethylene glycol bis(allyl carbonate) lens and the optical element are subjected to a <4-,. - 27 steel wool abrasion test, a ratio of haze developed for the uncoated lens to haze developed for the optical element is 1.5-2.5 or greater.

18. An optical element according to any one of claims 13 to 17, wherein the optical 5 element is an ophthalmic lens.

19. An optical element according to any one of claims 13 to 18, wherein the abrasion resistant coating is formed directly on the surface of the optical element. 10

20. A method of forming an abrasion resistant coating on a surface of an optical element, the method including: - providing an optical element having a surface to be coated; - coating a surface of the optical element with a coating composition according to any one of claims 1 to 12; and 15 - polymerising the coating composition to form the abrasion resistant coating on the surface of the optical element.

21. A method of forming an abrasion resistant coating according to claim 20, wherein the optical element is in accordance with any one of claims 13 to 19. ?0

22. A method of forming an abrasion resistant coating according to claim 20 or claim 21, wherein the step of coating the optical element includes applying the coating composition directly on the surface of the optical element. 25

23. A method of forming an abrasion resistant coating according to any one of claims 20 to 22, wherein the step of polymerising the coating composition includes a step of irradiating the coating composition with UV light.

24. A method of forming an abrasion resistant coating according to claim 23, wherein the 30 coating composition is irradiated with UV light for a period of 5 to 60 seconds at a dose greater than about 5 Jcm- 2 with a maximum intensity greater than about 0.5 Wcm-2.

25. A method of forming an abrasion resistant coating on a surface of an optical element, the method including: 35 - coating a surface of a section of a mould used to manufacture the optical element with a coating composition according to any one of claims 1 to 12; <filename> - 28 - at least partially polymerising the coating composition; - assembling a mould containing the mould section; - filling the mould with a cross-linkable polymeric casting composition; and - polymerising the casting composition so as to form the optical element with the 5 abrasion resistant coating on a surface. <filename>