AU709040B2

AU709040B2 - High index/high abbe number composition

Info

Publication number: AU709040B2
Application number: AU56807/96A
Authority: AU
Inventors: Ian Roger Bateman; Bohdan Grzegorz Cieslinski; David Robert Diggins; Huan Kiak Toh
Original assignee: Sola International Pty Ltd
Current assignee: Carl Zeiss Vision Australia Holdings Ltd
Priority date: 1995-05-30
Filing date: 1996-05-24
Publication date: 1999-08-19
Anticipated expiration: 2016-05-24
Also published as: AU5680796A

Description

WO 96/38486 PCT/AU96/00314 1 HIGH INDEX/HIGH ABBE NUMBER COMPOSITION The present invention relates to the manufacture of plastic optical articles such as video discs and ophthalmic lenses.

The most widely used plastic ophthalmic lens material is polymerised diethylene glycol bis (allyl carbonate). This polymer has proved a satisfactory material for the manufacture of ophthalmic lenses because of a combination of features, including excellent transmission, resistance to discolouration, high strength and high impact resistance. The material has a reasonable abrasion resistance and can be coated to improve that resistance.

Lenses formed from polymers including divinyl benzene are generally brittle and have a high yellowness index.

In Australian Patent Application 81216/87, the entire disclosure of which is incorporated herein by reference, applicant describes a cross-linkable casting composition including at least polyoxyalkylene glycol diacrylate or dimethacrylate and at least one poly functional unsaturated cross-linking agent. Whilst the lenses produced from the prior art compositions provide advances in the art, difficulties may be encountered in certain applications. For example, difficulties may be encountered in some patients in fitting lenses made from such compositions. Eye discomfort, including eye fatigue problems, may beencountered. Moreover, such lenses have been found to be cosmetically unattractive.

Further, in Australian Patent Application 75160/91, the entire disclosure of which is incorporated herein by reference, applicant describes a polyoxyalkylene glycol diacrylate or dimethacrylate; a monomer including a recurring unit derived from at least one radical-polymerisable bisphenol monomer capable of forming a homopolymer having a high refractive index of more than 1.55; and a urethane monomer having 2 to 6 terminal groups selected from a group comprising acrylic and methacrylic groups.

Japanese Patent Application 63-309509 to Showa Denko KK discloses the formation of a prepolymer of divinyl benzene and a polythiol compound which may be used in the formation of optical materials with high refractive indexes.

Japanese Patent Application 63-19498 to Mitsubishi Gas discloses a high WO 96/38486 PCT/AU96/00314 2 refractive index composition of divinyl benzene and a thiol compound. However optical lenses produced thereby exhibit unacceptable strain characteristics and cure times.

However, there remains a need in the prior art for optical articles of very high refractive indexes, high Abbe number, high rigidity, very low densities and excellent colour, that still retain excellent mechanical properties.

Accordingly, it is an object of the present invention to overcome, or at least alleviate, one or more of the difficulties related to the prior art.

Accordingly, the present invention provides a cross-linkable polymeric casting composition including an effective amount of an acrylic or methacrylic monomer which provides high rigidity and low colour dispersion (High Abbe number) to the final product; a di- or polythio compound; a di- or polyvinyl monomer; and optionally a polymerisable comonomer.

The casting composition may be heat and/or UV-curable.

The optical article formed from the casting composition of the present invention may exhibit a refractive index in the high to very high -index range, high Abbe number, low density and high rigidity.

By the term "high refractive index", as used herein, we mean a polymer having a refractive index of at least approximately 1.55, preferably 1.57. By the term "very high refractive index" as used herein, we mean a polymer having a refractive index of approximately 1.59 or above, preferably 1.60 or above.

By the term "low density", as used herein, we mean a density in the range of approximately 1.15 to 1.25 g cm-3.

By the term "Abbe number", as used herein, we mean the number expressing the extent to which the shorter and longer wavelengths of light are separated by refraction through a lens, that is the amount the lens disperses the various colours. The greater the number, the smaller the dispersion. The Abbe number may be calculated utilising the following formula: fD I nF nc where n refractive index D 589.3 nm (sodium) yellow F 486.1 nm blue green C 656.3 nm red By the term "high Abbe number" as used herein, we mean a polymer having an Abbe number of at least approximately 35, preferably 38 or above.

By the term "high rigidity" as used herein, we mean a polymer having a glass transition temperature (Tg) of at least approximately 65°C, preferably approximately 70 0 C, more preferably approximately 75°C or above.

The acrylic or methacrylic monomer (Component A) may be selected from acrylates or methacrylate derivatives of a cycloolefin. An acrylate or methacrylate derivative of tricyclodecane is preferred.

The acrylate or methacrylate derivative may be of the formula: n o-ewhere R can be H or CH3 a 1-3, b= 1-3, m 0-6, n =0-6.

Z is a spacer group selected from one or more of the following H3 CH2 2- 20 or CH2.. -CH2 or derivatives thereof; wherein p 1-4 A tricyclodecane dimethanol diacrylate or dimethacrylate is preferred.

A tricyclodecane dimethanol diacrylate or diacryloyl oxymethyl tricyclodecane of the following formula is preferred.

N

WI

0 0

CH

2

=CH-C-O-CH

2

CH

2 -0-C-CH-=CH 2

(DCPA)

The acrylic or methacrylic monomer may alternatively or in addition be selected from highly rigid, high Abbe No. polyfunctional acrylates or methacrylates. Pentaerythritol tetracrylate (PTA) is a preferred example.

The acrylic or methacrylic monomer (Component A) may be present in amounts sufficient to provide high Abbe number and high rigidity, but not so much as to cause brittleness or low tintability. Amounts of from approximately 7 to by weight, preferably approximately 15 to 55% by weight, more preferably approximately 15 to 45% by weight, based on the total weight of the casting composition have been found to be suitable.

The di- or polythio compound (Component B) may be of any suitable type. A di-, tri- or tetra polythiol compound may be used. A tri- or tetra-polythiol is preferred. The thiol may be selected from one or more of the following: 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol

[MDO]

CH2SH SCHSCH2CH2SH CH2SCH2CH2SH Trimethylolpropane Tris (3-mercaptopropionate) [TTMP] CH3CH2C(CH2 0 C CH2CH2SH)3

O

Pentaerythritol Tetrakis (2-mercaptoacetate) [PTMA] .1 C(CH2 0 C CH2SH)4 20 Trimethylolpropane Tris (2-mercaptoacetate) [TTMA] CH3CH2C(CH2 0 C CH2SH)3

II

0 r": 4-t-b utyl-1, ,2-be nzened ith iolI C (C H 3 3 0 0S

H

S H Bis-(2-mercaptoethyl)sulfide

HSCH

2

CH

2

SCH

2

CH

2

SH

4,4'-thiodibenzenethiol HSQSQ

-SH

benzenedithiol

~SH

Glycol Dimercaploacetate

H

2

COOCCH

2

-S

.H

Hr 2

COOCCH

2

S

Glycol Dimercaptopropionate Ethylene bis(3- Mercaptopropionate) H2000CCH2-CH2-SH Polyethylene Glycol Dimercaptoacetates H2, CH200CCH2-SH CH -CH200CCH 2

-SH

n 6 Polyethylene Glycol Di(3-Mercaptopropionates) CH2-CH200CCH2-CH2-SH CH2 -CH200OCCH2-CH2-SH n Pentaerythritol Tetrakis (3-mercapto-propionate) [PTMP]

C(CH

2 0 C CH 2

CH

2

SH)

4

II

0 Mercapto-methyl tetrahydrothiophene [MMTHT] HS SH Tris-(3-mercaptopropyl)isocyanurate [TMPIC] 0

II

C

HS-(CH

2 3

NN-(CH

2 3

-SH

I I

I

(CH

2 3

I

SH

4-mercaptomethyl-3,6-dithia-1,8-octanedithiol [MDO] is particularly preferred.

10 The di- or polythiol compound (Component B) may preferably be present in amounts of from approximately 15 to 60% by weight, more preferably 'approximately 20 to 55% by weight and particularly about 25 to 45% by weight based on the total weight of the casting composition.

The inclusion of a divinyl or polyvinyl monomer (Component C) provides a 15 reduction in flexibility, and thus an increase in hardness in optical articles produced therefrom.

.The divinyl or polyvinyl monomer may be a rigid cyclic vinyl monomer.

Component C may have the following formula: CH,= CH Z X wherein X is selected from one or more of the following Y Y Y Y Y Y O Y Y y

Y

,N I- C C I II N^ N I /NC~c o I

II

0 N IN N Z is a spacer group selected from one or more of the following CH2 _p 0- CH3

I

-CH2-C-O- (-CH2-CH2-S-) (-CH2-CH2-S-), or derivatives thereof; Y is hydrogen or halogen n 1 or 2 m=2-6 WO 96/38486 PCT/AU96/00314 8 p= 1-4 The divinyl or polyvinyl monomer may be a di- or tri- vinyl monomer. An aromatic divinyl is preferred. The aromatic divinyl monomer may include divinyl benzene, divinyl naphthene or derivatives thereof. 1,5-divinyl naphthene may be used. Divinyl benzene is particularly preferred.

The divinyl or polyvinyl monomer may preferably be present in amounts sufficient to provide rigidity and high index in optical articles formed from the casting composition, but not so much as to cause brittleness or low tintability.

Amounts of from approximately 5 to 50% by weight, preferably approximately to 40% by weight, more preferably about 20 to 30% by weight based on the total weight of the casting composition are preferred.

The cross-linkable polymeric casting composition may optionally further include a polymerisable comonomer (Component

D).

The polymerisable comonomer may be selected to improve the properties and/or processability of the cross-linkable polymeric casting composition. The polymerisable comonomer may be selected to improve tint rate, hardness, abrasion resistance and the like of the resulting polymer. The polymerisable comonomer may be an unsaturated or epoxy comonomer. The polymerisable comonomer may be selected from any suitable type, e.g. methacrylates, acrylates, vinyls, vinyl ethers, allyls, epoxides, and the like.

The polymerisable comonomer may preferably be selected from one or more of epoxidised monomer or oligomer vinyls, allylics, polyoxyalkylene glycol di-, tri-, tetra- and higher acrylates or methacrylates, polymerisable bisphenol monomers, urethane monomers having 2 to 6 terminal acrylic or methacrylic groups, fluorene acrylates or methacrylates, and thioacrylate or thiomethacrylate monomers.

Where an epoxidised monomer or oligomer is included, the epoxidised monomer may function to improve curing and casting characteristics. The epoxidised monomer or oligomer may fall into one or more of the following classes: internal, terminal, mono-functional, di-functional, tri-functional, tetrafunctional, aliphatic, aromatic, cyclic, structurally simple, structurally complex, esters, ethers, amines. An epoxidised soybean material may be used. The epoxidised monomer or oligomer may be selected from one or more of the following 1) Epoxidised soybean oil Triglycerides of a mixture of epoxidised a) oleic acid, b) linoleic acid, c) linolinic acid a)

CH

3

(CH

2 6

CH

2

CH-CHCH

2

(CH

2 6

COOH

V

CH

3

(CH

2 3

CH

2

CH-CHCH

2

CH-CHCH

2

(CH

2 6

COOH

CH

3

CH

2

CH-CHCH

2

CH-CH-CH

2

CH-CH(CH

2 7 C00H 2) Propylene Oxide 0H 2 -C H-C H 3

C

a a a a La a a 4' a, a a a.

a..

a a a a a a a a.

a a a a Ca a a i a 15 3) Hexanediol diglycidyl ether (HDGE)

CH

2 -CH-0H 2

-O-(CH

2 6

-O-CH

2

-CH-CH

2 4) 1,2 epoxy butane 0

CH

2

-H-CH

2

-CH

3 WO 96/38486 PCT/AU96/00314 Bisphenol fluorene diglycidyl ether (BPGE) 6) Epolight

CH

2

-O-CH

2 -CH-CH1 2 CHsCH-C-CH 2 -0CH 2

.CH-CH

2

C-O-CH

2

-CH-CH

2 7) AK-60 1

.C-O-CH

2

-CH-CH

2 1.

V

C-O-CH

2

-CH-CH

2 Ii 8) MY 721

AH-HC

H-CH

2 The epoxidised monomer may be present in amounts of from approximately 0.001% to 10% by weight, preferably 0.01% to more preferably approximately 0.01% to based on the total weight of the casting composition.

11 Where a vinyl comonomer is included, the vinyl comonomer may be selected from styrene, substituted styrenes, 3,9-divinyl-2,4,8,10- (DTU), a divinyl ester monomer of a bi- or polycyclic compound and mixtures thereof. The divinyl ester monomer of a bi- or polycyclic compound may be of the type described in copending provisional patent application entitled "UV Curable High Index Vinyl Esters" to Applicants, the entire disclosure of which is incorporated herein by reference.

The vinyl comonomers may be present in amounts of from 0 to approximately 20% by weight, preferably approximately 5 to 15% by weight, based on the total weight of the casting composition.

Where a thiodiacrylate or dimethacrylate is included, the thiodiacrylate or dimethacrylates may be selected from bis(4-methacryloylthioethyl)sulfide (BMTES) and bis(2-methacryloylthiophenyl)sulfide (BMTS). The thioacrylate or methacrylate may, be present in amounts of from 0 to approximately 20% by weight, preferably approximately 5 to 15% by weight, based on the total weight of the casting composition.

Where a fluorene diacrylate or dimethacrylate is included, the fluorene diacrylate or dimethacrylate monomer.may be selected from a bisphenol fluorene dihydroxy acrylate (BFHA) or a bisphenol fluorene dimethacrylate (BFMA) or 20 mixtures thereof.

The fluorene diacrylate or dimethacrylate monomer may be present in amounts of from 0 to approximately 20% by weight, preferably approximately 1 to 10% by weight.

The polyoxy alkylene glycol diacrylate or dimethacrylate compound 25 according to the present invention, when present, may include ethylene oxide or propylene oxide repeating units in its backbone. A polyethylene glycol dimethacrylate is preferred. Suitable materials include dimethylacrylates where the number of repeating ethylene oxide groups is between 4 and 14. Suitable materials include those sold under the trade names NK Ester 4G, 6G, 9G or 16G.

A 9G monomer is preferred.

The polyoxy alkylene glycol diacrylate or dimethacrylate component may be present in amounts of from 0 to approximately 20% by weight, preferably 4 9 9S** *4 9 .9 9 4 49 94 4.

94 44 S 9 9 9

C

94 9 99 .9 4944 4 1~ 12 approximately 5% to 15% by weight, based on the total weight of the casting composition.

The high index bisphenol monomer component in the. cross-linkable casting composition when present may be selected from: dimethacrylate and diacrylate esters of bisphenol A; dimethacrylate and diacrylate esters of 4,4'bishydroxy-ethoxy-bisphenol A and the like.

Preferred high index bisphenol compounds include bisphenol A ethoxylated dimethacrylate and tetra brominated bisphenol A ethoxylated dimethacrylates. A bisphenol A ethoxylate dimethacrylate sold under the trade designation ATM 20 by Ancomer has been found to be suitable.

The high index bisphenol monomer may be present in amounts of from 0 to approximately 20% by weight, preferably 5 to 15% by weight based on the total weight of the casting composition.

o a *7 .1 12a The cross-linkable casting composition according to the present invention may include a polymerisation curing agent.

The polymerisation curing agent may be a radical heat cationic or radical initiator. A radical heat initiator is preferred. The compositions may be cured by a combination of UV radiation and heat.

The amount of curing agent may vary with the monomers selected. It has been possible to operate with a relatively low level of curing agent of between approximately 0.05 and preferably 0.4% to 1.0% by weight.

The following curing agents have been found to be suitable.

AIBN (Azo radical heat initiator) Azodiisobutyronitrile Trigonox TX-29 (Dialkyl Peroxide radical heat initiator) 1,1-di-(-butyl peroxy-3,3,5-trimethyl cyclohexane) TBPEH (Alkyl Perester radical heat initiator) t-butyl per-2-ethylhexanoate (Diacyl Peroxide radical heat initiator) Benzoyl Peroxide (Peroxy Dicarbonate radical heat initiator) Ethyl Hexyl Percarbonate a* 4 a k WO 96/38486 PCT/AU96/00314 13 (Ketone Peroxide radical heat initiator) Methyl ethyl ketone peroxide Cyracure UVi -6974 (cationic photoinitiator) Triaryl sulfonium hexafluoroantimonate Lucirin TPO (radical photoinitiator) 2,4,6-Trimethylbenzoyldiphenylphosphine oxide Vicure 55 (radical photoinitiator) methyl phenylglycoxylate Bis(t-butyl peroxide) diisopropylbenzene t-butyl perbenzoate t-butyl peroxy neodecanoate Amicure

DBU

Amicure

BDMA

DABCO

Amicure DBU and/or Amicure BIDMA are preferred.

Initiator may be a single component or combination of initiator components.

Other additives may be present which are conventionally used in casting compositions such as inhibitors, dyes, UV stabilisers and materials capable of modifying refractive index. Mould release agents may be added. Such additives may include: UV Absorbers including Ciba Geigy Tinuvin P 2(2'-hydroxy-5'methyl phenyl) benzotriazole Cyanamid Cyasorb UV 531 -2-hyd roxy-4-n-octoxybenzop he none Cyanamid Cyasorb UV541 1-2(2-hydroxy-5-t-octylphenyl)- benzotriazole Cyanamid UV 2098 2 hydroxy-4-(2-acryloyloxyethoxy) benzophenone National Starch and Chemicals Permasorb MA 2 hydroxy-4-(2 hydroxy-3methacryloxy)propoxy benzophenone -Cyanamid UV24 2, 21 -dihydroxy-4-methoxybenzophenone -BASF UVINUL 400 2,4 dihydroxy-benzophenone -BASE UVINUL D-49 2,2'-dihydroxy-4,4'dimethoxy- benzophenone -BASF UVINUL D-50 2,2t, 4,4' tetra hyd roxy benzophenone 14 -BASF UVINUL D-35-ethyl-2-cyano-3,3-diphenyl acrylate -BASF UVINU L N-539-2-ethylhexyl-2-cyano-3, 3-diphenyl acrylate -Ciba Geigy Tinuvin 213 Hindered amine light stabilisers (HALS), including Ciba Geigy Tinuvin 765/292 bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Ciba Geigy 770 bis (2,2,6,6-tetramethyl-4- piperidinyl) sebacate Antioxidants including Ciba Geigy Irganox 245 triethylene glycol-bis-3- (3-tertbutyl-4-hydroxy-5methyl phenyl)propionate Irganox 1010 -2,2-bis[[3-[3,5-bis(1, 1-dimethylethyl)-.4-hydroxyphenyl]-1 oxopropoxy]methyl]-1. 3-propaned iyl 3, 5-bis(1, 1-dimethyl ethyl)-4-hydroxy benzene propanoate Irganox 1076 octadecyl 3-(3',5'-di-tert-butyl(-4'- hydroxyphenyl) propionate Anticolouring agents including 9, 10 dihydro-9-oxa-1 0-phosphaphenanthrene-1 -oxide Cure modifiers including Dodecyl mercaptan Butyl mercaptan 20 Thiophenol -Nitroso compounds such as 01301 from Wako -Nofmner from Nippon Oils and Fats :4:::Other monomeric additives can be present in amounts up to 10% by weight as viscosity modifiers, and include monomers such as methacrylic acid, :54C 25 vinyl silanes, and other functional monomers. Other monomeric additives may be included to improve processing and/or material properties, these include: methacrylic acid, maleic anhydride, acrylic acid adhesion promoters/modifiers such as Sartomer 9008, Sartomer 9013, Sartomer 9015 etc.

dye-enhancing, pH-adjusting monomers like Alcolac SIPOMER 2MIM a charge-reducing cationic monomer to render the material more antistatic, example Sipomer 05-80 or Q9-75 WO 96/38486 PCTIAU96/00314 mould release agents such as Phosphoric acid esters, e.g. octyl acid phosphate, etc, Alkyl quaternary ammonium salts, e.g. cetyl trimethyl ammonium bromine, etc., Zonyl Series, e.g. Zonyl FSO 100, Zonyl FSN 100, etc., Zelec Series, e.g. Zelec DP, Zelec UN, etc., and Unidain DS Series, e.g. DS 401, DS 202, etc.

The crosslinkable polymeric casting composition according to the present invention may be utilised in the preparation of an optical article. The optical article may be characterised by having an increased very high refractive index and Abbe number relative to known prior art articles. The optical article may exhibit excellent colour and low density.

In a preferred aspect of the present invention there is provided a method for preparing a polymeric article which method includes providing a cross-linkable polymeric casting composition including an effective amount of A: an acrylic or methacrylic monomer which provides high rigidity and low colour dispersion (High Abbe number) to the final product; B: a di- or polythio compound; C: a di- or polyvinyl monomer; and optionally D: a polymerisable comonomer; and a heat and/or UV curing agent; mixing the polymeric casting composition and curing agent; and subjecting the mixture to a cross-linking step.

The casting composition may be formed into a suitable article by mixing in a convenient vessel the components making up the material, and then adding the curing catalyst. The mixed material may then be degassed or filtered. As the curing time is substantially reduced, the casting process may be undertaken on a continuous or semi-continuous basis.

In a further aspect of the present invention there is provided a polymeric article prepared by the method as described above.

The polymeric article may be an optical article. The optical article may WO 96/38486 PCT/AU96/00314 16 provide characteristics equal to or greater than those achievable with articles made from diethylene glycol bis(allyl carbonate) but with a considerably reduced cure time and substantially increased throughput. The optical article may be further characterised by having reduced weight and/or thickness relative to the prior art, excellent optical properties provided by the high rigidity, high Abbe number, very low Yellowness Index and low density, whilst retaining good abrasion resistance and impact resistance.

The overall refractive index may be in the high to very high refractive index range of approximately 1.58 to 1.70, preferably 1.59 to 1.65.

Accordingly in a further preferred aspect of the present invention there is provided an optical article having a high Abbe number and high to very high refractive index in the range of from approximately 1.58 to 1.70 prepared from a cross-linkable polymer casting composition including an effective amount of A: an acrylic or methacrylic monomer which provides high rigidity and low colour dispersion (High Abbe number) to the final product; B: a di- or polythio compound; C: a di- or polyvinyl monomer; and optionally D: a polymerisable comonomer.

The optical articles prepared by the method of this invention include camera lenses, ophthalmic lenses and video discs.

The present invention will now be more fully described with reference to the accompanying examples. It should be understood, however, that the description following is illustrative only and should not be taken in any way as a restriction on the generality of the invention described above.

17 EXAMPLE 1 A cross-linkable casting composition having the following components was prepared Percent Diacryloyl oxymethyl tricyclodecane (DCPA) 32 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol (MDO) 31 Divinyl Benzene 21 Pentaerythritol tetracrylate (PTA) 16 100 The monomer mix was prepared in a beaker together with any suitable free radical initiator, for example 1.0% Trigonox TX29.

The casting material was used to fill the space between a pair of glass moulds separated by a plastic gasket at their periphery and held together by a clip. Cure time was 8 hours with heating at a temperature of 40 to 120°C. A satisfactory lens having a high Abbe number of 42 and high refractive index was formed.

EXAMPLES 2 TO 35 AND COMPARATIVE EXAMPLES 1 TO 3 The procedure of Example 1 was repeated utilising the components set 20 out below. Results are given in Tables 1 and 2 below.

*o ft "4 7~ r RJ191 TABLE 1 Formulations Properties No. DCPA PTA DCPM A9300* DVB MDO MMTHT Component Epoxy Compound RI Abbe Tg D No. 1. 32 16 21 31 1.6 42 2. 32 11 26 31 1.60 41 94 3. 46 27 27 1.60 41 103 4. 43 28 29 1.60 40 91 15 32 22.5 30.5 1.60 41 108 6. 15 33 22 30 1.60 41 104 7. 45 25 25 (ATM2O) (Epolight 1.60 4

OOME)

8. 32 14 23 31 1.60 41 9 9. 39 10 20 31 1.59 42 113 47 26 27 1.60 41 100 11 1A40 A4 0 00 0o I I.

33 1.60 1.60 4~)IA4E1 1 1 I I I 42 I It I .;j /.U 29 1.60 67 92 L I I I I I 1,.

-6 9, *0 C 9 As 9 A. 9 0*t *.e 0 9 A. 9s *9*A 0 9 9 *A 00 .0 *9 9 A '99 9

A'>

Table 1 continued Formulations Proper-ties No. DCPA PTA DCPM A9300* DVB MDO MMTHT Component Epoxy Compound RI Abbe Tg D No. 13 37 7.5 25.5 30 1.60 40.5 14 34 10 25 31 1.60 41 88 34 15.5 20.5 30 1.60 42 89 16 35 16 17 32 1.60 42.5 17 30.5 19 19.5 31 1.59 42 18 15 32 22 31' 1.60 42.5 19 48 24.5 27.5 1.60 41.5 43.5 26.5 30 1.60 39.5 88 21 20 15 33 32 1.607 38.3 108 22 32 36 27 1.602 38.5 23 10 25., 30 35 1.608 38.5 102 9 9 9 *9*g to 0* S. *9 4* 0 S S S S. 4) *4 5. S5 Formulations Properties No. DCPA PTA DCPM A9300* DVB MDO MMTHT Component Epoxy Compound RI Abbe Tg D No. 0

C)

24 35 7 20 38 1.604 40.4 22.5 17.5 25 35 1.605 39.5 78 26 16 24 25 35 1.604 39.6 *A9300 ATM20 ***Epolight 1001 *NK Ester 9C tris-hydroxyethyl isocyanurate triacrylate ethoxylated bis-phenol A dimethacrylate MF =CH 3

-CH

2

-C(CH

2

-O-CH

2

-CH-CH

2 3 0 =polyethylene glycol dimethacrylate =Dimethyloltricyclodecane dimethacrylate DCPM x 99 9* 9 99* *9*4 too 0. 0&09 4,999 99 *9 9999 999 99. *9 99 9 9 .9 99 9 9 99 9. 99 9 *9 99 *p 9 Formulations Properties No. DCPA PTA DCPM A9300* DVB MDO MMTHT Component Epoxy Compound Ri Abbe Tg D No. 27 33.0 15.0 22.0 30.0 1.595 41.2 86 28 29.5 19.0 20.0 31.5 1.595 40.9 88 29 10.0 38.0 16.5 35.5 1.597 40.8 18.5 29.5 18.5 33.5 1.597 41.4 88 31 12.5 35 20.5 32.0 1.593 41.8 32 35.0 14.5 20.5 30.0 1.593 42.1 33 49.0 0.0 22.0 29.0 1.595 41.6 34 15.0 33.0 0 18.0 34.0 1.597 41.0 86 50 20 30 1.590 40.3 79 *A9300 ATM20 **Epolight tris-hydroxyethyl isocyanurate triacrylate Ester 90 polyethylene glycol dimethacrylate ethoxylated bis-phenol A dimethacrylate DCPM =Dimethyloltricyclodecane dimethacrylate 10OMF CH 3

CH

2

-C(C

2

-O-C

2

-CH-CH)

\0/ EP C:%NiRIWECRE S79.O Tr

~N

*4 *e 4. 4 4 *e 4 4 4 4. 4* *4 *44* 4 4 *4 4 444 4.4 4 4 *4 44 4* *4 4. 4 44 44 9 TABLE 2 Formulations Pro perties No. DVB TMPT PETP BMME PETG ME MDO RI Abbe Tg 0

C)

No.

1 35 65 1.66 29 2 70 25 5 1.614 31 3 70 20 10 111.625

TMPT

P ETP

BMME

PETG

DME

=trim ethylolp ropa ne tris(P-thiop ropio nate) -pentaerythritol tetrakis (P-thiopropionate) I 4-bis (mercaptomethyl) benzene -pentaerythritol tetrakis (a-thioglycolate) -1,2-dimercaptoethane 21a Comparative Examples 4-6 This Example compares the composition of Example No. 10 referred to above with corresponding compositions in which the DCPA is replaced with different diacrylates or dimethyacrylates disclosed in EP 59811 and JP 6 123856.

Formulation wt% A. diacrylate or dimethacrylate monomer 37 B. 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol MDO C. divinylbenzene 25.5 D. pentaerythritol tetraacrylate Example Component A Rl Abbe Tg DCPA 1.6 40.5 900°C CE4 MPSMA 1.654 20.5 1090°C NS110 1.611 35.5 84°C CE6 9G 1.585 38.4 below "DCPA" is diacryloyloxymethyltricyclodecane and provides a composition of the present invention.

"MSPSMA" is

C

H

3 CH 3

CH

2 C-C-S S SC-C= CH2 0 0 "NS110" is bisphenol A ethoxylated dimethacrylate (page 11 of EP 59811) "9G" is polyethyleneglycol dimethacrylate (page 11 of EP 59811) Comparative Examples 4-6 demonstrate that when the composition of the invention is modified to replace the tricyclodecane monomer with another diacrylate or dimethacrylate there is a significant reduction in the Abbe No. and in some cases also a significant indication in glass transition temperature (Tg) or EP C:\W1NWORD ELLENLSPECIRLEFF29417.DOC 1

;)I

Y V I 21 b refractive index (RI).

The MPSMA monomer referred to in JP 612385 reduced the Abbe number from 40.5 to 20.5.

The NS-110 monomer (ATM-20) referred to in EP 59811 lowered the Abbe number to 35.5.

The 9G monomer referred to in EP 59811 reduced the Abbe, reduced the refractive index to below 1.59 and also reduced glass transition temperature (Tg) to below room temperature.

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S. S~ EP C :MtWORDEI I rSPECRLEWFF29417.DOC WO 96/38486 PCT/AU96/00314 22 Finally, it is to be understood that various other modifications and/or alterations may be made without departing from the spirit of the present invention as outlined herein.

Claims

1. A cross-linkable polymeric casting composition including an effective amount of A: an acrylic or methacrylic monomer selected from acrylates or methacrylate derivatives of a cycloaliphatic olefin which provides high rigidity and low colour dispersion (High Abbe number) to the final product; B: a di- or polythio compound; C: a di- or polyvinyl monomer; and optionally D: a polymerisable comonomer.

2. A cross-linkable polymeric casting composition according to Claim 1, wherein the acrylate or methacrylate derivative is of the formula CH 2 b 9 0 .9* .9 9 9 p. 99 0 9 9 *9*9 *9 9 S @9 9 990 0 p 99 99 p. 9 9 p 9 9p 9 *p 9 99@ 9 where R can be H or CH 3 a 1-3, b=1-3, m=0-6, n=0.6. Z is a spacer group selected from one or more of the following CI-12 P-O- CH

3 I -CH2-C-O CI- 2 -CH 2 -S- or derivatives thereof; wherein p 1-4. 25 3. A cross-linkable polymeric casting composition according to Claim 2, wherein the acrylate or methacrylate derivative is a tricyclodecane dimethanol diacrylate of the following formula EP C:\WINWORD'ELLEN\SPECIRLE56807-96.DOC 0 0 CH 2 =CH-C-O-CH 2 CH 2 -0-C-CH=CH 2

4. A cross-linkable polymeric casting composition according to Claim 1 wherein component A is present in amounts of from approximately 20 to 60% by weight based on the total weight of the casting composition.

A cross-linkable polymeric casting composition according to Claim 4, wherein component A is present in amounts of from approximately 30 to 55% by weight, based on the total weight of the casting composition.

6. A cross-linkable polymeric casting composition according to Claim 1, wherein component B is a di-, tri- or tetra- polythiol compound.

7. A cross-linkable polymeric casting composition according to Claim 6, wherein the polythiol is selected from one or more of the following: 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol [MDO] CH2SH *CHSCH2CH2SH CH2SCH2CH 2 SH EP* H:pps enE PECIRLE 80796DOC C CC 4-t-butyl- 1,2-benzenedithiol Bis(2-mercaptoethyl)sulfide HSCH 2 CH 2 SCH 2 CH 2 SH 'C C C.. Ce.. 0 C CC.. C. e e C C. CC C 0 C CC C C 0*Ce C C C C Re.. CR C C CC Ce Re C C CRC p CC C C. C CC C C 4,4'-thiodibenzenethiol HS -OS OSH benzenedithiol L:) EP H:PSiwr~leELN\PCRE,879.O Mercapto-methyl tetra hydroth iop hene [MMTHTJ HS\4 SH (g) Tris(3mercaptoprlioy)isocte TP 0 I I o N 'z 0 *00 to H 2 3 6H so so0 **of0

8. A cross-linkable polymeric casting composition according to Claim 7, 00*wherein the polythiol is A-mercaptometLhyk3-,6dithia1,8-octanedithiol [MDO].

9. A cross-linkable polymeric casting composition according to Claim 7, wherein component B is present in amounts of from approximately 15 to 60% by weight, based on the total weight of the casting composition.

EP H:ap0nodelnELEPCREW79.O

11. A cross-linkable casting composition according to Claim 1, wherein component C is a rigid cyclic vinyl monomer of the formula (C H 2 =CH S X nm wherein X is selected from one or more of the following Y Y Y Y 0 Y Sa 0 Y Y A: CH 2 -a 0 so t oS 0 *000 60 0 0 at. Y Y X-OY NC C I i C 11 0 N 'gP C:WNPAODELENksPECIRLE%5687-98.DOC 27a S is a spacer group selected from one or more of the following CH 3 -OH 2 H2CH 2 -C-O- -CH2-)p Ior (-cH 2 -CH 2 or derivatives thereof;, Y is hydrogen or halogen n 0, 1 or 2 p= 1- 4 EP CAVNOMIIF\PCRES 79.O 28

12. A cross-linkable polymeric casting composition according to Claim 11, wherein the divinyl or polyvinyl monomer is an aromatic divinyl monomer selected from the group consisting of divinyl benzene, divinyl naphthene or derivatives thereof.

13. A cross-linkable polymeric casting composition according to Claim 11, wherein component C is present in amounts of from approximately 5 to 50% by weight, based on the total weight of the casting composition.

14. A cross-linkable polymeric casting composition according to Claim 13, wherein component C is present in amounts of from approximately 15 to 40% by weight, based on the total weight of the casting composition.

A cross-linkable polymeric casting composition according to Claim 1, wherein component D is an unsaturated or epoxy comonomer selected from the group consisting of methacrylates, acrylates, vinyl, vinyl ethers, allyls, epoxides and mixtures thereof.

16. A cross-linkable polymeric casting composition according to Claim 20 wherein component D is an epoxidised monomer or oligomer selected from the group consisting of internal, terminal, mono-functional, di-functional, tri-functional, .o s; tetra-functional, aliphatic, aromatic, cyclic, structurally simple, structurally complex, esters, ethers, amines, or mixtures thereof. •!o 25

17. A cross-linkable polymeric casting composition according to Claim 16, wherein the epoxidised monomer or oligomer is present in amounts of from approximately 0.001% to 10% by weight, based on the total weight of the casting composition.

18. A method for preparing a polymeric article, which method includes EP C:WINWORDOELLENSPECIRLE\5807-96.DOC providing a cross-linkable polymeric casting composition including an effective amount of A: an acrylic or methacrylic monomer selected from acrylates or methacrylate derivatives of a cycloaliphatic olefin which provides high rigidity and low colour dispersion (High Abbe number) to the final product; B: a di- or polythio compound; C: a di- or polyvinyl monomer; and optionally D: a polymerisable comonomer; and a heat and/or UV curing agent; mixing the polymeric casting composition and curing agent; and subjecting the mixture to a cross-linking step.

19. A method according to Claim 18, wherein the polymeric article is a lens. An optical article having a high rigidity, high Abbe number and high to very high refractive index in the range of from 1.58 to 1.70 prepared from a cross- linkable polymer casting composition including an effective amount of

20 A: an acrylic or methacrylic monomer selected from acrylates or methacrylate derivatives of a cycloaliphatic olefin which provides high rigidity and high Abbe number to the final product; B: a di- or polythio compound; 25 C: a di- or polyvinyl monomer; and optionally D: a polymerisable comonomer.

21. An optical article according to Claim 20, wherein the optical article further exhibits low density.

22. A cross-linkable polymeric casting composition substantially as EP C:%WINORD\ELLENWPECIRLEN5887-96,DOC hereinbefore described with reference to any one of the non-comparative examples.

23. A cross-linkable polymeric casting composition according to Claim 1 substantially as herein described with reference to any one of Examples 1 to 26. DATED: 26 May 1999 PHILLIPS ORMONDE FITZPATRICK Attorneys for: SOLA INTERNATIONAL HOLDINGS LTD. S S SSS S S S 5* S S 5 555 5 x I KON H:\APP$\WINWORDELLENXELLEN\SPECIRLE\56807-96.DOC