WO2000064956A1 - Photocurable composition for preparing lenses - Google Patents

Photocurable composition for preparing lenses Download PDF

Info

Publication number
WO2000064956A1
WO2000064956A1 PCT/AU2000/000349 AU0000349W WO0064956A1 WO 2000064956 A1 WO2000064956 A1 WO 2000064956A1 AU 0000349 W AU0000349 W AU 0000349W WO 0064956 A1 WO0064956 A1 WO 0064956A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition according
group
photocurable composition
hydrogen
formula
Prior art date
Application number
PCT/AU2000/000349
Other languages
French (fr)
Inventor
Huan Kiak Toh
Fang Chen
Original Assignee
Sola International Holdings Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sola International Holdings Ltd filed Critical Sola International Holdings Ltd
Priority to AU39476/00A priority Critical patent/AU3947600A/en
Publication of WO2000064956A1 publication Critical patent/WO2000064956A1/en

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals

Definitions

  • the present invention relates to photocurable compositions and their use in forming high index lenses.
  • thiol-ene system involves polythiol olefin copolymerization.
  • the thiol-ene system has the potential of allowing lenses to be prepared with high refractive index to allow lens thickness to be minimised and to be more attractive.
  • the thiol-ene system is difficult to cure efficiently particularly in resin thicknesses of at least 1mm which are generally required for opthalmic lenses.
  • the thiol-ene system involves a complex range of reactions which are difficult to control and may result in an unacceptable proportion of unreacted monomer and poor rigidity.
  • the invention provides a photocurable resin composition for preparing lenses including: a polythiol compound; an aromatic monomer containing at least two vinyl functional groups; an acrylate monomer containing at least two unsaturated groups and selected from acrylates, methacrylates, acrylic acid anhydrides and methacrylic anhydrides; and a photoinitiator preferably including a phosphine oxide.
  • the acrylate monomer is preferably of Formula I:
  • R and R' are independently selected from hydrogen and Ci to C alkyl and most preferably are hydrogen or methyl;
  • X is a bond or a group of Formula -O(L)- wherein L is a linking group optionally substituted with one or more acrylic or methacrylic groups.
  • linking groups include alkylene, preferably of 1 to 6 carbon atoms, carbocyclic, heterocyclic and polyaikylene oxides. Such linking groups may be further substituted with from 1 to 3 acrylate and/or methacrylate groups. Suitable examples of linking groups include alkylene glyol di(meth)- acrylates and polyaikylene glycol di(meth)acrylates.
  • L examples include groups of Formula Ila or lib
  • Z is a spacer group selected from one or more of the following
  • G is selected from the group consisting of
  • M is selected from the group consisting of a bond
  • R ⁇ , R 3 and R 4 are independently selected from the group consisting of hydrogen and alkyl of 1 to 6 carbon atoms; and n is an integer having a value of 0 to 10,
  • Y is hydrogen or a halogen, preferably fluorine, chlorine or bromine.
  • Preferred compounds of Formula I include compounds wherein X is a bond and the most preferred acrylate monomer of this type is methacrylic acid anhydride. Compounds of Formula I in which X is a bond have been found to significantly improve curing efficiency.
  • acrylate monomers are selected from the group of compounds of formula
  • R and R 1 are independently selected from hydrogen and methyl; compounds of formula: where R is methyl or hydrogen; and compounds of formula:
  • R is methyl or hydrogen
  • m is an integer of 2 to 15 and most preferably 9.
  • the acrylate component is typically present in an amount of from 10 to 40% by weight and preferably from 15 to 25% by weight of the total composition.
  • compositions of the invention include a photoinitiator which has sufficient absorption in the far UV and near visible regions of the spectrum.
  • Photoinitiators exhibiting strong absorption in the range of from 350 to 450nm are particularly preferred.
  • the preferred chemical class of initiators is the phosphine oxides particularly the acylphosphine oxides including bisacyl phosphine oxides or their derivatives such as ester derivatives.
  • the most preferred photoinitiators are 2,4,6-trimethylbenzoyl-diphenylphosphine oxide
  • IRGACURE 819 from Ciba bis-(2,6-dimethoxybenzoyl)-2,4,4- trimethylpentyl phosphine oxide (known by the brand name BAPO-1 and available in admixture with an hydroxy- ⁇ , ⁇ -dialkylacetophenone from Ciba.
  • Photoinitiator combinations may be used.
  • acylphosphine oxides may be used in combination with benzophenones, benzoin eithers or hydroxy- ⁇ , ⁇ -dialkylacetophenones.
  • Specific examples of other photoinitiators include: -methyl-1 -[4-(methylthio)phenyl]-2-morpholinopropane-1 -one (Irgacure 907)
  • Suitable mixture of initiators containing phosphine oxides include:
  • IRGACURE 1700 - a mixture of 25% BAPO-1 and 75% DAROCURE
  • IRGACURE 1800 a mixture of 25% BAPO-1 and 75% Irgacure 184, and
  • IRGACURE 1850 - a mixture of 50% BAPO-1 and 50% IRGACURE 184.
  • the amount of photoinitiator present in the compositions of the invention is typical in the range from 0.1 to 2% by weight. We have obtained particularly good results by using from 0.2 to 1.5% by weight of an acylphosphine oxide photoinitiator.
  • the aromatic monomer containing at least two vinyl functional groups is preferably of Formula III
  • Z is a spacer group selected from one or more of the following
  • n is zero, that is the linking group is not present, and X is an aromatic group particularly benzene.
  • the most preferred said monomer containing at least two vinyl groups is divinyl benzene.
  • the amount of said monomer containing at least two vinyl functional groups is typically in the range of from 20 to 40% by weight and more preferably from 26 to 34% by weight based on the total composition.
  • an aromatic divinyl compound be present in a stoichiometric (molar) excess with respect to the polythiol compound. We have obtained particularly good results using divinyl benzene.
  • compositions containing divinyl benzene, a polythiol compound and an acrylate type monomer, preferably where the divinyl benzene is present in excess of the polythiol result in lenses high refractive index lenses and good mechanical properties when a photoinitiator having significant absorption in the range 350 to 450nm is used (particularly an acylphosphine oxide) in an amount of from 0.1 to 2% by weight of the total composition.
  • a particularly preferred embodiment of the invention proves a photocurable composition for the preparation of lenses including divinyl benzene; a polythiol compound wherein the divinyl benzene is present in a stoichiometric excess of the polythiol compound; an acrylate type monomer (preferably methacrylic acid anhydride); and a photo initiator, preferably an acylphosphine oxide, having significant absorption at a wavelength in the range of from 350 to 450nm in an amount of from 0.1 to 2% by weight of the total composition.
  • the polythiol compound used in the composition of the invention will include at least two thiol groups and preferably at least three thiol groups.
  • the polythiol compound is preferably selected from one or more of the following:
  • the thiol compound may preferably be present in amounts of from approximately 30 to 50% by weight, more preferably approximately 35 to 45% by weight, based on the total weight of the casting composition.
  • compositions of the invention may include one or more UV absorbers without having a significantly deleterious effect on curing efficiency.
  • UV absorbers reduce the penetration of light in thick compositions they have in many cases been found to lead to inefficient curing particularly at the centre of the cast.
  • UV absorbers examples include: 2(2'-hydroxy-5'methyl phenyl) benzotriazole, (Ciba Geigy "Tinuvin P"),
  • the period of irradiation of UV-visible light may be reduced significantly when compared with previously known high index lens casting compositions and is typically from several minutes to an hour. Indeed it is preferred that irradiation occurs for a period of from 0.1 to 5 minutes.
  • the invention utilises the post irradiation heat treatment.
  • the composition will typically include a heat curing agent adapted to induce curing a relatively high temperature of for example from 80°C to 130°C.
  • heat curing agents examples include: AIBN (Azo radical heat initiator) Azodiisobutyronitrile, - Trigonox TX-29 (Dialkyl Peroxide radical head intiator)
  • additives examples include: - Amicure DBU,
  • Amicure DBU and/or Amicure BDMA are preferred.
  • Dialkyl peroxide radical heat initiators are particularly preferred.
  • Fatty alkyl peroxides such as 2,5-dimethyl hexane 2,5-di-t-butylperoxide are the most preferred.
  • the amount of heat initiator is typically in the range of from 0.05 to 1 % by weight and generally the thermal treatment will be carried out by maintaining a temperature of at least 80°C for a period of at least 10 minutes. When present the heat initiator is generally used in amounts of at least 0.05%.
  • Example 1 The composition listed in the table below was cast into lens moulds to provide a thickness of 2.0mm
  • composition was irradiated using a EPIQ 6000 V-bulb spectrum lamp (Fusion UV curing Systems Corporation) having a power of 240w/cm with one pass under the lamp at a rate of 9mm/second. Post irradiation heat treatment was carried out at 100°C for 1 hour.
  • EPIQ 6000 V-bulb spectrum lamp Fusion UV curing Systems Corporation
  • the resulting lens was found to have a refractive index of 1.599 and Abbe number of 36.5.
  • Example 1 The procedure of Example 1 was repeated with the exception that the heat initiator was omitted.
  • the composition was cured under the conditions used in Example 1.
  • the heat treatment condition was 120°C for 1.5 hours.
  • Example 1 used in this example with the exception that the photoinitiator used was a mixture of 1g of TPO and 1.0g of
  • DAROCURE 1173 available from Ciba, has as the active agent 2-hydroxy-2-methyl-1 -phenylpropan-1 -one.
  • a 2.0mm thick lens was cured by passing it twice beneath the lamp at a speed of 24mm/sec and was heat treated at 100°C for 1 hour.
  • Example 1 The procedure of Example 1 was repeated except that methacrylic anhydride was replaced with the same amount of ethylene glycol dimethacrylate. Effective case was provided under the conditions used in Example 1.
  • Formulation Examples 5 to 9 were prepared from the compositions shown in Table 1 and were cast into semi-finished lenses of 8mm thickness.
  • the lenses were cured by subjecting the photochemical compositions to the following conditions, (a) UV curing using a FUSION V lamp with the back surface uppermost for a period of about 0.5 minutes. (b) Maintain the composition at about 120 to 130°C for about one and half hours; and (c) Subjecting the lens with the front surface uppermost to further irradiation for a period of about 0.5 minutes.
  • the properties of the resulting cured lenses are provided in the table. Following formulations were casted into thick semi-finished lenses (8 mm) and stock lenses with the corresponding curing conditions, giving low strain and fully cured lenses.

Abstract

A photocurable composition for preparation of a lens including: a polythiol compound; an aromatic monomer containing at least two vinyl groups; an acrylate monomer containing at least two unsaturated groups and selected from the group consisting of acrylates, methacrylates, acrylic acid anhydrides and methacylic anhydrides; and a photoinitiator.

Description

PHOTOCURABLE COMPOSITION FOR PREPARING LENSES
The present invention relates to photocurable compositions and their use in forming high index lenses.
The manufacture of lenses such as opthalmic lenses by photocuring of a resin composition has been previously described, for example in our prior Applications PCT/AU 96/00247 and PCT/AU97/00310. One photocurable system known as the thiol-ene system involves polythiol olefin copolymerization. The thiol-ene system has the potential of allowing lenses to be prepared with high refractive index to allow lens thickness to be minimised and to be more attractive. However we have found that the thiol-ene system is difficult to cure efficiently particularly in resin thicknesses of at least 1mm which are generally required for opthalmic lenses. Further the thiol-ene system involves a complex range of reactions which are difficult to control and may result in an unacceptable proportion of unreacted monomer and poor rigidity.
Alternative systems such as urethane acrylate systems disclosed in PCT/AU97/00247 may be cured efficiently. Such systems however do not generally allow the high refractive indexes theoretically possible with the thiol- ene system to be readily attained. Furthermore the preparation of lenses, which are typically of thickness of 1 to 15 mm, creates significant difficulties for compositions containing vinyl substituted aromatics. It is difficult to achieve even curing of a cast of this thickness since the depth of penetration of active rays in a photosensitive composition is generally small. This is especially a problem for compositions containing divinyl benzene or the like.
As a result it has not generally been possible to achieve the balance of good mechanical properties and high refractive index required for the commercial use of photosensitive compositions in preparing lenses.
There is therefore a need for a photocurable lens composition and method of preparing lenses which allows lenses to be cured rapidly to provide a high refractive index and the required mechanical properties.
The invention provides a photocurable resin composition for preparing lenses including: a polythiol compound; an aromatic monomer containing at least two vinyl functional groups; an acrylate monomer containing at least two unsaturated groups and selected from acrylates, methacrylates, acrylic acid anhydrides and methacrylic anhydrides; and a photoinitiator preferably including a phosphine oxide.
The acrylate monomer is preferably of Formula I:
Figure imgf000004_0001
wherein R and R' are independently selected from hydrogen and Ci to C alkyl and most preferably are hydrogen or methyl; X is a bond or a group of Formula -O(L)- wherein L is a linking group optionally substituted with one or more acrylic or methacrylic groups.
Examples of linking groups include alkylene, preferably of 1 to 6 carbon atoms, carbocyclic, heterocyclic and polyaikylene oxides. Such linking groups may be further substituted with from 1 to 3 acrylate and/or methacrylate groups. Suitable examples of linking groups include alkylene glyol di(meth)- acrylates and polyaikylene glycol di(meth)acrylates.
Further examples of L include groups of Formula Ila or lib
CHR 1
Figure imgf000004_0002
Iia
Figure imgf000005_0001
lib wherein
Z is a spacer group selected from one or more of the following
CH3 fCH' O — — CH — C-O- or
V -CH2— CH2 — S— )-
, or derivatives thereof;
wherein p = 1-4 RR22 iiss hhyyddrrogen or hydroxy; G is selected from the group consisting of
Figure imgf000005_0002
Figure imgf000006_0001
wherein M is selected from the group consisting of a bond,
Figure imgf000006_0002
methylene and — CH2— S — CH2—
Rι, R3 and R4 are independently selected from the group consisting of hydrogen and alkyl of 1 to 6 carbon atoms; and n is an integer having a value of 0 to 10,
Y is hydrogen or a halogen, preferably fluorine, chlorine or bromine. Preferred compounds of Formula I include compounds wherein X is a bond and the most preferred acrylate monomer of this type is methacrylic acid anhydride. Compounds of Formula I in which X is a bond have been found to significantly improve curing efficiency.
Further particularly preferred acrylate monomers are selected from the group of compounds of formula
Figure imgf000006_0003
wherein R and R1 are independently selected from hydrogen and methyl; compounds of formula:
Figure imgf000007_0001
where R is methyl or hydrogen; and compounds of formula:
Figure imgf000007_0002
wherein R is methyl or hydrogen, and m is an integer of 2 to 15 and most preferably 9.
The acrylate component is typically present in an amount of from 10 to 40% by weight and preferably from 15 to 25% by weight of the total composition.
The compositions of the invention include a photoinitiator which has sufficient absorption in the far UV and near visible regions of the spectrum.
Photoinitiators exhibiting strong absorption in the range of from 350 to 450nm are particularly preferred. The preferred chemical class of initiators is the phosphine oxides particularly the acylphosphine oxides including bisacyl phosphine oxides or their derivatives such as ester derivatives. The most preferred photoinitiators are 2,4,6-trimethylbenzoyl-diphenylphosphine oxide
(available under the brand name LUCIRIN TPO from BASF), bis-(2,4,6- trimethylbenzoyl)phenyl phosphine oxide (available under the brand
IRGACURE 819 from Ciba) and bis-(2,6-dimethoxybenzoyl)-2,4,4- trimethylpentyl phosphine oxide (known by the brand name BAPO-1 and available in admixture with an hydroxy-α,α-dialkylacetophenone from Ciba.
Another suitable product is LUCIRIN LR 8893X brand initiator from BASF) ethyl
2,4,6-trimethyl benzoyl phenyl phosphinate.
Photoinitiator combinations may be used. For example, acylphosphine oxides may be used in combination with benzophenones, benzoin eithers or hydroxy-α,α-dialkylacetophenones. Specific examples of other photoinitiators include: -methyl-1 -[4-(methylthio)phenyl]-2-morpholinopropane-1 -one (Irgacure 907)
Figure imgf000008_0001
(hydroxycyclohexyl) phenyl ketone (Irgacure 184)
Figure imgf000008_0002
(2-benzyl-2-N-dimethylamino-1-(4-morpholinophenyl)-1-butanone) (Irgacure 369)
Figure imgf000008_0003
(Benzyl Dimethyl Ketal) (Lucirin BDK; Irgacure 651)
Figure imgf000008_0004
2-(carbamoylazo)-substituted (Vicure 30)
CH
I
CH3— C— N=N— CH2— NH2 CN
1-methoxy-2-phenyl-1 ,2-ethandione (VICURE 55)
Figure imgf000009_0001
α-hydroxy-α,α-dimethylacetophene (DAROCURE 1173)
Figure imgf000009_0002
2-n-propoxy-9H-thioxanthen-9-one (WB 4744)
Figure imgf000009_0003
Ethyl 4-(dimethylamino)benzoate (Quantacure EPD)
Figure imgf000009_0004
Examples of suitable mixture of initiators containing phosphine oxides include:
IRGACURE 1700 - a mixture of 25% BAPO-1 and 75% DAROCURE
1 173,
IRGACURE 1800 - a mixture of 25% BAPO-1 and 75% Irgacure 184, and
IRGACURE 1850 - a mixture of 50% BAPO-1 and 50% IRGACURE 184.
The amount of photoinitiator present in the compositions of the invention is typical in the range from 0.1 to 2% by weight. We have obtained particularly good results by using from 0.2 to 1.5% by weight of an acylphosphine oxide photoinitiator.
The aromatic monomer containing at least two vinyl functional groups is preferably of Formula III
Figure imgf000010_0001
wherein X is
Figure imgf000010_0002
Z is a spacer group selected from one or more of the following
CH3
-CH ,_- — CH2-). ■O- CH2— C-O — or
f — CH2 — CH2 — S — ) , or derivatives thereof;
Y is hydrogen or halogen; n = 0, 1 or 2; p = 1 - 4.
In the preferred compounds of Formula III n is zero, that is the linking group is not present, and X is an aromatic group particularly benzene. The most preferred said monomer containing at least two vinyl groups is divinyl benzene. The amount of said monomer containing at least two vinyl functional groups is typically in the range of from 20 to 40% by weight and more preferably from 26 to 34% by weight based on the total composition. In the composition of the present invention it is particularly preferred that an aromatic divinyl compound be present in a stoichiometric (molar) excess with respect to the polythiol compound. We have obtained particularly good results using divinyl benzene. This was contrary to what was expected because photopolymer compositions containing divinyl benzene in combination with acrylates are generally difficult to cure particularly in thick casts. The presence of an excess of divinyl compound would merely be expected to exacerbate these difficulties. We have found that compositions containing divinyl benzene, a polythiol compound and an acrylate type monomer, preferably where the divinyl benzene is present in excess of the polythiol result in lenses high refractive index lenses and good mechanical properties when a photoinitiator having significant absorption in the range 350 to 450nm is used (particularly an acylphosphine oxide) in an amount of from 0.1 to 2% by weight of the total composition.
Accordingly a particularly preferred embodiment of the invention proves a photocurable composition for the preparation of lenses including divinyl benzene; a polythiol compound wherein the divinyl benzene is present in a stoichiometric excess of the polythiol compound; an acrylate type monomer (preferably methacrylic acid anhydride); and a photo initiator, preferably an acylphosphine oxide, having significant absorption at a wavelength in the range of from 350 to 450nm in an amount of from 0.1 to 2% by weight of the total composition. The polythiol compound used in the composition of the invention will include at least two thiol groups and preferably at least three thiol groups. The polythiol compound is preferably selected from one or more of the following:
(a) Pentaerythritol Tetrakis (3-mercapto-propionate) [PTMP]
C(CH2 O C CH2CH2SH)4 II
O
(b) Trimethylolpropane Tris (3-mercaptopropionate) [TTMP]
CH3CH2C(CH2 O C CH2CH2SH)3
(c) 4-mercaptomethyl-3,6-drthia-1 ,8-octanedithiol [ DO]
Figure imgf000011_0001
(d) Pentaerythritol Tetrakis (3-mercaptoacetate) [PTMA]
C(CH2 O C CH2SH)4
O
(e) Tnmethylolpropane Tris (3-mercaptoacetate) [TTMA]
CH3CH2C(CH2 O C CH2SH)3
O
(f) 4-t-butyl-1 ,2-benzenedithiol
Figure imgf000012_0001
(g) 2-mercaptoethylsulfιde
HSCH2CH2SCH2CH2SH (h) 4,4'-thiodibeπzenethiol
Figure imgf000012_0002
(i) benzenedithiol
Figure imgf000012_0003
(j) Glycol Dimercaptoacetate H2COOCCH2-SH
H2COOCCH2-SH
(k) Glycol Dimercaptopropionate Ethylene bis(3-Mercaptopropionate) H2COOCCH2-CH2-SH
H2COOCCH2-CH2-SH (I) Polyethylene Glycol Dimercaptoacetates
Figure imgf000013_0001
n
(m) Polyethylene Glycol Di(3-Mercaptopropionates)
Figure imgf000013_0002
(n) 2,5-bis(mercaptomethyl)-1 ,4-dithiane
(o) 3,6-dithia-1 ,8-octanedithiol
(p) TGBMA (a mixture of oligomers)
Figure imgf000013_0003
I = 0, 1,2,3 m = 0, 1,2, 3 n =0, 1,2,3
Figure imgf000014_0001
(q) DMPMA
Figure imgf000014_0002
The thiol compound may preferably be present in amounts of from approximately 30 to 50% by weight, more preferably approximately 35 to 45% by weight, based on the total weight of the casting composition.
We have found that the compositions of the invention may include one or more UV absorbers without having a significantly deleterious effect on curing efficiency. As UV absorbers reduce the penetration of light in thick compositions they have in many cases been found to lead to inefficient curing particularly at the centre of the cast.
Examples of preferred UV absorbers include: 2(2'-hydroxy-5'methyl phenyl) benzotriazole, (Ciba Geigy "Tinuvin P"),
2-hydroxy-4-n-octoxybenzo-phenone, (Cyanamid "Cyasorb UV" 531), 2(2-hydroxy-5-t-octylphenyl)-benzotriazole, (Cyanamid "Cyasorb UV5411"), 2 hydroxy-4-(2-acryloyloxyethoxy)-benzophenone (Cyanamid "UV 2098"), 2 hydroxy-4-(2 hydroxy-3-methacryloxy)propoxy benzophenone (National Starch and Chemicals "Permasorb MA"),
2,2'-dihyroxy-4-methoxybenzophenone (Cyanamid "UV24"), 2,4 dihydroxy-benzophenone (BASF "UVINUL 400"), 2,2'-dihydroxy-4,4'dimethoxy-benzophenone (BASF "UVINUL D-49"), 2,2', 4,4' tetrahydroxy benzophenone (BASF "UVINUL D-50"), ethyl-2-cyano-3,3-diphenyl acrylate (BASF "UVINUL D-35") 2-ethexyl-2-cyano-3,3-diphenyl acrylate (BASF "UVINUL N-539") and Ciba Geigy Tinuvin 213.
The compositions of the invention are preferably used in casting of lense of thickness in the range of from 1 to 15mm. Accordingly in a further embodiment the invention provides a method of preparing lenses including forming a cast of the hereinabove described composition with a thickness in the range of from 1 to 15mm and irradiating the cast composition with light in the UV-visible range. Preferably the light includes a significant wavelength component in the range of from 350 to 450nm. The "FUSION V" brand lamp is a good source of the appropriate range of UV light.
The period of irradiation of UV-visible light may be reduced significantly when compared with previously known high index lens casting compositions and is typically from several minutes to an hour. Indeed it is preferred that irradiation occurs for a period of from 0.1 to 5 minutes.
In a preferred embodiment the invention utilises the post irradiation heat treatment. In this embodiment, the composition will typically include a heat curing agent adapted to induce curing a relatively high temperature of for example from 80°C to 130°C.
Examples of heat curing agents include: AIBN (Azo radical heat initiator) Azodiisobutyronitrile, - Trigonox TX-29 (Dialkyl Peroxide radical head intiator)
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, (Ketone Peroxide radical heat initiator) Methyl ethyl ketone peroxide, 1 , 1 -bis(t-butylperoxy)cyclohexane, - 2,2-bis(t-butylperoxy)butane,
Dicumyl peroxide, t-Butyl cumyl peroxide, 2,5-Dimethyl hexane 2,5-di-t-butyl peroxide, Di-t-butyl peroxide, - Bis(t-butyl peroxide) diisopropylbenzene, t-butyl perbenzoate, and t-butyl peroxy neodecanoate
Examples of other additives include: - Amicure DBU,
Amicure BDMA and
DABCO
Amicure DBU and/or Amicure BDMA are preferred.
Dialkyl peroxide radical heat initiators are particularly preferred. Fatty alkyl peroxides such as 2,5-dimethyl hexane 2,5-di-t-butylperoxide are the most preferred.
The amount of heat initiator is typically in the range of from 0.05 to 1 % by weight and generally the thermal treatment will be carried out by maintaining a temperature of at least 80°C for a period of at least 10 minutes. When present the heat initiator is generally used in amounts of at least 0.05%.
The invention will now be described with reference to the following examples. It should be understood, however, that the description following is illustrative only and should not be taken as a restriction on the generability of the invention described above.
Example 1 The composition listed in the table below was cast into lens moulds to provide a thickness of 2.0mm
AMOUNT
DVB 32.5g
Methacrylic anhydride 20.0g
TG BMA 39.0g
PTMA 8.5g
UV 5411 0.2g
Irganox 1010 0.2g
TPO (Lucirin) 1.2g
TX-29 0.5g
The composition was irradiated using a EPIQ 6000 V-bulb spectrum lamp (Fusion UV curing Systems Corporation) having a power of 240w/cm with one pass under the lamp at a rate of 9mm/second. Post irradiation heat treatment was carried out at 100°C for 1 hour.
The resulting lens was found to have a refractive index of 1.599 and Abbe number of 36.5.
Example 2
The procedure of Example 1 was repeated with the exception that the heat initiator was omitted. The composition was cured under the conditions used in Example 1. The heat treatment condition was 120°C for 1.5 hours.
Example 3
The composition of Example 1 used in this example with the exception that the photoinitiator used was a mixture of 1g of TPO and 1.0g of
DAROCURE 1173. DAROCUR 1173, available from Ciba, has as the active agent 2-hydroxy-2-methyl-1 -phenylpropan-1 -one. A 2.0mm thick lens was cured by passing it twice beneath the lamp at a speed of 24mm/sec and was heat treated at 100°C for 1 hour. Example 4
The procedure of Example 1 was repeated except that methacrylic anhydride was replaced with the same amount of ethylene glycol dimethacrylate. Effective case was provided under the conditions used in Example 1.
Examples 5-9
Formulation Examples 5 to 9 were prepared from the compositions shown in Table 1 and were cast into semi-finished lenses of 8mm thickness.
The lenses were cured by subjecting the photochemical compositions to the following conditions, (a) UV curing using a FUSION V lamp with the back surface uppermost for a period of about 0.5 minutes. (b) Maintain the composition at about 120 to 130°C for about one and half hours; and (c) Subjecting the lens with the front surface uppermost to further irradiation for a period of about 0.5 minutes.
The properties of the resulting cured lenses are provided in the table. Following formulations were casted into thick semi-finished lenses (8 mm) and stock lenses with the corresponding curing conditions, giving low strain and fully cured lenses.
Figure imgf000019_0001
DVB - divinyl benzene A-9300
Figure imgf000020_0001
DCP-A - Diacryloyl oxymethyl tricyclodecane
Figure imgf000020_0002
NK - Ester 9G Polyethylene Glycol Dimethacrylate.
CH2=
SR480 - ethoxylated (10) Bisphenol A dimethacrylate MAA - Methacrylic anhydride

Claims

Claims:
1. A photocurable composition for preparation of a lens including: a polythiol compound; an aromatic monomer containing at least two vinyl groups an acrylate monomer containing at least two unsaturated groups and selected from the group consisting of acrylates, methacrylates, acrylic acid anhydrides and methacrylic anhydrides; and a photoinitiator.
2. A photocurable composition according to claim 1 wherein the aromatic monomer containing at least two vinyl groups is present in an amount of from 20 to 40% by weight of the composition.
3. A photocurable composition according to claim 1 wherein aromatic monomer containing at least two vinyl groups is present in a stoichiometric excess compared with the number of moles of the polythiol compound and preferably in the range of from 26 to 34% by weight.
4. A photocurable composition according to claim 1 wherein the photoinitiator includes a phosphine oxide initiator.
5. A photocurable composition according to claim 1 wherein the acrylate monomer is of Formula I
Figure imgf000021_0001
wherein R and R' are independently selected from hydrogen and Ci to C4 alkyl and most preferably are hydrogen or methyl;
X is a bond or a group of Formula -O(L)- wherein L is a linking group optionally substituted with one or more acrylic or methacrylic groups.
6. A photocurable composition according to claim 5 wherein X is of formula -O(L)- and L is of formula CHR
Figure imgf000022_0001
Ila
Figure imgf000022_0002
wherein
Z is a spacer group selected from one or more of the following
Figure imgf000022_0003
-CH2— CH2 — S— )-
^ ~ ~ , or derivatives thereof; wherein p = 1-4
R2 is hydrogen or hydroxy;
G is selected from the group consisting of
Figure imgf000022_0004
Figure imgf000023_0001
wherein M is selected from the group consisting of a bond, H CH,
II I
— s— , — s— , — C— o CH3 methylene and — CH2 — S— CH2 —
R-i, R3 and R4 are independently selected from the group consisting of hydrogen and alkyl of 1 to 6 carbon atoms; n is an integer having a value of 0 to 10, and
Y is hydrogen or a halogen, preferably fluorine, chlorine or bromine.
7. A photocurable composition according to claim 1 wherein the acrylate monomer is selected from methacrylic acid anhydride; polyaikylene glycol dimethacrylates; polyaikylene glycol diacrylates; compounds of formula:
Figure imgf000023_0002
and compounds of formula
Figure imgf000023_0003
wherein the groups R are independently selected from hydrogen and methyl.
8. A photocurable composition according to claim 1 wherein the acrylate monomer is present in an amount of from 10 to 40% by weight of the total composition.
9. A photocurable composition according to claim 1 wherein the monomer containing at least two vinyl groups includes one or more compounds of Formula III
Figure imgf000024_0001
wherein X is
Figure imgf000024_0002
Z is a spacer group selected from one or more of the following
CH3 — CH2 — — ("C H2") — ° — — CH2— C-O — or
( — CH2— CH2— S- A , or derivatives thereof;
Y is hydrogen or halogen; n = 0, 1 or 2; m = 2 - 6 and p = 1 - 4.
10. A composition according to claim 1 wherein the compound containing at least two vinyl groups is divinyl benzene.
11. A composition according to claim 1 wherein the photoinitiator includes an acyl phosphine oxide.
12. A composition according to claim 11 wherein the acyl phosphine oxide is a bis-acyl phosphine oxide.
13. A composition according to claim 11 wherein the acylphosphine oxide is selected from the group consisting of bix-(2,4,6-trimethylbenzoyl)phenyl phosphine oxide, bis-(2,6-dimethylbenzoyl)-2,4,4-trimethylpentyl phosphine oxide and ethyl 2,4,6-trimethyl benzoyl phenyl phosphinate.
14. A composition according to claim 11 wherein the acyl phosphoric oxide is present in an amount of from 0.1 to 2% by weight of the total photocurable composition.
15. A composition according to claim 1 wherein the polythiol compound includes at least one compound selected from the group consisting of: Pentaerythritol tetrakis (3-mercapto-propionate) [PTMP], trimethylolpropane tris (3-mercaptopropionate) [TTMP], 4-mercaptomethyl-3,6-dithia-1 ,8-octanedithiol [MDO], pentaerythritol tetrakis (3-mercaptoacetate) [PTMA], trimethylolpropane tris (3-mercaptoacetate) [TTMA], 4-t-butyl-1 ,2-benzenedithiol, 2-mercaptoethyl- sulfide, 4,4'-thiodibenzenethiol, benzenedithiol, glycol dimercaptoacetate, glycol dimercaptopropionate ethylene bis(3-mercaptopropionate), polyethylene glycol dimercaptoacetates, polyethylene glycol di(3-mercaptopropionates), 2,5- bis(mercaptomethyl)-1 ,4-dithiane, 3,6-dithia-1 ,8-octanedithiol, TGBMA and DMPMA.
16. A composition according to claim 15 wherein the polythiol compound is TGBMA with or without PTMA.
17. A composition according to claim 1 wherein the polythiol compound is present in an amount of from 30 to 50% by weight of the total composition.
18. A composition according to claim 1 further comprising a heat curing agent adapted to induce curing at a temperature in the range of from 80°C to 140°C.
19. A method of preparing a lens comprising: forming a cast of a photocurable composition according to any one of the preceeding claims and having a thickness in the range of from 1 to 15 mm; subjecting the composition to UV radiation of wavelength having significant proportion in the wavelength range of from 350 to 450 nm; and
optionally heating the composition to a temperature in the range of from 80° to 140°C in the presence of a heat curing initiator.
PCT/AU2000/000349 1999-04-23 2000-04-20 Photocurable composition for preparing lenses WO2000064956A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU39476/00A AU3947600A (en) 1999-04-23 2000-04-20 Photocurable composition for preparing lenses

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPP9978 1999-04-23
AUPP9978A AUPP997899A0 (en) 1999-04-23 1999-04-23 Photocurable composition for preparing lenses

Publications (1)

Publication Number Publication Date
WO2000064956A1 true WO2000064956A1 (en) 2000-11-02

Family

ID=3814178

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2000/000349 WO2000064956A1 (en) 1999-04-23 2000-04-20 Photocurable composition for preparing lenses

Country Status (2)

Country Link
AU (1) AUPP997899A0 (en)
WO (1) WO2000064956A1 (en)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7465819B2 (en) 2006-01-24 2008-12-16 Chung Shan Institute Of Science And Technology Bisbiphenylacylphosphine oxide and preparation method therefore
JP2011157437A (en) * 2010-01-29 2011-08-18 Dic Corp Curable resin composition, cured product thereof, and plastic lens
US8846777B2 (en) 2008-04-22 2014-09-30 The Regents Of The University Of Colorado, A Body Corporate Thiol-vinyl and thiol-yne systems for shape memory polymers
US9701775B2 (en) * 2014-07-22 2017-07-11 Full Spectrum Laser, LLC Photopolymer resin dual initiation wavelengths for 3D printing
US20210363304A1 (en) * 2019-12-09 2021-11-25 Ares Materials Inc. Optically clear resin composition, flexible optical film and image display device
US11529230B2 (en) 2019-04-05 2022-12-20 Amo Groningen B.V. Systems and methods for correcting power of an intraocular lens using refractive index writing
US11583388B2 (en) 2019-04-05 2023-02-21 Amo Groningen B.V. Systems and methods for spectacle independence using refractive index writing with an intraocular lens
US11583389B2 (en) 2019-04-05 2023-02-21 Amo Groningen B.V. Systems and methods for correcting photic phenomenon from an intraocular lens and using refractive index writing
US11667742B2 (en) 2019-05-03 2023-06-06 Johnson & Johnson Surgical Vision, Inc. Compositions with high refractive index and Abbe number
US11678975B2 (en) 2019-04-05 2023-06-20 Amo Groningen B.V. Systems and methods for treating ocular disease with an intraocular lens and refractive index writing
US11708440B2 (en) 2019-05-03 2023-07-25 Johnson & Johnson Surgical Vision, Inc. High refractive index, high Abbe compositions
US11795252B2 (en) 2020-10-29 2023-10-24 Johnson & Johnson Surgical Vision, Inc. Compositions with high refractive index and Abbe number
US11931296B2 (en) 2019-04-05 2024-03-19 Amo Groningen B.V. Systems and methods for vergence matching of an intraocular lens with refractive index writing
US11944574B2 (en) 2019-04-05 2024-04-02 Amo Groningen B.V. Systems and methods for multiple layer intraocular lens and using refractive index writing

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02283731A (en) * 1989-04-24 1990-11-21 Toray Ind Inc Optical resin
JPH0445401A (en) * 1990-06-13 1992-02-14 Mitsubishi Gas Chem Co Inc Lens having high abbe's number
WO1996038486A1 (en) * 1995-05-30 1996-12-05 Sola International Holdings Ltd. High index/high abbe number composition
AU2455899A (en) * 1998-01-16 1999-08-02 Ppg Industries Ohio, Inc. Optical resin composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02283731A (en) * 1989-04-24 1990-11-21 Toray Ind Inc Optical resin
JPH0445401A (en) * 1990-06-13 1992-02-14 Mitsubishi Gas Chem Co Inc Lens having high abbe's number
WO1996038486A1 (en) * 1995-05-30 1996-12-05 Sola International Holdings Ltd. High index/high abbe number composition
AU2455899A (en) * 1998-01-16 1999-08-02 Ppg Industries Ohio, Inc. Optical resin composition

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7465819B2 (en) 2006-01-24 2008-12-16 Chung Shan Institute Of Science And Technology Bisbiphenylacylphosphine oxide and preparation method therefore
US7741505B2 (en) 2006-01-24 2010-06-22 Chung Shan Institute Of Science And Technology Bisbiphenylacylphosphine oxide and preparation method therefore
US7825274B2 (en) 2006-01-24 2010-11-02 Chung Shan Institute Of Science And Technology Bisbiphenylacylphosphine oxide and preparation method therefore
US8846777B2 (en) 2008-04-22 2014-09-30 The Regents Of The University Of Colorado, A Body Corporate Thiol-vinyl and thiol-yne systems for shape memory polymers
JP2011157437A (en) * 2010-01-29 2011-08-18 Dic Corp Curable resin composition, cured product thereof, and plastic lens
US9701775B2 (en) * 2014-07-22 2017-07-11 Full Spectrum Laser, LLC Photopolymer resin dual initiation wavelengths for 3D printing
US11583388B2 (en) 2019-04-05 2023-02-21 Amo Groningen B.V. Systems and methods for spectacle independence using refractive index writing with an intraocular lens
US11529230B2 (en) 2019-04-05 2022-12-20 Amo Groningen B.V. Systems and methods for correcting power of an intraocular lens using refractive index writing
US11583389B2 (en) 2019-04-05 2023-02-21 Amo Groningen B.V. Systems and methods for correcting photic phenomenon from an intraocular lens and using refractive index writing
US11678975B2 (en) 2019-04-05 2023-06-20 Amo Groningen B.V. Systems and methods for treating ocular disease with an intraocular lens and refractive index writing
US11931296B2 (en) 2019-04-05 2024-03-19 Amo Groningen B.V. Systems and methods for vergence matching of an intraocular lens with refractive index writing
US11944574B2 (en) 2019-04-05 2024-04-02 Amo Groningen B.V. Systems and methods for multiple layer intraocular lens and using refractive index writing
US11667742B2 (en) 2019-05-03 2023-06-06 Johnson & Johnson Surgical Vision, Inc. Compositions with high refractive index and Abbe number
US11708440B2 (en) 2019-05-03 2023-07-25 Johnson & Johnson Surgical Vision, Inc. High refractive index, high Abbe compositions
US20210363304A1 (en) * 2019-12-09 2021-11-25 Ares Materials Inc. Optically clear resin composition, flexible optical film and image display device
US11795252B2 (en) 2020-10-29 2023-10-24 Johnson & Johnson Surgical Vision, Inc. Compositions with high refractive index and Abbe number

Also Published As

Publication number Publication date
AUPP997899A0 (en) 1999-05-20

Similar Documents

Publication Publication Date Title
EP0598552B1 (en) Cross-linkable polymeric composition
WO2000064956A1 (en) Photocurable composition for preparing lenses
US5373033A (en) Casting composition
US5977276A (en) High index/high Abbe number composition
JP3030115B2 (en) Crosslinkable polymer casting composition
US4912185A (en) Cross-linkable casting compositions
EP0609061B1 (en) Polymerizable composition, polymer, organic glass and ophthalmic lens
US6313251B1 (en) High index/high abbe number composition
NL8105059A (en) LENS OF PLASTIC.
US6172140B1 (en) Acrylic thio monomers
EP0745621B1 (en) Polymerisable composition based on thio(meth)acrylate monomer, transparent polymer compositions and their optical use
JP3344408B2 (en) Curable resin composition
JPH05194672A (en) High refractive index optical material
EP0598551A2 (en) Cross-linkable polymeric composition
JPH08511814A (en) Telomer composition
JP3270100B2 (en) High refractive index optical material
EP1271186A1 (en) Composition for optical material, optical material and lenses
US6518393B2 (en) Polymerizable compositions for manufacturing transparent polymeric substrates, resulting transparent polymeric substrates and their applications in the optical field
JPH01182314A (en) Composition for lens having high abbe's number
WO1996014594A1 (en) High refractive index lenses
JPH07206944A (en) Composition for forming plastic lens and plastic lens produced by using the composition
JPH07216027A (en) Polymerizable composition, polymer, organic glass and lens for spectacle
AU709040B2 (en) High index/high abbe number composition
JPH02141702A (en) High abbe number lens
JP3149028B2 (en) Resin for high refractive index lens

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 10019999

Country of ref document: US

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP