GB2127422A - Prostheses contact lenses and polymers therefor - Google Patents
Prostheses contact lenses and polymers therefor Download PDFInfo
- Publication number
- GB2127422A GB2127422A GB08323215A GB8323215A GB2127422A GB 2127422 A GB2127422 A GB 2127422A GB 08323215 A GB08323215 A GB 08323215A GB 8323215 A GB8323215 A GB 8323215A GB 2127422 A GB2127422 A GB 2127422A
- Authority
- GB
- United Kingdom
- Prior art keywords
- methacrylate
- acrylate
- polymer according
- polymer
- siloxane
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
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
- G02B1/043—Contact lenses
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
Abstract
A dimensionally stable organosilicon polymer has pendant functional groups which are hydrolysable by means of biologically compatible aqueous liquids. The present invention further provides a prosthesis, contact lens or contact lens blank which is composed of an organosilicon polymer and which has a renewable wettable surface. Preferably the organosilicon polymers are prepared by copolymerization of a compound of the general formula I: <IMAGE> wherein: each B, which may be the same as or different from each other, represents -OR1, R1 being a C1-C5 alkyl group or phenyl, t has a value of from 1 to 5 and R2 is C1-C5 alkyl, hydrogen or another organosiloxy group as defined in the general formula I.
Description
SPECIFICATION
Prosthesis, contact lenses, and polymerstherefor This invention relatesto polymersandto articles produced from such polymers including prostheses and contact lenses.
A wide variety of siloxy-activated acrylate type monomers has been used to manufacture polymers for contact lenses. Such polymers however have frequently shown poorwettability and the prior art has employed numerous methods to improve the wettability of contact lenses fabricated from these polymers. Such treatments have included the deposition of hydrophilic polyelectrolyte complex coatings (e.g. U.K. Published Patent Application No.
201 2070A), the generation of hydrophilic (polar) groups on the lens surface by plasma glow discharge (e.g. U.S. Patent No. 4143949), and the grafting of hydrophilic monomers to the lens surface.
Such treatments however are unsatisfactory because, being superficial only, the wettability is frequently lost after a short period of wear by the patient. Moreover, a lens which has been so treated may not subsequently be altered by cutting or polishing (e.g.to remove scratches) sincethiswould destroy the wettable surface.
According to a first aspect of the present invention there is provided a dimensionally stable, organosilicon polymer having pendant functional groups which groups are hydrolysable by means of biologically compatible aqueous liquids.
According to a second aspect ofthe present invention there is provided a prosthesis or contact lens which is composed of an organosilicon polymer and which hasa renewable wettable surface.
By the present invention a polymer is provided which has hydrolysablefunctional groups, so that when a surface of the polymer is contacted by a biologically compatible aqueous liquid, e.g. water, the functional groups at the surface are hydrolysed thus to render the surface wettable. Others of the functional groups which remain within the body of the polymer will not be hydrolysed so that, upon a fresh exposure of polymer (e.g. by cutting or polishing) to a said biologically compatible liquid further hydrolyzation will occurthus providing a renewable wettable surface.
The functional groups may be provided in a siloxy monomer or prepolymerwhich is polymerized with any other suitable monomer or prepolymerto produce a polymer having desired characteristics, in such a way that the functional groups are not eliminated during the polymerization.
Examples of suitable functional groups which may be bonded to a Si atom of a siloxy monomer or prepolymer are
-OR,
wherein R represents C1-C5 alkyl or phenyl;
halo (preferably--C1); dialkyl amino wherein the alkyl groups are each
C1-C5 and may be the same or different; and dialkyl oximo wherein the alkyl groups are each C1-Cs and may be the same or different: and -C-N The alkoxy groups are preferred, most particularly methoxy groups.
Alternatively or additionally a siloxy monomer or prepolymer (which may or may not contain hydrolysable functional groups of its own) may be copolymerized with one or more monomers or prepolymers which will provide the resultant polymerwiththe required hydrolysablefunctional groups.
Examples of suitable monomersarethoseinclud- ing cyclic carboxylic anhydrides, amides esters and acetals as shown below:
Carboxylic acid anhydride(cyclic) wC -c O=C C=O / D\ Amide v C O=C N R R Ester (vinyl) YySC-rVllOrM-C sICorv C (acrylic) O C=0 -l (=0 O R R Acetal t - C cleavage point by H2D) R The non-hydrolysable organo-silicon monomers which may be used with such hydrolysable monomers may be any of those used in priorartformulations.
Examples of such monomers are disclosed, for example, in U.S. Patents Nos. 3808178,4120570 and 4216303, the contents of which are incorporated herein by reference.
Generally any hydrolysable silane containing polymerisableethylenic bonds such as vinyl or acrylic may be employed to provide the hydrolysable functional groups.
Preferred systems employ organo-silicon monomers or prepolymers of the following general formula I:
wherein:
each B, which may be the same as or differentfrom each other, represents OR" R1 being a C1-C5 alkyl group orphenyl, thas a valueoffrom 1 to 5 and R2 is C1-C5 alkyl, hydrogen or another organo siloxy group as defined in the general formula I.
Preferably the compound is gamma methacryloxy propyl trimethoxy ortriethoxy silane.
In preferred embodiments a compound of the aboveformula I is polymerised with a monomer derivedfrom acrylic or methacrylic acid such as
methyl acrylate and methacrylate
ethylacrylate and methacrylate
propyl acrylate and methacrylate
isopropyl acrylate and methacrylate
butyl acrylate and methacrylate
amyl acrylate and methacrylate
hexyl acrylate and methacrylate
heptyl acrylate and methacrylate
octyl acrylate and methacrylate
2-ethylhexyl acrylate and methacrylate
nonyl acrylate and methacrylate
decyl acrylate and methacrylate
undecyl acrylate and methacrylate
lauryl acrylate and methacrylate
cetyl acrylate and methacrylate
octadecyl acrylate and methacrylate
diacetone acrylamide hydroxy ethyl or
propyl methacrylate and acrylate diethyleneglycol monomethacrylate phenylacrylateand methacrylate
The compounds of general formula I may be also be copolymerized with other siloxane monomers such as are referred to in the said U.S. Patents, in the presence or absence ofthe aforesaid acrylic or methacrylic monomer, or in the presence or absence of one or more other organic monomers such as
N-vinyl pyrrolidone or styrene.
Preferred formulations incorporate gamma methacryloxypropyl trimethoxy silane, a said acrylic or methacrylic monomer, and a monomer or prepo lymer ofthefollowing general formula II:
wherein: m has avalue offrom 1 to 6, ncan befrom Oto an integer preferably less than or equal to 6 and each A, which may be the same as or different from each other, represents a C1-C5 alkyl group, a phenyl group or-CH = CH2.
A preferred compound ofthe general formula Ills vinyl methyl siloxane prepolymerwhich may be considered to have the following formula
Vinyl methyl siloxane prepolymer
although as supplied commercially it probably also contains other prepolymers including cyclics. The
Applicants have employed vinyl methyl siloxane as commercially available.
Preferred monomer mixtures contain up to 30% by weight of the vinyl siloxane, up to 60% by weight of a monomer of general formula land the balance being a said monomer derived from acrylic or methacrylic acid although, to increase the rigidity ofthe polymerized composition, a cross-linking agent may be incorporated in amounts which may be as high as 20 or30% by weight ofthetotal composition.
The cross-linking agent may be selected from one or more of
divinyl tetramethyl disiloxane
ethylene glycol dimethacrylate
allyl methacrylate and
pentaerythritol tetraacrylate
polyethylene glycol dimethacrylate
triethylene glycol dimethacrylate
tetraethylene glycol dimethacrylate
divinyl benzene although any suitable cross-linking agent can be employed.
The compositions may be chemically polymerized or polymerized by electromagnetic irradiation, e.g.
Y-irradiation, electron beam irradiation, etc. In the case of chemical polymerization a free radical initiator or catalyst is generally added and the mixture subjected to controlled heat, preferably in a stepwise manner to ensure orderly and efficient incorporation ofthe monomers into the polymer. The temperatures selected are preferably from 40-90 C,the polymerization being effected preferably for not less than 3 days.
Conventional free radical polymerization initiators may be employed such as azobis butyronitrile, benzoyl peroxide, tertiarybutyl peroxypivalate, chlorobenzyl peroxide, etc. The polymer can be cast into discs, rods or sheets for subsequent machining or directly into a lens shaped configuration. When polishing lenses preparedfrom such formulations it is generally advisable to use a water based polish.
In the case of Y-irradiation, suitable source may be employed, such as a Cobalt-60 source. The
Y-irradiation dosage is suitably from 2 to 5 Mega Rads.
Embodiments ofthe present invention will now be described byway of example only by referenceto the following Examples. Wetting angle is measured by the drop method, advancing.
EXAMPLE 1
Gamma methacryloxypropytrimethoxy silane; 50% by weight
Methyl methacrylate: 50% by weight
The above constituents were weighed, thoroughly mixed in the proportions stated and then filtered and degassed at room temperature. Up to 1 % by weight azobisbutyronitrile (AZBN) was added as a polymerization initiator and polymerization was effected at above ambienttemperature with gentle stepwiseheatingtoforma rod of polymer which was transparent, machinable, had good wettability and a water uptakeafter3 days immersion of approximately 2.4% by weight. It had a renewable hydrolysable surfce.The oxygen permeability was ascertained by a polarographic electrode technique to be 5.7DK xl 10- at 200 where DK has the following units: (cm2/sec) (m102/ml x mmHg)Thewetting angle was 510.
EXAMPLE2
By following the procedure of Example 1 a polymer was prepared from a mixture of 40 parts byweight gamma methacryloxypropyl trimethoxy silane 50 parts by weight methyl methacrylate, 10 parts by weight hydroxy ethyl methacrylate and 0.1 parts by weightAZBN.The resultantpolymerwastranspa- rent, machinable and had a water uptake of 236%. It had a renewable hydrolysable surface.
EXAMPLE3
By following the procedure of Example 1 a polymer was prepared from a mixture of 50 parts by weight gamma methacryloxypropyltrimethoxysilane,30 parts by weight methyl methacrylate, 20 parts by weig ht diacetone acrylamide,0.1 0.1 by weight AZBN and 20 parts by weight of allyl methacrylate as cross-linker. The resulantpolymerwastransparent and had a renewable hydrolysable surface.
EXAMPLE4
Following the procedure of Example 1 a polymer was prepared from a mixture of 17.5 parts by weight of vinyl methyl siloxane 54 parts by weight methyl methacrylate, 22.5 parts by weight of gamma methacryloxypropyl triethoxy silane, 0.1 part by weight AZBN and 10 parts by weight of allyl methacrylate as cross-linking agent.The resultant polymer was transparent with a refractive index of 1.45. It had a hardness of 80.46 (shore D) and a water uptake of 0.672%. It had a renewable hydrolysable surface, DKwas 12.4 and the wetting angle was 620.
EXAMPLE 5
A polymer was prepared exactly as in example 4 but using ethyl methacrylate instead of methyl methacrylate and gamma methacryloxypropyl trimethoxysiloxane in place ofthetriethoxy. The resultant polymer was transparent, machinable, had a water uptake of 0.92% oxygen permeability of 20.1
DK. The polymer had a renewwable hydrolysable surface.
EXAMPLE 6
A polymerwas prepared exactly as in Example 5 but using 24 and 30 parts by weight respectively of ethyl and methyl methacrylate instead of ethyl methacrylate alone. The resultant polymer was transparent, machinable had a water uptake of 1.1% and a DK of 13.2. The polymer had a renewable hydrolysable surface.
EXAMPLE 7
A polymer was prepared as in Example 1 using 7 parts by weight vinyl methyl siloxane,i8parts of gamma methacryloxypropyl trimethoxy silane, 15 parts by weight hexyl methacrylate, 30 parts by weight methyl methacrylate, 10 parts byweightallyl methacrylate and 0.1 part by weightAZBN. The resultant polymer was transparent, machinable and had a water uptake of 1.34%. The polymer had a renewable hydrolysable surface. DK was 8.7 and the wetting angle was 70".
EXAMPLE8
A polymer was prepared following the procedures of Example 1 from a mixture of 16.5 parts by weight vinyl methyl siloxane, 41 parts by weight methyl methacrylate, 22.5 parts by weight gamma methacry loxypropyltrimethoxysilane, 0.1 part byweight AZBN and 20 parts by weight of ethyleneglycol dimethacrylate as a cross-linking agent. The resultant polymer was translucent and machinable, with a water uptake of 1.3% and a DK of 12.4. The polymer had a renewable hydrolysable surface.
EXAMPLE 9
A polymer was prepared following the procedure of Example 1 but employing a mixture of 28 parts by weight of vi nyl methyl siloxane, 48 parts by weight of methyl methacrylate,18.9 parts by weight of gamma methacryloxypropyl trimethoxy silane 0.1 part by weightAZBN and 5.3 parts by weight of triethylene glycol dimethacrylate as a cross-linking agent. The resultant polymer was transparent, machinable had a water uptake of 0.21 % and a DK of 16.9. The polymer had a renewable hydrolysable surface (wetting angle 680).
EXAMPLE 10
A polymer was prepared according to the procedure of Example 1 but employing a mixture of 17.5 parts byweightvinyl methyl siloxane, 55 parts by weight methyl methacrylate,22.5 parts by weight gamma methacryloxypropyl trimethoxy silane, 0.1 part byweightAZBN and 5.0 parts by weight of divinyl tetramethyl disiloxane as a cross-linking agent. The resultant polymerwastransparentand machinable and had a water uptake of 1.49%. The polymer had a renewable hydrolysable surface.
EXAMPLE 11
A polymerwas prepared by q-irradiating a mixture containing 15 parts by weight of vinyl methyl siloxane, 60 parts by weight methyl methacrylate and 25 parts byweightofgamma methacryloxypropyl trimethoxy silane. The resultant polymer was transparent, machinable, had a water uptake of 0.55% and a DK of 5.11. The wetting angle was 62.5 .
The present invention provides a polymer whose characteristics such as transparency, hardness (or softness), wettability and oxygen permeability can be tailored to meet a particular requirement. Specifically the present invention is capable of providing polymers suitable for contact lenses which can be eyecompatible, relatively bacterilgically inert, scratchresistant, machinable and polishable, hard or soft, transparent or opaque, and wettable. Preferred polymers are hard and transparent with low wetting angles and high oxygen permeability.
In the preferred polymers ofthe present invention it isbelievedthatthemonomerofgeneralformula I contributes to monomer solution/polymerization compatibility, to oxygen permeability and, importantly, to lens wettability (and hence to wearer comfort), due to the presence ofthe hydrolysable groups B, whilst the acrylic or methacrylic acid monomer, if present, contributes to the optical and cutting qualities. The compound of the general formula II, if present, contributes to oxygen permeability.
Itisfinallyto be noted that colouring matter can be introduced into the monomer mixtures in orderthat tinted contact lenses can be produced.
Claims (24)
1. A dimensionally stable organosilicon polymer having pendantfunctional groups which groups are hydrolysable by means of biologically compatible aqueous liquids.
2. A polymer according to claim 1, wherein the functional groups are selected from
-OR,
wherein R represents C1-C5 alkyl or phenyl;
halo:
dialkyl amino wherein the alkyl groups are each C1-C5 and may be the same or different; and dialkyl oximo wherein the alkyl groups are each C1-C5 and may bethe same or different: and -C=-N, present in a polymerisable silane monomeror prepolymer.
3. A polymer according to claim 2, wherein the functional groups comprise methoxy and/or ethoxy groups.
4. A polymer according to claim 2, which is
prepared by polymerizing a silane of the following general formula I:
wherein:
each B, which may be the same as or differentfrom each other, represents-OR1, R1 being a C1-C5 alkyl group or phenyl, thas a value offrom 1 to 5 and R2 is
C1-C5 alkyl, hydrogen or another organo siloxy group as defined inthe general formula
5. A polymer according to claim 4, wherein the silane comprises gamma methacryloxypropyl trimethoxysiloxane.
6. A polymer according to claim 4, wherein the silane comprises gamma methacryloxypropyl triethoxy siloxane.
7. A polymer according to claim 4,5 or 6, which is the resuit of polymerizing a said silane with a monomer derived from acrylic or methacrylic acid.
8. A polymer according to claim 7, wherein said monomer derived from acrylic or methacrylic acid is selected from
methyl acrylate and methacrylate
ethyl acrylate and methacrylate
propyl acrylate and methacrylate
isopropyl acrylate and methacrylate
butyl acrylate and methacrylate
amyl acrylate and methacrylate
hexyl acrylate and methacrylate
heptyl acrylate and methacrylate
octyl acrylate and methacrylate
2-ethylhexyl acrylate and methacrylate
nonyl acrylate and methacrylate
decyl acrylate and methacrylate
undecyl acrylate and methacrylate
lauryl acrylate and methacrylate
cetyl acrylate and methacrylate
octadecyl acrylate and methacrylate
diacetone diacrylamide
hydroxy ethyl or propyl methacrylate and acrylate
diethylene glycol monomethacrylate.
phenyl acrylate and methacrylate.
9. A polymer according to claims 4,5 or 6 which is the result of polymerizing a said silane with N-vinyl pyrrolidone or styrene.
10. A polymer according to any preceding claim, which includessiloxane unitswhich do not contain, when in the resultant polymer, hydrolysable functional groups.
11. A polymer according to claims 4 and 10 when dependent thereupon, wherein the silane of general formula I is copolymerized with a vinyl siloxane of the following general formula ll:
wherein: m has a value offrom 1 to 6, n can be from Oto an integer preferably less than or equal to 6 and each A, which may be the same as or different from each other, represents a C1-C5 alkyl group or a phenyl group.
12. A polymer according to claim 11, wherein the vinyl siloxane comprises vinyl methyl siloxane.
13. A polymer according to claim 11, which additionally incorporates one or more monomers as defined in claim 7 or 8.
14. Apolymeraccording to claim 13, which contains upto30 parts by weight ofthevinyl siloxane, upto 60 parts by weight of a compound of general formula I and tire balance being substantially a said monomer derived from acrylic or methacrylic acid, or styrene or N-vinyl pyrrolidone.
15. Apolymeraccording to claim 14which incorporates a cross-linking agent.
16. A polymer according to claim 1, wherein the hydrolysable functional groups are derived from one or more organic monomers or prepolymers containing such hydrolysable functional groups, which monomers or prepolymers have been copolymerized with a siloxane.
17. A polymer according to claim 15, wherein the or each organic monomer or prepolymer is selected from cyclic carboxylic anhydrides, amides, esters and acetals.
18. A polymer according to claim 15, wherein the siloxane also contains said hydrolysablefunctional groups.
19. A polymer according to claim 1 andsubstan tiallyas hereinbefore described with reference to any one oftheforegoing individual Examples 1 to 11.
20. An article madefrom a polymer as claimed in any preceding claim.
21. An article according to claim 19 in the form of a prosthesis.
22. An article according to claim 19 in the form of a contact lens or contact lens blank.
23. A prosthesis, contact lens or contact lens blank which is composed of an organosilicon polym erandwhich has a renewablewettablesurface.
24. A polymer as claimed in claim 14 or 15 and in the form of a prosthesis, contact lens or contact lens blank.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08323215A GB2127422B (en) | 1982-08-27 | 1983-08-30 | Prostheses contact lenses and polymers therefor |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8224630 | 1982-08-27 | ||
| GB08323215A GB2127422B (en) | 1982-08-27 | 1983-08-30 | Prostheses contact lenses and polymers therefor |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8323215D0 GB8323215D0 (en) | 1983-09-28 |
| GB2127422A true GB2127422A (en) | 1984-04-11 |
| GB2127422B GB2127422B (en) | 1987-02-25 |
Family
ID=26283685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08323215A Expired GB2127422B (en) | 1982-08-27 | 1983-08-30 | Prostheses contact lenses and polymers therefor |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2127422B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0762149A2 (en) * | 1995-09-11 | 1997-03-12 | Menicon Co., Ltd. | Water-absorptive soft ocular lens material, water-absorptive soft ocular lens shaped product made thereof, water-absorptive soft ocular lens made thereof and process for its production |
| EP0770888A3 (en) * | 1995-10-24 | 1997-12-29 | Menicon Co., Ltd. | Low water-absorptive ocular lens material, low water-absorptive ocular lens shaped product made thereof, low water-absorptive ocular lens made thereof and process for its production |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB868188A (en) * | 1958-12-05 | 1961-05-17 | Midland Silicones Ltd | Organosilicon co-polymers |
| GB1200756A (en) * | 1966-08-10 | 1970-08-05 | Rank Xerox Ltd | Silicon-containing terpolymers |
| GB1205671A (en) * | 1967-01-05 | 1970-09-16 | Dow Corning | Primer for room temperature vulcanizing polyurethanes |
| GB1205051A (en) * | 1966-08-10 | 1970-09-16 | Rank Xerox Ltd | Electrostatographic developers |
| GB1218408A (en) * | 1967-09-08 | 1971-01-06 | Dynamit Nobel Ag | Improvements in or relating to the copolymerisation of vinyl trialkoxysilanes |
| GB1247346A (en) * | 1968-01-12 | 1971-09-22 | Fibreglass Ltd | Chemical composition for use in coating glass fibres |
| GB1291159A (en) * | 1969-07-23 | 1972-10-04 | Dynamit Nobel Ag | Improvements in or relating to vinylchloride copolymers and to shaped structures obtained therefrom |
| GB1372453A (en) * | 1971-01-15 | 1974-10-30 | Hoechst Ag | Process for making fibrous material water-repellent |
| GB2014591A (en) * | 1978-02-15 | 1979-08-30 | Polymer Technology Corp | Silicon-containing copolymers for contact lenses |
| WO1980000253A1 (en) * | 1978-07-17 | 1980-02-21 | S Chang | Hydrophilic,soft and oxygen permeable copolymer compositions |
| GB1604519A (en) * | 1977-07-25 | 1981-12-09 | Bausch & Lomb | Polysiloxane polymers and contact lens and other biomedical articles formed therefrom |
| US4306042A (en) * | 1980-09-02 | 1981-12-15 | Neefe Russell A | Method of making a contact lens material with increased oxygen permeability |
| GB2086914A (en) * | 1980-10-08 | 1982-05-19 | G C Shika Kogya Kk | Compositions for use in Dentistry |
-
1983
- 1983-08-30 GB GB08323215A patent/GB2127422B/en not_active Expired
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB868188A (en) * | 1958-12-05 | 1961-05-17 | Midland Silicones Ltd | Organosilicon co-polymers |
| GB1200756A (en) * | 1966-08-10 | 1970-08-05 | Rank Xerox Ltd | Silicon-containing terpolymers |
| GB1205051A (en) * | 1966-08-10 | 1970-09-16 | Rank Xerox Ltd | Electrostatographic developers |
| GB1205671A (en) * | 1967-01-05 | 1970-09-16 | Dow Corning | Primer for room temperature vulcanizing polyurethanes |
| GB1218408A (en) * | 1967-09-08 | 1971-01-06 | Dynamit Nobel Ag | Improvements in or relating to the copolymerisation of vinyl trialkoxysilanes |
| GB1247346A (en) * | 1968-01-12 | 1971-09-22 | Fibreglass Ltd | Chemical composition for use in coating glass fibres |
| GB1291159A (en) * | 1969-07-23 | 1972-10-04 | Dynamit Nobel Ag | Improvements in or relating to vinylchloride copolymers and to shaped structures obtained therefrom |
| GB1372453A (en) * | 1971-01-15 | 1974-10-30 | Hoechst Ag | Process for making fibrous material water-repellent |
| GB1604519A (en) * | 1977-07-25 | 1981-12-09 | Bausch & Lomb | Polysiloxane polymers and contact lens and other biomedical articles formed therefrom |
| GB2014591A (en) * | 1978-02-15 | 1979-08-30 | Polymer Technology Corp | Silicon-containing copolymers for contact lenses |
| WO1980000253A1 (en) * | 1978-07-17 | 1980-02-21 | S Chang | Hydrophilic,soft and oxygen permeable copolymer compositions |
| US4306042A (en) * | 1980-09-02 | 1981-12-15 | Neefe Russell A | Method of making a contact lens material with increased oxygen permeability |
| GB2086914A (en) * | 1980-10-08 | 1982-05-19 | G C Shika Kogya Kk | Compositions for use in Dentistry |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0762149A2 (en) * | 1995-09-11 | 1997-03-12 | Menicon Co., Ltd. | Water-absorptive soft ocular lens material, water-absorptive soft ocular lens shaped product made thereof, water-absorptive soft ocular lens made thereof and process for its production |
| EP0762149A3 (en) * | 1995-09-11 | 1997-12-10 | Menicon Co., Ltd. | Water-absorptive soft ocular lens material, water-absorptive soft ocular lens shaped product made thereof, water-absorptive soft ocular lens made thereof and process for its production |
| US5817726A (en) * | 1995-09-11 | 1998-10-06 | Menicon Co., Ltd. | Water-absorptive soft ocular lens material, water-absorptive soft ocular lens shaped product made thereof, water-absorptive soft ocular lens made thereof and process for its production |
| EP0770888A3 (en) * | 1995-10-24 | 1997-12-29 | Menicon Co., Ltd. | Low water-absorptive ocular lens material, low water-absorptive ocular lens shaped product made thereof, low water-absorptive ocular lens made thereof and process for its production |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8323215D0 (en) | 1983-09-28 |
| GB2127422B (en) | 1987-02-25 |
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