GB2181440A - Hydrophilic copolymer suitable for contact lenses - Google Patents
Hydrophilic copolymer suitable for contact lenses Download PDFInfo
- Publication number
- GB2181440A GB2181440A GB08621275A GB8621275A GB2181440A GB 2181440 A GB2181440 A GB 2181440A GB 08621275 A GB08621275 A GB 08621275A GB 8621275 A GB8621275 A GB 8621275A GB 2181440 A GB2181440 A GB 2181440A
- Authority
- GB
- United Kingdom
- Prior art keywords
- hydrophilic copolymer
- glycol dimethacrylate
- diethylene glycol
- methacrylate
- mixture
- 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
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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
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials For Medical Uses (AREA)
- Eyeglasses (AREA)
Abstract
A hydrophilic copolymer suitable for contact lenses is prepared by copolymerization of (A) 70-99.5 wt.% of diethylene glycol monomethacrylate, (B) 0.5-30 wt.% vinyl monomers selected from the group comprising esters and amides of methacrylic acid and acrylic acid, e.g. butyl methacrylate, dodecyl methacrylate, 2-ethoxyethyl methacrylate or N-t-butylacrylamide and (c) 0.01-2 wt.% of a crosslinking agent containing at least two olefinic double bonds in the molecule, e.g. ethylene glycol dimethacrylate.
Description
SPECIFICATION
Hydrophilic copolymer suitable for contact lenses and medical application and a method for producing thereof
The invention pertains to a hydrophilic copolymer suitable for contact lenses and medical application and to a method of its production
They are known water-swelling elastomers with various equilibrium content of water suitable for the production of soft hydrophilic contact lenses and also for various medical purposes.
Poly(2-hydroxyethyl methacrylate) (poly-HEMA) proved excellently suitable for applications where good mechanical properties are required and the water content about 40 wt.% is sufficient.
However, some applications need highly swelling materials (e.g. contact lenses for permanent wearing) often even with a lower shear modulus but a sufficient elongation. Nevertheless. the known hydrophilic polymers with a high swelling capacity have their mechanical properties unsuitable to such extent, that they cannot be used for this purpose. Therefore, they were developed lightly crosslinked copolymers of highly hydrophilic N-vinylpyrrolidone with hydrophobic alkyl methacrylate (Brit. Pat. No. 1514810), which have more suitable mechanical properties in addition to the high swelling capacity but contain an undesirable extractable portion.A homologue of 2-hydroxyethyl methacrylate, diethylene glycol methacrylate (DEGMA; 2,2'-oxydiethanol monomethacrylate) gives polymers strongly swelling due to its ether oxygen atom in the ester chain which, however, do not exhibit suitable mechanical properties even in a crosslinked state and cannot be used for some applications.
The above said disadvantages are overcome in a hydrophilic copolymer suitable above all for contact lenses and medical applications, which can be prepared according to the invention by copolymerisation of 70 to 99.5 wt.% of diethylene glycol methacrylate (DEGMA; 2,2'-oxydiethanol monomethacrylate) with 0.5 to 30 wt.% of vinyl monomers selected from the group comprising esters and amides of methacrylate acid and acrylic acid in the presence of radical initiators. The radical initiators are selected from the group comprising azo compounds, peroxides, peroxocarbonates, peroxosulfates, photoinitiators based on benzoin ethers and their derivatives, and initiation redox systems, advantageously peroxosulfate-disulfite, peroxosulfate-alkylamines, benzoyl peroxide-alkylamines, and used in the concentration 0.01 to 3 wt.%.
Methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, dodecyl methacrylate, ethoxyethyl methacrylate, n-butyl acrylate, N-tert-butylacrylamide and N-ethylacrylamide are advantageously used as the vinyl monomers.
The copolymerization may be carried out also in the presence of polar solvents, as are advantageously glycerol, glycols and their derivatives, water, dimethylformamide, dimethylsulfoxide, dimethylacetamide, diacetine, isopropylalcohol, or their mixtures.
They were prepared the copolymers of diethylene glycol methacrylate with a selected ester or amide of methacrylic acid or acrylic acid in the presence of diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and ethylene glycol dimethacrylate or an arbitrary diester of methacrylic acid or acrylic acid with the corresponding alkylene glycol, methylene-bis-acrylamide, ethylene-bis-methacrylamide, hexamethylene-bis-methacrylamide, and others, always in such a way that at least 3 components enter the polymerization, two of which are monoesters and the third one is a crosslinking agent, while one of the monoesters is diethylene glycol monomethacrylate.Diethylene glycol monomethacrylate contains the diester diethylene glycol dimethacrylate from its synthesis, which diester may act as a crossliking component alone, or becomes a part of a mixture of crosslinking agents, or has to be a mixture of crosslinking agents, or has to be removed or decreased to a minimum in diethylene glycol methacrylate, if other crosslinking system is used.
At the above specified content of monomesters and the kept allowed concentration of a diester or diesters of acrylic acid or methacrylic acid, or amide or amides of acrylic acid or methacrylic acid, the resulting hydrophilic terpolymer of higher copolymer attains such mechanical properties that it can be used for the preparation of contact lenses or for medical purposes. The content of water in the final three-dimensional hydrogel continuously increases with the increasing content of the DEGMA component in the mixture. Hydrogels with suitable mechanical properties at the equilibrium water content 50 to 70 wt% are obtained with the component ratio according to the invention.
The copolymers according to the invention have pronouncedly better mechanical properties that the homopolymer of DEGMA, often comparable with the mechanical properties of HEMA polymers and always suitable for the applications according to the invention. The copolymers according to the invention are virtually free of water-soluble extractables and do not contain ionogenic groups in their structure. Therefore, thy can be expected lower deposits of eye proteins with contact lenses made from these copolymers in comparison to copolymers containing, e.g., methacrylic acid or its salts. The copolymers according to the invention secure a sufficiently high equilibrium content of water in the resulting gel at the retained optical and mechanical properties, so that they may be used for the production of contact lenses for permanent wearing.
The invention is illustrated in detail in the following examples of performance without, however, limiting its scope by any means.
Example 1
The mixture with composition 90 wt.% of ethylene glycol methacrylate (further DEGMA) and 10 wt.% of butyl methacrylate containing 0.5 wt.% of diethylene glycol dimethacrylate was polymerized with 0.2 wt.% of azobisisobutyronitrile related to the total amount of monomers for 16 hours at 600C. The resulting material contains after swelling 59 wt.% of water and had
G=0.100 MPa, elongation 112% and strength 0.185 MPa.
Example 2
The mixture with composition 95% of DEGMA and 5 wt.% of butyl methacrylate containing 0.5 wt.% of diethylene glycol dimethacrylate was polymerized with 0.2 wt.% azobisisobutyronitrile related to the total weight of monomers for 16 hours at 600C. The resulting material contains after swelling 68 wt.% of water at G=0.1 MPa, elongation 129% and strength 0.215
MPa.
Example 3
The mixture with composition 95 wt.% DEGMA and 5 wt.% of butyl methacrylate containing 0.6 wt.% of diethylene glycol dimethacrylate and 0.15 wt.% of ethylene glycol dimethacrylate was mixed in the amount of 70% with 30 wt.% of 2-hydroxyethyl methacrylate (further HEMA).
This mixture was polymerized with 0.2 wt.% of azobisisobutyronitrile related to the total weight of monomers for 16 hours at 60"C. The resulting material(contained after swelling 54 wt.% of water at G=0.139 MPa, elongation 165%, strength 0.320 MPa, and KV=1.35 (Kv is the coefficient of linear expansion during the swelling in H20).
Example 4
The mixture with composition 95 wt.% DEGMA and 5 wt.% of butyl methacrylate containing 0.6 wt.% of diethylene glycol dimethacrylate and 0.15 wt.% of ethylene glycol dimethacrylate was mixed in the amount of 60 wt.% with 40 wt.% HEMA. This mixture was polymerized with 0.2 wt.% of azobisisobutyronitrile related to the total weight of monomers for 16 hours at 60"C.
The resulting material contains after swelling 49 wt.% of water at G=0.365 MPa, strength 0.235 MPa, and Kv1.31 Example 5
The mixture with composition 95% DEGMA and 5 wt.% of butyl methacrylate containing 0.6 wt.% of diethylene glycol dimethacrylate and 0.15 wt.% of ethylene glycol dimethacrylate was mixed in the amount of 50 wt.% with 50 wt.% HEMA. This mixture was polymerized with 0.2 wt.% of azobisisobutyronitrile related to the total amount of monomers for 16 hours at 60"C.
The resulting material contains after swelling 48 wt.% of water at G=0.548 MPa and Kv= 1.38.
Example 6
The mixture with composition 95 wt.% DEGMA and 5 wt.% of 2-ethoxyethyl methacrylate containing 0.5 wt.% of diethylene glycol dimethacrylate was polymerized with 0.2 wt.% of azobisisobutyronitrile related to the total amount of monomers for 16 hours at 60"C. The resulting material contains after swelling 69 wt.% of water at G=0.077 MPa and Kv= 1.56.
Example 7
The mixture with composition 90 wt.% DEGMA and 10 wt.% of 2-ethoxyethyl methacrylate containing 0.2 wt.% of diethylene glycol dimethacrylate and 0.7 wt.% of triethylene glycol dimethacrylate was polymerized with 0.2 wt.% of azobisisobutyronitrile related to the total amount of monomers for 16 hours at 60"C. The resulting material contains after swelling 67 wt.% of water at G=0.087 MPa, elongation 146% and strength 0.194 MPa.
Example 8
The mixture with composition 80 wt.% DEGMA and 20 wt.% of 2-ethoxyethyl methacrylate containing 0.4 wt.% of ethylene glycol dimethacrylate and 0.20 wt.% of triethylene glycol dimethactylate was polymerized with 0.2 wt.% of azobisisobutyronitrile related to the total weight of monomers for 16 hours at 60"C. The resulting material contains after swelling 60 wt.% of water at G=0.178 and Kv=1.41.
Example 9
The mixture with composition 70 wt.% DEGMA and 30 wt.% of 2-ethoxyethyl methacrylate containing 0.5 wt.% of diethylene glycol methacrylate was polymerized with 0.2 wt.% of azobisisobutyronitrile related to the total weight of monomers for 16 hours at 60"C. The resulting material contains after swelling 49 wt.% of water at G=0.181 MPa and K,=1.28.
Example 10
The mixture with composition 97 wt.% DEGMA and 3 wt.% of N-tert-butylacrylamide containing 0.6 wt.% of diethylene glycol dimethacrylate and 0.15 wt.% of ethylene glycol dimethacrylate was ploymerized with 0.2 wt.% of azobisisobutyronitrile related to the total weight of monomers for 16 hours at 60"C. The resulting material contains after swelling 62 wt.% of water at G=0.170 MPa.
Example 11
The mixture with composition 95 wt.% DEGMA and 5 wt.% of N-tert-butylacrylamide containing 0.5 wt.% of diethylene glycol dimethacrylate was polymerized with 0.2 wt.% of azobisisobutyronitrile related to the total weight of monomers for 16 hours at 60"C. The resulting material contains after swelling 68 wt.% of water at G=0.108 MPa.
Example 12
The mixture with composition 95 wt.% DEGMA and 5 wt.% of dodecyl methacrylate containing 0.5 wt.% of diethylene glycol dimethacrylate was polymerized with 0.4 wt.% of azobisisobutyronitrile related to the total weight of monomers for 16 hours at 60"C. The resulting material contains after swelling 67 wt.% of Dwater at G=0.118 MPa and KV=1.51.
Example 13
The mixture with composition 95 wt.% DEGMA and 5 wt.% of dodecyl methacrylate containing 0.5 wt.% of diethylene glycol dimethacrylate was polymerized with 0.2 wt.% of azobisisobutyronitrile related to the total weight of monomers for 16 hours at 60"C. The resulting material contains after swelling 67 wt.% of water of G=0.110 MPa and KV=1.51.
Example 14
The mixture with composition 90 wt.% DEGMA and 10 wt.% of dodecyl methacrylate containing 0.6 wt.% of diethylene glycol dimethacylate and 0.15 wt.% ethylene glycol dimethacrylate was polymerized with 0.2 wt.% of azobisisobutyronitrile related to the total weight of monomers for 16 hours at 60"C. The resulting material contains after swelling 62 wt.% of water at G=0.120 MPa and KV=1.43.
Example 15
The mixture with composition 80 wt.% DEGMA and 20 wt.% of dodecyl methacrylate containing 0.6 wt.% of diethylene glycol dimethacrylate and 0.15 wt.% of ethylene glycol dimethacrylate was polymerized with 0.2 wt.% of azobisisobutyronitrile related to the total weight of monomers for 16 hours at 60"C. The resulting material contains after swelling 55 wt.% of water at G=0.125 MPa.
Example 16
The mixture with composition 95 wt.% DEGMA and 5 wt.% of tert-butyl methacrylate containing 0.3 wt.% of ethylene glycol dimethacrylate, 0.20 wt.% of diethylene glycol dimethacrylate and 0.3 wt.% of triethylene glycol dimethacrylate was polymerized with 0.2 wt.% of azobisisobutyronitrile related to the total weight of monomers for 16 hours at 60"C. The resulting material contains after swelling 66 wt.% of water at G=0.117 MPa and KV=1.51.
Example 17
The mixture with composition 90 wt.% DEGMA and 10 wt.% of tert-butyl methacrylate containing 0.5 wt.% of ethylene glycol dimethacrylate was polymerized with 0.2 wt.% of azobisisobutyronitrile related to the total weight of monomers for 16 hours at 60"C. The resulting material contains after swelling 55 wt.% of water at G=0.395 MPa and Kv= 1.36.
Example 18
The mixture with composition 95 wt.% DEGMA and 5 wt.% of tert-butyl methacrylate containing 0.20 wt.% of ethylene glycol dimethacrylate and 0.15 wt.% of diethylene glycol dimethacrylate was polymerized with 0.2 wt.% of azobisisobutyronitrile related to the total weight of monomers for 16 hours at 60"C. The resulting material contains after swelling 67 wt.% of water at G=0.110 MPa.
Example 19
The mixture with composition 95 wt.% DEGMA and 5 wt.% of tert-butyl methacrylate contain ing 0.6 wt.% of ethylene glycol dimethacrylate and 0.6 wt.% of diethylene glycol dimethacrylate was polymerized with 0.2 wt.% of azobisisobutyronitrile related to the total weight of monomers for 16 hours at 60"C. The resulting material contains after swelling 63 wt.% of water at
G=0.132 MPa.
Example 20
The mixture with composition 95 wt.% of DEGMA and 5 wt.% of dodecyl methacrylate containing 0.15 wt.% of ethylene glycol dimethacrylate was polymerized with 0.2 wt.% of azobisisobutyronitrile related to the total weight of monomers for 16 hours at 60"C. The resulting material contains after swelling 68 wt.% of water at G=0.095 MPa.
Example 21
The mixture with composition 95 wt.% DEGMA and 5 wit.% of dodecyl methacrylate containing 0.6 wt.% of ethylene glycol dimethacrylate and 0.6 wt.% of diethylene gylcol dimethacrylate was polymerized with 0.2 wt.% of azobisiisobutyronitrile related to the total weight of monomers for 16 hours at 600C. The resulting material contains after swelling 65 wt.% of water at
G=0.117 MPa.
Example 22.
The mixture with composition 90 wt.% DEGMA and 10 wt.% of tert-butyl methacrylate containing 0.5 wt.% of diethylene glycol dimethacrylate was polymerized with 0.1 wt.% of diisopropyl peroxocarbonate related to the total weight of monomers for 16 hours at 60"C. The resulting material contains after swelling 55.3 wt.% of water at G=0.390 MPa.
Example 23.
The mixture with composition 90 wt.% DEGMA and 10 wt.% of tert-butyl methacrylate containing 0.5 wt.% of diethylene glycol dimethacrylate was polymerized with 0.2 wt.% of ammonium peroxosulfate related to the total amount of monomers for 1 hour at 78"C. The resulting material contains after swelling 55.1 wt.% of water at G=0.390 MPa.
Example 24.
The mixture with composition 90 wt.% DEGMA and 10 wt.% of tert-butyl methacrylate containing 0.6 wt.% of diethylene glycol dimethacrylate and 0.15 wt.% of ethylene glycol dimethacrylate was polymerized with 0.5 wt.% benzoin ethyl ether related to the total weight of monomers for 15 min under UV radiation. The resulting material contained after swelling 55 wt.% of water at G=0.395 MPa.
Example 25
The mixture with composition 90 wt.% DEGMA and 10 wt.% of tert-butyl methacrylate containing 0.5 wt.% of diethylene glycol dimethacrylate was polymerized with 0.5 wt.% of benzoin methyl ether related to the total weight of monomers for 15 min under UV radiation.
The resulting material contains after swelling 55.6 wt.% of water at G=0.385 MPa.
Example 26
The mixture with composition 95 wt.% DEGMA and 5 wt.% of 2-ethoxyethyl methacrylate containing 0.45 wt.% of ethylene glycol dimethacrylate and 0.2 wt.% of diethylene glycol dimethacrylate was polymerized with 0.1 wt.% of diisopropyl peroxocarbonate related to the total weight of monomers for 16 hours at 60"C. The resulting material contains after swelling 69.1 wt.% of water at G=0.077 MPa.
Example 27
The mixture with composition 95 wt.% of DEGMA and 5 wt.% of 2-ethoxyethyl methacrylate containing 0.2 wt.% of diethylene glycol dimethacrylate and 0.7 wt.% of triethylene glycol dimethacrylate was polymerized with 0.2 wt.% of ammonium peroxosulfate related to the total weight of monomers for 1 hour at 78"C. The resulting material contains after swelling 68.8 wt.% of water at G=0.079 MPa.
Example 28
The mixture with composition 95 wt.% DEGMA and 5 wt.% of 2-ethoxyethyl methacrylate containing 0.5 wt.% of diethylene glycol dimethacrylate was polymerized with 0.5 wt.% of benzoin ethyl ether related to the total weight of monomers for 15 min under UV radiation. The resulting material contains after swelling 69 wt.% of water at G=0.077 MPa.
Example 29
The mixture with composition 95 wt.% DEGMA and 5 wt.% of 2-ethoxyethyl methacrylate containing 0.6 wt.% of diethylene glycol dimethacrylate and 0.15 wt.% of ethylene glycol dimethacrylate was polymerized with 0.5 wt.% of benzoin methyl ether related to the total weight of monomers for 15 min under UV radiation. The resulting material contains after swelling 69 wt.% of water at G=0.078 MPa.
Claims (9)
1. Hydrophilic copolymer suitable for contact lenses and medical application which is prepared by copolymerization of 70 to 99.5 wt.% of diethylene glycol monomethacrylate with 0.5 to 30 wt.% of vinyl monomers selected from the group comprising esters and amides of methacrylic acid and acrylic acid in the presence of 0.01 to 2 wt.% of a crosslinking agent having at least two olefinic double bonds in the molecule and in the presence of radical initiators.
2. The hydrophilic copolymer according to Claim 1, wherein the vinyl monomers selected from the group comprising esters and amides of methacrylic acid and acrylic acid are methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, dodecyl methacrylate, ethoxyethyl methacrylate, n-butyl acrylate, N-tert-butylacrylamide, and N-ethylacrylamide.
3. The hydrophilic copolymer according to Claims 1 and 2, wherein the crosslinking agent is selected from the group comprising multifunctional esters or amides of acrylic acid and methacrylic acid.
4. The hydrophilic copolymer according to Claims 1 through 3, wherein the radical initiators are selected from the group comprising azo compounds, peroxides, peroxocarbonates, peroxosulfates, photoinitiators based on benzoin ethers and their derivatives, and initiation redox systems.
5. The hydrophilic copolymer according to Claims 1 through 4, wherein the copolymerization is carried out in the presence of polar solvents, advantageously in the presence of glycerol, glycols and their derivatives, water, dimetylformamide, dimethylsulfoxide, dimethylacetamide, diacetine, isopropylalcohol, or their mixtures.
6. Method for the production of the hydrophilic copolymer according to Claims 1 through 5, wherein at least 70 wt.% of diethylene glycol monomethacrylate is copolymerized with at utmost 30 wt.% of vinyl monomers, selected from the group comprising esters and amides of methacrylic acid and acrylic acid, in the presence of 0.01 to 2 wt.% of a crosslinking agent having at least two olefinic double bonds and in the presence of radical initiators.
7. The method according to Claim 6, wherein the copolymerization is carried out in the presence of a polar solvent or a mixture of polar solvents.
8. Hydrophilic copolymer as claimed in Claim 1 substantially as described in any one of the examples disclosed herein.
9. Method as claimed in Claim 6 substantially as described with reference to any one of the examples disclosed herein.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS856341A CS256437B1 (en) | 1985-09-04 | 1985-09-04 | Hydrophilic copolymer especially for contact lenses and medicinal application and method of its production |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8621275D0 GB8621275D0 (en) | 1986-10-08 |
| GB2181440A true GB2181440A (en) | 1987-04-23 |
| GB2181440B GB2181440B (en) | 1990-04-25 |
Family
ID=5410226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8621275A Expired - Fee Related GB2181440B (en) | 1985-09-04 | 1986-09-03 | Hydrophilic copolymer suitable for contact lenses and medical application and a method for producing thereof |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS62116616A (en) |
| CA (1) | CA1293577C (en) |
| CS (1) | CS256437B1 (en) |
| DE (1) | DE3630187A1 (en) |
| FR (1) | FR2586690B1 (en) |
| GB (1) | GB2181440B (en) |
| IT (1) | IT1197469B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996004189A1 (en) * | 1994-08-05 | 1996-02-15 | Smithkline Beecham P.L.C | Container for moisture-sensitive material |
| AU711609B2 (en) * | 1994-08-05 | 1999-10-14 | West Pharmaceutical Services Cornwall Limited | Container for moisture-sensitive material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10035119A1 (en) | 2000-07-19 | 2002-01-31 | Basf Ag | Partially branched polymers |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB814009A (en) * | 1956-04-24 | 1959-05-27 | Otto Wichterle | Three-dimensional hydrophilic high polymeric articles |
| GB1035877A (en) * | 1963-09-07 | 1966-07-13 | Ceskoslovenska Akademie Ved | Method of manufacturing contact lenses from hydrogels capable of swelling |
| GB1291650A (en) * | 1969-03-04 | 1972-10-04 | Ceskoslovenska Akademie Ved | Method of preparing novel hydrophilic copolymers with low softening points |
| GB1424587A (en) * | 1973-02-27 | 1976-02-11 | Union Optics Corp | Copolymers and hydrogels of unsaturated esters |
| GB1435966A (en) * | 1972-05-02 | 1976-05-19 | Ceskoslovenska Akademie Ved | Process for producing hydrophilic polymers containing -cn groups |
| GB1495043A (en) * | 1974-05-27 | 1977-12-14 | Hoya Lens Co Ltd | Soft contact lenses and a process and composition for use in their manufacture |
| GB1569493A (en) * | 1976-02-25 | 1980-06-18 | Hoya Lens Corp | Process of producing soft contact lenses |
| GB1593659A (en) * | 1976-11-26 | 1981-07-22 | American Optical Corp | Hydrophilic copolymers |
| EP0100381A1 (en) * | 1982-07-30 | 1984-02-15 | Hoya Corporation | Soft contact lens |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS252224B1 (en) * | 1985-07-31 | 1987-08-13 | Otto Wichterle | Hydrophilic copolymer suitable eapecially for contact lenses and medicinal utilization and method of its producion |
-
1985
- 1985-09-04 CS CS856341A patent/CS256437B1/en unknown
-
1986
- 1986-09-03 IT IT8621585A patent/IT1197469B/en active
- 1986-09-03 CA CA000517427A patent/CA1293577C/en not_active Expired - Fee Related
- 1986-09-03 FR FR868612372A patent/FR2586690B1/en not_active Expired - Fee Related
- 1986-09-03 GB GB8621275A patent/GB2181440B/en not_active Expired - Fee Related
- 1986-09-04 JP JP61206927A patent/JPS62116616A/en active Pending
- 1986-09-04 DE DE19863630187 patent/DE3630187A1/en not_active Withdrawn
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB814009A (en) * | 1956-04-24 | 1959-05-27 | Otto Wichterle | Three-dimensional hydrophilic high polymeric articles |
| GB1035877A (en) * | 1963-09-07 | 1966-07-13 | Ceskoslovenska Akademie Ved | Method of manufacturing contact lenses from hydrogels capable of swelling |
| GB1291650A (en) * | 1969-03-04 | 1972-10-04 | Ceskoslovenska Akademie Ved | Method of preparing novel hydrophilic copolymers with low softening points |
| GB1435966A (en) * | 1972-05-02 | 1976-05-19 | Ceskoslovenska Akademie Ved | Process for producing hydrophilic polymers containing -cn groups |
| GB1424587A (en) * | 1973-02-27 | 1976-02-11 | Union Optics Corp | Copolymers and hydrogels of unsaturated esters |
| GB1495043A (en) * | 1974-05-27 | 1977-12-14 | Hoya Lens Co Ltd | Soft contact lenses and a process and composition for use in their manufacture |
| GB1569493A (en) * | 1976-02-25 | 1980-06-18 | Hoya Lens Corp | Process of producing soft contact lenses |
| GB1593659A (en) * | 1976-11-26 | 1981-07-22 | American Optical Corp | Hydrophilic copolymers |
| EP0100381A1 (en) * | 1982-07-30 | 1984-02-15 | Hoya Corporation | Soft contact lens |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996004189A1 (en) * | 1994-08-05 | 1996-02-15 | Smithkline Beecham P.L.C | Container for moisture-sensitive material |
| US5947274A (en) * | 1994-08-05 | 1999-09-07 | Smithkline Beecham P.L.C. | Desiccating container for moisture-sensitive material |
| AU711609B2 (en) * | 1994-08-05 | 1999-10-14 | West Pharmaceutical Services Cornwall Limited | Container for moisture-sensitive material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62116616A (en) | 1987-05-28 |
| FR2586690B1 (en) | 1991-11-29 |
| CS256437B1 (en) | 1988-04-15 |
| IT1197469B (en) | 1988-11-30 |
| FR2586690A1 (en) | 1987-03-06 |
| GB8621275D0 (en) | 1986-10-08 |
| GB2181440B (en) | 1990-04-25 |
| CA1293577C (en) | 1991-12-24 |
| CS634185A1 (en) | 1987-09-17 |
| IT8621585A0 (en) | 1986-09-03 |
| DE3630187A1 (en) | 1987-03-05 |
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| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19930903 |