CA1281490C - Hydrogel polymers - Google Patents
Hydrogel polymersInfo
- Publication number
- CA1281490C CA1281490C CA000528273A CA528273A CA1281490C CA 1281490 C CA1281490 C CA 1281490C CA 000528273 A CA000528273 A CA 000528273A CA 528273 A CA528273 A CA 528273A CA 1281490 C CA1281490 C CA 1281490C
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- CA
- Canada
- Prior art keywords
- cross
- linked
- substituted
- hydrogel polymer
- weight
- 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.)
- Expired - Lifetime
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Classifications
-
- 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
- C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
-
- 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
Abstract
A B S T R A C T
Hydrogel Polymers A cross-linked, hydrogel polymer for contact lenses with a water uptake of between 60 and 70% by weight based on the total weight of hydrogel is formed from a mixture of monomer components containing (1) N-vinyl-2-pyrrolidone, (2) alkyl methacrylate and (3) a compound of formula
Hydrogel Polymers A cross-linked, hydrogel polymer for contact lenses with a water uptake of between 60 and 70% by weight based on the total weight of hydrogel is formed from a mixture of monomer components containing (1) N-vinyl-2-pyrrolidone, (2) alkyl methacrylate and (3) a compound of formula
Description
~ 8~90 -HYDROGEL POLYMERS
This invention relates to cross-linked hydrogel polymers and to their preparation and use. More particularly this invention relates to hydrogel polymers which are useful for the manufacture of medical prostheses and especially of contact lenses.
It is well known to make contact lenses from hydrogel polymers. However, the requirements needed o~ an ideal hydrogel polymer for this use are such that it may be argued that none of the hydrogel materials currently used to form contact lenses are entirely satisfactory. Indeed the numerous proposals made in the patent literature for hydrogel contact lenses during the last twenty to thirty years shows how the search for the ideal polymer has been pursued by a number of workers. These previously known hydrogel polymers succeed in fulfilling some of the requirements needed but are unsatisfactory on others. The requirements of an ideal lens polymer include (1) hard and machinable when unhydrated and when hydrated they should (2) :;~
~ IL281490 have good elastic recovery, (3) be clear, (~) have high permeability to water and oxygen on hydration. Previously some Or these requirements have proved to be mutually incompatible, so it has proved difficult to produce a hydrogel polymer which has a high water content, that is has a high permeability to water and oxygen, yet has also adequate strength or to produce a hydrogel polymer which has strength without it being relatively inelastic.
I have no~ found hydrogel polymers, as hereinafter defined, that satis~y the above requirements with regard to ~trength and elasticity and which surprisingly have a high water content and which can show a wide range of tensile strength and elastic properties over a narrow range o~
suitable water content values.
lS Accordingly the present invention provides a cross-linked, hydrogel polymer material capable of an uptake o~ water o~ between 60 and 70% by weight based on the total weight of hydrogel, said material being formed ~rom a mixture of monomer components containing (1) N-vinyl-2-pyrrolidone, ~2) alkyl methacrylate in which the alkyl group may be a straight chain or branched chain and contain from l to 6 carbon atoms which may be substituted by a hydroxyl group and (3~ a compound of formula (l) Rl ~A CH2=C-COOR2 (I).
, ;., . ,.,~ , . .. .
128~490 in which R1 is hydrogen or a lower alkyl group and ~2 is either a substituted or unsubstituted aryl group or an alkyl group containg 1 to 6 carbon atoms substituted by a substituted or unsubstituted aryl group or by a substituted or unsubstituted aryloxy group or by a cycloalkyloxy group wherein when substituted,the aryl or arlyoxy groups are substituted by one or two alkyl groups of straight or branched chain containing from 1 to 4 carbon atoms, one or two ~lkoxy groups of straight lC or branched chain containing from 1 to 4 carbon atoms, or one or two halogen atoms.
Suitably the hydrogel polymer material can be capable of an uptake of water of between 60 and 70% by weight based on the total weight of hydrogel. This will provide the hydrogel polymer with a sufficiently high permeability to water and oxygen to reduce the risk of causing anoxia (lack of oxygen) or oedema to the cornea during wear. These disorders can occur on wearing contact lenses of lower water content for example 3B%. Preferably the hydrogel polymer material will be capable of an uptake of water of between 65 and 68~ by weight.
The first and hydrophilic monomeric component used to form the hydrogel polymer material is a water soluble N-vinyl lactam, N-vinyl-2-pyrrolidone~ Suitably the mixture of ~.~
~LX~90 monomers components used to ~orm the hydrogel polymer materials of the present invention may contain ~rom 55 to 70~
by weight of N-vinyl-2-pyrrolidone and preferably will contain from 56 to 67% by weight.
s The second component used to form the hydrogel polymer material of the invention may be a hydrophilic or hydrophobic component depending upon the required properties of the final ~ 4 -12 814~
hydrogel and will comprise alkyl methacrylate which may be as a single monomer or as a mixture of two or more such monomers.
The alkyl group may be a straight chain or branched chain and contain from 1 to 6 carbon atoms which optionally may be 5 substituted by a substituent such as a hydroxyl group. A
suitable alkyl methacrylate is methyl methacrylate however a preferred methacrylate is a hydroxyalkyl methacrylate of which the most preferred is 2-hydroxyethyl methacrylate.
Suitably the mixture of monomer components used to form lO the hydrogel polymer material of the invention can contain from 15 to 30% by weight of methacrylate and preferably wlll contain from 18 to 30%.
The third component used to form the hydrogel material of the present invention is a compound of formula R' CH2 = C-OOR2 in which Rl is hydrogen or a lower alkyl group containing from 1 to 4 carbon atoms and R2 is either a substituted or unsubstituted aryl group or an alkyl group containing from 1 to 6 carbon atoms subsituted by substituted or unsubstituted aryl group or by substituted or unsubstituted aryloxy group or by cycloalkyloxy group.
- 5 - ~z~490 It is preferred for the Group Rl to be methyl that is the compound of the formula given is a methacrylate ester.
It is preferred that the substituted alkyl group R2 should contain one or especially two carbon atoms.
The aryl substituent described above usually comprises one or two six-membered carbocyclic rings. It can be a mononuclear, fused binuclear or other binuclear radical but preferably is a mononuclear radical such as phenyl or the corresponding phenoxy or phenyl-S-, phenyl-S(O)- or phenyl-S( 2 ) - -Examples of suitable aryl substituents include phenyl~2-naphthyl, phenyl-S-, phenyl-S(O)- or phenyl-S(O 2 ) - or the corresponding phenoxy, 2-naphthyloxy, (3-phenyl)phenoxy, (4-phenyl)phenoxy, (3-benzyl)phenoxy or (4-benzyl)phenoxy.
Optionally the aryl or aryloxy group can be substituted by one or two alkyl groups of straight or branched chain containing from 1 to 4 carbon atoms, one or two alkoxy groups of straight or branched chain containing from 1 to 4 carbon atoms, or one or two halogen atoms. Preferably the aryl or aryloxy groups are unsubstituted.
~ ':
The alkyl group of the cycloalkyloxy group usually comprises 5 or 6 carbon atoms and preferably contains six carbon atoms, that is cyclohexyl.
. ~ - 6 - ~81~90 The preferred third component is phenethyl methacrylate.
Other preferred third components include phenoxyethyl methacrylate and cyclohexyloxy methacrylate.
Suitably the mixture of monomer components used to form the hydrogel polymer material of the invention may contain from 10 to 25% of a compound of formula (I).
The hydrogel polymer materials described above are cro~s-linked by the addition to the monomer components of a di-functional compound in an amount which will give the required degree of cross-linking. Usually the amount of cross-linking agent used will be between 0.1 and 5% by weight, depending upon the type used and preferably will be between 0.2 and 2%. Suitable cross-linking agents include those having symetrical molecules like methylene biacrylamide and ethylene glycol dimethyacrylate but it is preferred that in the cross-linking agent the functional groups differ in reactivity, usually by virtue of their point of attachment to the remainder of the molecule. Particular examples are monoesters of methacrylic acid with unsaturated aliphatic radicals, for example allyl methacrylate.
The present invention also provides a method of producing a cro~s-linking hydrogel polymer material in which the monomer components 1, 2 and 3 are mixed together with the cross-.
~Z~490 linking agent and a catalyst which promotes free-radical polymerisation. The mixture is heated to 35C to 50C for upto 50 hours in the absence of oxygen, then for 1 to 3 hours at 60C to 80C and finally at 1 to 3 hours at 100C to 120C.
While this invention is predominantly concerned with polymers formed from three monomer components, the polymers may be formed from mixtures containi~ng additional copolymerisable monomers provided of course they do not lO adversely affect the desired properties of the hydrogel.
The present invention also provides a contact lens manufactured from the hydrogel polymer material.
In one preferred aspect the present invention provides a cross-linked, hydrogel polymer material capable of an uptake 15 of water of between 60 and 70% by weight based on the total weight of hydrogel, said material being the polymerisation product of a mixture of monomers containing from 56 to 67% by weight of N-vinyl-2-pyrrolidone, from 18 to 30~ by weight of alkyl methacrylate selected from the group consisting of methyl methacrylate and hydroxyethyl methacrylate, from 10 to 25% of phenethyl methacrylaté and from 0.1 to 5% by weight of cross-linking agent.
The present invention also provides a contact lens formed from this hydrogel polymer.
~` ~ ~
~ 8 - ~ 49~ 1 Example 1 - Preparation of Hydrogel Polymer Material A mixture of the following monomer components was prepared, N-vinyl-2-pyrrolidone (56.2 parts by weight), phenethyl methacrylate (10 parts by weight), 2-hydroxyethyl methacrylate (33.3 parts by weight) and a cross-linking agent allyl methacrylate (0.27 parts by weight). A free-radical polymerisation catalyst azobisisobutyronitrile (0.15 parts by weight) was added and dissolved. The mixture was filtered, placed in a mould and degassed. The initial polymerisation was carried out on a constant temperature enclosure at 38 to 42C with exclusion of oxygen over a period of upto 45 hours.
The second stage of the polymerisation was carried out at 65C
to 75C for upto 3 hours and finally at 100C to 120C, for example 110C for a further 3 hours.
The resultant polymer material, in this case in the form of a disc of 15mm diameter and 4mm thick, was immersed in 25ml of a 0.9~ by weight aqueous sodium chloride solution at 20C and allowed to reach equilibrium, that is when no further change in the weight of the hydrated polymer was observed over a 24 hour period. The water uptake was 65.1g.
The ultimate tensile strength (UTS) was measured by the method described in ASTMD 1708 in which dumbell-shaped samples of the hydrated polymer were placed at a gauge lengtyh of 1.54cm in the jaws of an Instron (trade mark) test machine -` - 9 ~8~49C) which moved apart at a speed of 5cm/min, the sample being immersed in saline for the duration of the test. The results are shown in MPa. The 10% T denotes the force required for 10% elongation, and is measured from the graph obtained during the UTS test above. The ultimate tensile strength is a measure of the strength of the material and 10% T an indication of its stiffness.
Contact lenses may be made from the hydrogel polymer materials as follows. The polymer is made in the form of a lO button that is a cylinder which has a diameter of about 12.7mm and a thickness of 6mm. The polymer in its unhydrated state is hard and may be machined using a lathe and cutter. Knowing the swellability factor of the polymer that is the amount by which the polymer swells on hydration, the button is shaped to 15 the appropriate dimensions and then hydrated in sterile physiologioal saline at room temperature whereupon the polymer swells to an overall diameter of between 17.3 and 17.5 mm to give a clear, flexible contact lens.
Example 2 - Preparation of Hydrogel Polymeric Material A similar preparation to that described in Example 1 was carried out using the following mixture of monomeric components N-vinyl-2-pyrollidone (61 parts by weight) phenethyl methacrylate (17.4 parts by weight) and 2-hydroxy ethyl methacrylate (21.2 parts by weight) and the same amount 25 of cross-linking agent and catalyst as in Example 1.
- 1 0 - ~LZ8l 490 On hydration the water uptake was 65.2% by weight.
The invention will be further described with reference to the following table, which indicates certain properties of the preferred methacrylic esters when polymerised with N-vinyl-2-pyrollidone and also shows the properties of certain other polymers.
.
~ 0 S1~J~J
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o .- o . O
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el ~) . . . . o 5 3 ~ Oc~ 0 X :~-J~
0~
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.,1 O
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~2~3149C) Examples 5 - 8 A second series of hydrogel polymers was prepared in a similar manner to Example 1 in which the monomer mixture had the following compositions, Example Water N-vinyl-2- Phenethyl- MMA
Content pyrrolidone methacrylate ,~ by weight % by weight % by weight % by weight hydrogel 65.0 65.0 10.0 24.6 6 65.0 68.0 17.4 14.2 7 68.0 68.5 10.0 21.0 8 68.0 71.2 17.4 10.9 The cross-linking agent used was allyl methacrylate (0.27%) and the free-radical catalyst was azo bis isobutyronitrile (0.15%).
~ .. .
This invention relates to cross-linked hydrogel polymers and to their preparation and use. More particularly this invention relates to hydrogel polymers which are useful for the manufacture of medical prostheses and especially of contact lenses.
It is well known to make contact lenses from hydrogel polymers. However, the requirements needed o~ an ideal hydrogel polymer for this use are such that it may be argued that none of the hydrogel materials currently used to form contact lenses are entirely satisfactory. Indeed the numerous proposals made in the patent literature for hydrogel contact lenses during the last twenty to thirty years shows how the search for the ideal polymer has been pursued by a number of workers. These previously known hydrogel polymers succeed in fulfilling some of the requirements needed but are unsatisfactory on others. The requirements of an ideal lens polymer include (1) hard and machinable when unhydrated and when hydrated they should (2) :;~
~ IL281490 have good elastic recovery, (3) be clear, (~) have high permeability to water and oxygen on hydration. Previously some Or these requirements have proved to be mutually incompatible, so it has proved difficult to produce a hydrogel polymer which has a high water content, that is has a high permeability to water and oxygen, yet has also adequate strength or to produce a hydrogel polymer which has strength without it being relatively inelastic.
I have no~ found hydrogel polymers, as hereinafter defined, that satis~y the above requirements with regard to ~trength and elasticity and which surprisingly have a high water content and which can show a wide range of tensile strength and elastic properties over a narrow range o~
suitable water content values.
lS Accordingly the present invention provides a cross-linked, hydrogel polymer material capable of an uptake o~ water o~ between 60 and 70% by weight based on the total weight of hydrogel, said material being formed ~rom a mixture of monomer components containing (1) N-vinyl-2-pyrrolidone, ~2) alkyl methacrylate in which the alkyl group may be a straight chain or branched chain and contain from l to 6 carbon atoms which may be substituted by a hydroxyl group and (3~ a compound of formula (l) Rl ~A CH2=C-COOR2 (I).
, ;., . ,.,~ , . .. .
128~490 in which R1 is hydrogen or a lower alkyl group and ~2 is either a substituted or unsubstituted aryl group or an alkyl group containg 1 to 6 carbon atoms substituted by a substituted or unsubstituted aryl group or by a substituted or unsubstituted aryloxy group or by a cycloalkyloxy group wherein when substituted,the aryl or arlyoxy groups are substituted by one or two alkyl groups of straight or branched chain containing from 1 to 4 carbon atoms, one or two ~lkoxy groups of straight lC or branched chain containing from 1 to 4 carbon atoms, or one or two halogen atoms.
Suitably the hydrogel polymer material can be capable of an uptake of water of between 60 and 70% by weight based on the total weight of hydrogel. This will provide the hydrogel polymer with a sufficiently high permeability to water and oxygen to reduce the risk of causing anoxia (lack of oxygen) or oedema to the cornea during wear. These disorders can occur on wearing contact lenses of lower water content for example 3B%. Preferably the hydrogel polymer material will be capable of an uptake of water of between 65 and 68~ by weight.
The first and hydrophilic monomeric component used to form the hydrogel polymer material is a water soluble N-vinyl lactam, N-vinyl-2-pyrrolidone~ Suitably the mixture of ~.~
~LX~90 monomers components used to ~orm the hydrogel polymer materials of the present invention may contain ~rom 55 to 70~
by weight of N-vinyl-2-pyrrolidone and preferably will contain from 56 to 67% by weight.
s The second component used to form the hydrogel polymer material of the invention may be a hydrophilic or hydrophobic component depending upon the required properties of the final ~ 4 -12 814~
hydrogel and will comprise alkyl methacrylate which may be as a single monomer or as a mixture of two or more such monomers.
The alkyl group may be a straight chain or branched chain and contain from 1 to 6 carbon atoms which optionally may be 5 substituted by a substituent such as a hydroxyl group. A
suitable alkyl methacrylate is methyl methacrylate however a preferred methacrylate is a hydroxyalkyl methacrylate of which the most preferred is 2-hydroxyethyl methacrylate.
Suitably the mixture of monomer components used to form lO the hydrogel polymer material of the invention can contain from 15 to 30% by weight of methacrylate and preferably wlll contain from 18 to 30%.
The third component used to form the hydrogel material of the present invention is a compound of formula R' CH2 = C-OOR2 in which Rl is hydrogen or a lower alkyl group containing from 1 to 4 carbon atoms and R2 is either a substituted or unsubstituted aryl group or an alkyl group containing from 1 to 6 carbon atoms subsituted by substituted or unsubstituted aryl group or by substituted or unsubstituted aryloxy group or by cycloalkyloxy group.
- 5 - ~z~490 It is preferred for the Group Rl to be methyl that is the compound of the formula given is a methacrylate ester.
It is preferred that the substituted alkyl group R2 should contain one or especially two carbon atoms.
The aryl substituent described above usually comprises one or two six-membered carbocyclic rings. It can be a mononuclear, fused binuclear or other binuclear radical but preferably is a mononuclear radical such as phenyl or the corresponding phenoxy or phenyl-S-, phenyl-S(O)- or phenyl-S( 2 ) - -Examples of suitable aryl substituents include phenyl~2-naphthyl, phenyl-S-, phenyl-S(O)- or phenyl-S(O 2 ) - or the corresponding phenoxy, 2-naphthyloxy, (3-phenyl)phenoxy, (4-phenyl)phenoxy, (3-benzyl)phenoxy or (4-benzyl)phenoxy.
Optionally the aryl or aryloxy group can be substituted by one or two alkyl groups of straight or branched chain containing from 1 to 4 carbon atoms, one or two alkoxy groups of straight or branched chain containing from 1 to 4 carbon atoms, or one or two halogen atoms. Preferably the aryl or aryloxy groups are unsubstituted.
~ ':
The alkyl group of the cycloalkyloxy group usually comprises 5 or 6 carbon atoms and preferably contains six carbon atoms, that is cyclohexyl.
. ~ - 6 - ~81~90 The preferred third component is phenethyl methacrylate.
Other preferred third components include phenoxyethyl methacrylate and cyclohexyloxy methacrylate.
Suitably the mixture of monomer components used to form the hydrogel polymer material of the invention may contain from 10 to 25% of a compound of formula (I).
The hydrogel polymer materials described above are cro~s-linked by the addition to the monomer components of a di-functional compound in an amount which will give the required degree of cross-linking. Usually the amount of cross-linking agent used will be between 0.1 and 5% by weight, depending upon the type used and preferably will be between 0.2 and 2%. Suitable cross-linking agents include those having symetrical molecules like methylene biacrylamide and ethylene glycol dimethyacrylate but it is preferred that in the cross-linking agent the functional groups differ in reactivity, usually by virtue of their point of attachment to the remainder of the molecule. Particular examples are monoesters of methacrylic acid with unsaturated aliphatic radicals, for example allyl methacrylate.
The present invention also provides a method of producing a cro~s-linking hydrogel polymer material in which the monomer components 1, 2 and 3 are mixed together with the cross-.
~Z~490 linking agent and a catalyst which promotes free-radical polymerisation. The mixture is heated to 35C to 50C for upto 50 hours in the absence of oxygen, then for 1 to 3 hours at 60C to 80C and finally at 1 to 3 hours at 100C to 120C.
While this invention is predominantly concerned with polymers formed from three monomer components, the polymers may be formed from mixtures containi~ng additional copolymerisable monomers provided of course they do not lO adversely affect the desired properties of the hydrogel.
The present invention also provides a contact lens manufactured from the hydrogel polymer material.
In one preferred aspect the present invention provides a cross-linked, hydrogel polymer material capable of an uptake 15 of water of between 60 and 70% by weight based on the total weight of hydrogel, said material being the polymerisation product of a mixture of monomers containing from 56 to 67% by weight of N-vinyl-2-pyrrolidone, from 18 to 30~ by weight of alkyl methacrylate selected from the group consisting of methyl methacrylate and hydroxyethyl methacrylate, from 10 to 25% of phenethyl methacrylaté and from 0.1 to 5% by weight of cross-linking agent.
The present invention also provides a contact lens formed from this hydrogel polymer.
~` ~ ~
~ 8 - ~ 49~ 1 Example 1 - Preparation of Hydrogel Polymer Material A mixture of the following monomer components was prepared, N-vinyl-2-pyrrolidone (56.2 parts by weight), phenethyl methacrylate (10 parts by weight), 2-hydroxyethyl methacrylate (33.3 parts by weight) and a cross-linking agent allyl methacrylate (0.27 parts by weight). A free-radical polymerisation catalyst azobisisobutyronitrile (0.15 parts by weight) was added and dissolved. The mixture was filtered, placed in a mould and degassed. The initial polymerisation was carried out on a constant temperature enclosure at 38 to 42C with exclusion of oxygen over a period of upto 45 hours.
The second stage of the polymerisation was carried out at 65C
to 75C for upto 3 hours and finally at 100C to 120C, for example 110C for a further 3 hours.
The resultant polymer material, in this case in the form of a disc of 15mm diameter and 4mm thick, was immersed in 25ml of a 0.9~ by weight aqueous sodium chloride solution at 20C and allowed to reach equilibrium, that is when no further change in the weight of the hydrated polymer was observed over a 24 hour period. The water uptake was 65.1g.
The ultimate tensile strength (UTS) was measured by the method described in ASTMD 1708 in which dumbell-shaped samples of the hydrated polymer were placed at a gauge lengtyh of 1.54cm in the jaws of an Instron (trade mark) test machine -` - 9 ~8~49C) which moved apart at a speed of 5cm/min, the sample being immersed in saline for the duration of the test. The results are shown in MPa. The 10% T denotes the force required for 10% elongation, and is measured from the graph obtained during the UTS test above. The ultimate tensile strength is a measure of the strength of the material and 10% T an indication of its stiffness.
Contact lenses may be made from the hydrogel polymer materials as follows. The polymer is made in the form of a lO button that is a cylinder which has a diameter of about 12.7mm and a thickness of 6mm. The polymer in its unhydrated state is hard and may be machined using a lathe and cutter. Knowing the swellability factor of the polymer that is the amount by which the polymer swells on hydration, the button is shaped to 15 the appropriate dimensions and then hydrated in sterile physiologioal saline at room temperature whereupon the polymer swells to an overall diameter of between 17.3 and 17.5 mm to give a clear, flexible contact lens.
Example 2 - Preparation of Hydrogel Polymeric Material A similar preparation to that described in Example 1 was carried out using the following mixture of monomeric components N-vinyl-2-pyrollidone (61 parts by weight) phenethyl methacrylate (17.4 parts by weight) and 2-hydroxy ethyl methacrylate (21.2 parts by weight) and the same amount 25 of cross-linking agent and catalyst as in Example 1.
- 1 0 - ~LZ8l 490 On hydration the water uptake was 65.2% by weight.
The invention will be further described with reference to the following table, which indicates certain properties of the preferred methacrylic esters when polymerised with N-vinyl-2-pyrollidone and also shows the properties of certain other polymers.
.
~ 0 S1~J~J
o ~ ~ J J
a~. . . . . .
t~l o O o o o O
O ~ .
~1 S
a) ~
~ ~ ~4In~r~ o c--.,1 ~ ~ . . ~ . . I I
o .- o . O
a~
S
el ~) . . . . o 5 3 ~ Oc~ 0 X :~-J~
0~
~ S:
S b~
~ In O
E~ 3 0 O ~
J N
,Ct ~
S
O
.,1 O
1:., bO .
I a~15~Ot'O 0~ O
N 3 .. .
~0:N~ ~ t .
Z
bO~
O ~ ~0 c,~ 3 0 ~ s a a) ~l a C~.
E ~ ~ t _ e cc m ~
~ 0 X ~X
~:1 E ~:1 o , ~
~2~3149C) Examples 5 - 8 A second series of hydrogel polymers was prepared in a similar manner to Example 1 in which the monomer mixture had the following compositions, Example Water N-vinyl-2- Phenethyl- MMA
Content pyrrolidone methacrylate ,~ by weight % by weight % by weight % by weight hydrogel 65.0 65.0 10.0 24.6 6 65.0 68.0 17.4 14.2 7 68.0 68.5 10.0 21.0 8 68.0 71.2 17.4 10.9 The cross-linking agent used was allyl methacrylate (0.27%) and the free-radical catalyst was azo bis isobutyronitrile (0.15%).
~ .. .
Claims (17)
1. A cross-linked, hydrogel polymer material capable of an uptake of water of between 60 and 70% by weight based on the total weight of hydrogel, said material being formed from a mixture of monomer components containing (1) N-vinyl-2-pyrrolidone, (2) alkyl methacrylate in which the alkyl group may be a straight chain or branched chain and contain from 1 to 6 carbon atoms which may be substituted by a hydroxyl group and (3) a compound of formula (1) (I) in which R1 is hydrogen or a lower alkyl group and R2 is either a substituted or unsubstituted aryl group or an alkyl group containg 1 to 6 carbon atoms substituted by a substituted or unsubstituted aryl group or by a substituted or unsubstituted aryloxy group or by a cycloalkyloxy group wherein when substituted, the aryl or arlyoxy groups are substituted by one or two alkyl groups of straight or branched chain containing from 1 to 4 carbon atoms, one or two alkoxy groups of straight or branched chain containing from 1 to 4 carbon atoms, or one or two halogen atoms.
2. A cross-linked, hydrogel polymer according to claim 1 in which the monomer mixture contains from 55 to 70% by weight of N-vinyl-2-pyrrolidone.
3. A cross-linked, hydrogel polymer according to claim 1 in which the monomer mixture contains from 15 to 30% by weight of alkyl methacrylate.
4. A cross-linked,hydrogel polymer according to claim 3 in which the alkyl methacrylate is hydroxyethyl methacrylate.
5. A cross-linked,hydrogel polymer according to claim 3 in which the alkyl methacrylate is methyl methacrylate.
6. A cross-linked,hydrogel polymer according to claim 1 in which the monomer mixture contains from 10 to 25% by weight of a compound of formula (I).
7. A cross-linked,hydrogel polymer according to claim 6 in which R1 is methyl.
8. A cross-linked, hydrogel polymer according to claim 6 in which R2 is an alkyl group containing two carbon atoms substituted by a substituted or unsubstituted aryl group or by a substituted or unsubstituted aryloxy group or by a cylcoalkyloxy group in which the aryl or cycloalkyl groups comprise a six-membered carbocyclic ring and in which the substituted aryl groups are substituted by one or two alkyl groups of straight or branched chains containing 1 to 4 carbon atoms, one or two alkoxy groups of straight or branched chain containing from 1 to 4 carbon atoms or one or two halogen atoms.
9. A cross-linked,hydrogel polymer according to claim 8 in which R2 is a phenethyl group.
10. A cross-linked,hydrogel polymer according to claim 8 in which R2 is a cyclohexyloxyethyl group.
11. A cross-linked,hydrogel polymer according to claim 1 in which the polymer is cross-linked with between 0.1 and 5% by weight of cross-linking agent.
12. A cross-linked,hydrogel polymer according to claim 10 in which the polymer is cross-linked with between 0.2 and 2% by weight of a cross-linking agent having two functional groups which differ in reactivity.
13. A contact lens comprised of a polymer as defined in claim 1.
14. A cross-linked, hydrogel polymer material capable of an uptake of water of between 60 and 70% by weight based on the total weight of hydrogel, said material being the polymerisation product of a mixture of monomers containing from 56 to 67% by weight of N-vinyl-2-pyrrolidone, from 18 to 30% by weight of alkyl methacrylate selected from the group consisting of methyl methacrylate and hydroxyethyl methacrylate, from 10 to 25% of phenethyl methacrylate and from 0.1 to 5% by weight of cross-linking agent.
15. A cross-linked, hydrogel polymer material according to claim 14 in which there is present from 0.2 to 2%
of a cross-linking agent having two functional groups which differ in reactivity.
of a cross-linking agent having two functional groups which differ in reactivity.
16. A method of producing the cross-linked, hydrogel polymer material of claim 1 in which the monomer components 1, 2 and 3 are mixed together with a cross-linking agent and a catalyst which promotes free-radical polymerisation, in said method the mixture being heated to 35°C to 50°C
for up to 50 hours in the absence of oxygen, then for 1 to 3 hours at 60°C to 80°C and finally for 1 to 3 hours at 100°C to 120°C.
for up to 50 hours in the absence of oxygen, then for 1 to 3 hours at 60°C to 80°C and finally for 1 to 3 hours at 100°C to 120°C.
17
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB868601949A GB8601949D0 (en) | 1986-01-28 | 1986-01-28 | Hydrogel polymers |
| GB8601949 | 1986-01-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1281490C true CA1281490C (en) | 1991-03-12 |
Family
ID=10592010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000528273A Expired - Lifetime CA1281490C (en) | 1986-01-28 | 1987-01-27 | Hydrogel polymers |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4749761A (en) |
| EP (1) | EP0234749B1 (en) |
| AT (1) | ATE80402T1 (en) |
| AU (1) | AU591962B2 (en) |
| CA (1) | CA1281490C (en) |
| DE (1) | DE3781570T2 (en) |
| ES (1) | ES2052552T3 (en) |
| GB (1) | GB8601949D0 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3927667A1 (en) * | 1989-08-22 | 1991-02-28 | Espe Stiftung | USE OF PHOTOPOLYMERIZABLE MATERIALS AS INTROCULAR LENS FILLING MATERIAL IN THE FIGHT AGAINST CATARACT AND OTHER EYE DISEASES |
| US5712356A (en) * | 1993-11-26 | 1998-01-27 | Ciba Vision Corporation | Cross-linkable copolymers and hydrogels |
| EP0655470B1 (en) * | 1993-11-26 | 1999-05-12 | Novartis AG | Cross-linkable copolymers and hydrogels |
| US6342570B1 (en) | 1994-11-14 | 2002-01-29 | Novartis Ag | Cross-linkable copolymers and hydrogels |
| US6132462A (en) * | 1995-12-22 | 2000-10-17 | Santen Pharmaceutical Co., Ltd. | Copolymers formed from three components and intraocular lenses made thereof |
| CN1152584A (en) * | 1995-12-22 | 1997-06-25 | 参天制药株式会社 | Three constituents copolymer and eye lens made from it |
| US6326448B1 (en) | 1997-08-20 | 2001-12-04 | Menicon Co., Ltd. | Soft intraocular lens material |
| JP3641110B2 (en) * | 1997-08-20 | 2005-04-20 | 株式会社メニコン | Materials for soft intraocular lenses |
| US6235396B1 (en) | 1998-06-26 | 2001-05-22 | Younger Mfg | Optical lens comprising a polyvinylalcohol layer covalently bonded to a bulk lens polymer |
| CA2693808C (en) * | 2007-07-19 | 2015-10-20 | Alcon, Inc. | High ion and metabolite flux lenses and materials |
| CN101980669A (en) * | 2008-03-27 | 2011-02-23 | 爱尔康公司 | Hydrogel intraocular lens and method of forming same |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3639524A (en) * | 1969-07-28 | 1972-02-01 | Maurice Seiderman | Hydrophilic gel polymer insoluble in water from polyvinylpyrrolidone with n-vinyl-2-pyrrolidone and methacrylic modifier |
| US3937680A (en) * | 1973-05-29 | 1976-02-10 | Global Vision, Inc. | Hydrophilic gel terpolymers from hydrophilic n-vinyl monomers, hydroxyalkyl acrylates or methacrylates and polymerizable unsaturated carboxylic acids |
| AR208398A1 (en) * | 1974-03-29 | 1976-12-27 | Smith & Nephew Res | A LIGHTLY INTERLACED HYDROGEL COPOLYMER |
| AR207867A1 (en) * | 1974-07-04 | 1976-11-08 | Smith & Nephew Res | A LIGHTLY INTERLACED HYDROGEL COPOLYMER |
| JPS5374049A (en) * | 1976-11-04 | 1978-07-01 | Toray Industries | Soft contact lens material |
| DE3002664C2 (en) * | 1980-01-25 | 1989-05-18 | Titmus Eurocon Kontaktlinsen Gmbh & Co Kg, 8750 Aschaffenburg | Soft contact lens |
| GB2087408B (en) * | 1980-11-04 | 1984-05-23 | Patel Pravin Gordhanbhai Da Co | Cross-linked hydrophilic polymers |
| JPS59195621A (en) * | 1983-04-22 | 1984-11-06 | Toyo Contact Lens Co Ltd | Soft contact lens |
| JPS6126608A (en) * | 1984-07-17 | 1986-02-05 | Kansai Paint Co Ltd | Aqueous pigment dispersion |
| US4620954A (en) * | 1985-06-07 | 1986-11-04 | Ciba Vision Care Corp. | Hydrogel from ultraviolet-initiated copolymerization |
-
1986
- 1986-01-28 GB GB868601949A patent/GB8601949D0/en active Pending
-
1987
- 1987-01-27 US US07/007,326 patent/US4749761A/en not_active Expired - Fee Related
- 1987-01-27 CA CA000528273A patent/CA1281490C/en not_active Expired - Lifetime
- 1987-01-28 ES ES87300710T patent/ES2052552T3/en not_active Expired - Lifetime
- 1987-01-28 EP EP87300710A patent/EP0234749B1/en not_active Expired - Lifetime
- 1987-01-28 AT AT87300710T patent/ATE80402T1/en not_active IP Right Cessation
- 1987-01-28 AU AU68062/87A patent/AU591962B2/en not_active Ceased
- 1987-01-28 DE DE8787300710T patent/DE3781570T2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| ATE80402T1 (en) | 1992-09-15 |
| EP0234749A3 (en) | 1988-11-17 |
| AU591962B2 (en) | 1989-12-21 |
| GB8601949D0 (en) | 1986-03-05 |
| EP0234749A2 (en) | 1987-09-02 |
| ES2052552T3 (en) | 1994-07-16 |
| US4749761A (en) | 1988-06-07 |
| DE3781570D1 (en) | 1992-10-15 |
| DE3781570T2 (en) | 1993-03-04 |
| EP0234749B1 (en) | 1992-09-09 |
| AU6806287A (en) | 1987-07-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |