Biologically stabilized compositions comprising collagen as the major component with ethylenically unsaturated compounds used as contact lenses

Claim 2

A polymerized hydrophilic water-swellable, biologically stable composition made from a mixture of components consisting essentially of: (a) solubilized collagen; and (b) an ethylenically unsaturated monomer which is characterized by a polymerizable carbon-to-carbon double bond and is composed of atoms of the group consisting of (i) carbon, hydrogen, oxygen and nitrogen in the form of amido and optionally oxygen in the form of carbonyl, (ii) carbon, hydrogen, and oxygen in the form of carbonyloxy and hydroxyl, and optionally oxygen in the form of etheric oxygen, (iii) carbon, hydrogen, carbonyloxy oxygen and etheric oxygen, (iv) carbon, hydrogen, carbonyloxy oxygen, and oxygen in the form of vicinal-epoxy, and (v) carbon, hydrogen, carbonyloxy oxygen, and amino nitrogen; (c) said polymerized hydrophilic composition containing from 50 to about 70 weight percent of solubilized collagen and from less than 50 to about 30 weight percent of ethylenically unsaturated monomeric units, based on the total weight of the components.

Claim 3

The polymerized hydrophilic composition of claim 1 wherein the components expressed as weight percent, based on the total weight of said components, are as follows: ______________________________________ COMPONENT WEIGHT PERCENT ______________________________________ Ethylenically Unsaturated Monomer <50 to ˜30 Solubilized Collagen 50 to ˜70 Modifier 0 to 35 Crosslinking Agent 0 to 5 ______________________________________

Claim 4

The polymerized hydrophilic composition of claim 1 wherein the components expressed as weight percent, based on the total weight of said components, are as follows: ______________________________________ COMPONENT WEIGHT PERCENT ______________________________________ Ethylenically Unsaturated Monomer <50 to ˜40 Solubilized Collagen 50 to ˜60 Modifier 0 to 20 Crosslinking Agent 0 to 2 ______________________________________

Claim 5

The polymerized hydrophilic composition of claim 1 wherein said ethylenically unsaturated monomer is of the group consisting of the following: (a) the unsubstituted, N-substituted and N,N-disubstituted 2-alkenamides wherein each N substituent is hydrogen or a (C 1 -C 6 )alkyl, and wherein the 2-alkenoyl group of the 2-alkenamide molecule contains from 2-6 carbon atoms; (b) the vicinal-epoxyalkyl 2-alkenoates wherein the vicinal-epoxyalkyl group contains from 2 to 4 carbon atoms and wherein the 2-alkenoate group contains from 2-6 carbon atoms; (c) the hydroxy(alkoxy) n alkyl 2-alkenoates wherein the alkyl and alkoxy groups contain from 2 to 4 carbon atoms, wherein n is an integer of from zero to 4, and wherein the 2-alkenoate group contains from 2 to 6 carbon atoms; (d) the alkoxy(alkoxy) n alkyl 2-alkenoates wherein the alkyl and alkoxy groups contain from 2 to 4 carbon atoms, with the proviso that the terminal alkoxy group contains from 1 to 4 carbon atoms, wherein n is an integer of from zero to 4, and wherein the 2-alkenoate group contains from 2 to 6 carbon atoms; (e) the dialkylaminoalkyl 2-alkenoates wherein the alkyl groups contain from 1 to 4 carbon atoms and wherein the 2-alkenoate group contains from 2 to 6 carbon atoms; and (f) N-vinylpyrrolidone.

Claim 6

A shape-retaining hydrogel comprised of a polymerized hydrophilic composition made from a mixture of components consisting essentially of: (a) solubilized collagen; and (b) an ethylenically unsaturated monomer which is characterized by a polymerizable carbon-to-carbon double bond and is composed of atoms of the group consisting of (i) carbon, hydrogen, oxygen and nitrogen in the form of amido and optionally oxygen in the form of carbonyl; (ii) carbon, hydrogen, and oxygen in the form of carbonyloxy and hydroxyl, and optionally oxygen in the form of etheric oxygen, (iii) carbon, hydrogen, carbonyloxy oxygen and etheric oxygen, (iv) carbon, hydrogen, carbonyloxy oxygen, and oxygen in the form of vicinal-epoxy, and (v) carbon, hydrogen, carbonyloxy oxygen, and amino nitrogen; (c) said polymerized hydrophilic composition containing from 50 to about 70 weight percent of solubilized collagen and from less than 50 to about 30 weight percent of ethylenically unsaturated monomeric units, based on the total weight of the components, and (d) said hydrogel having a water content upwards to 95 weight percent.

Claim 7

A shape-retaining hydrogel comprised of a polymerized hydrophilic composition made from a mixture of components consisting essentially of: (a) solubilized collagen; and (b) an ethylenically unsaturated monomer which is characterized by a polymerizable carbon-to-carbon double bond and is composed of atoms of the group consisting of (i) carbon, hydrogen, oxygen and nitrogen in the form of amido and optionally oxygen in the form of carbonyl; (ii) carbon, hydrogen, and oxygen in the form of carbonyloxy and hydroxyl, and optionally oxygen in the form of etheric oxygen, (iii) carbon, hydrogen, carbonyloxy oxygen and etheric oxygen, (iv) carbon, hydrogen, carbonyloxy oxygen, and oxygen in the form of vicinal-epoxy, and (v) carbon, hydrogen, carbonyloxy oxygen, and amino nitrogen; (c) said polymerized hydrophilic composition containing from 50 to about 70 weight percent of solubilized collagen and from less than 50 to about 30 weight percent of ethylenically unsaturated monomeric units, based on the total weight of the components, and (d) said hydrogel having a water content upwards to 95 weight percent.

Claim 8

The hydrogel of claim 5 wherein the components expressed as weight percent, based on the total weight of said components, are as follows: ______________________________________ COMPONENT WEIGHT PERCENT ______________________________________ Ethylenically Unsaturated Monomer <50 to ˜30 Solubilized Collagen 50 to ˜70 Modifier 0 to 35 Crosslinking Agent 0 to 5 ______________________________________ and wherein said hydrogel has a water content of from about 55 to about 95 weight percent.

Claim 9

The hydrogel of claim 5 wherein the components expressed as weight percent, based on the total weight of said components, are as follows: ______________________________________ COMPONENT WEIGHT PERCENT ______________________________________ Ethylenically Unsaturated Monomer <50 to ˜40 Solubilized Collagen 50 to ˜60 Modifier 0 to 20 Crosslinking Agent 0 to 2 ______________________________________ and wherein said hydrogel has a water content of from about 65 to about 90 weight percent.

Claim 10

The shape-retaining hydrogel of claim 5 which is crosslinked and which is characterized by biocompatibility with living tissue, substantial non-biodegradability, and oxygen permeability, and wherein said ethylenically unsaturated monomer is of the group consisting of the following: (a) the unsubstituted, N-substituted and N,N-disubstituted 2-alkenamides wherein each N substituent is hydrogen or a (C 1 -C 6 )alkyl, and wherein the 2-alkenoyl group of the 2-alkenamide molecule contains from 2-6 carbon atoms: (b) the vicinal-epoxyalkyl 2-alkenoates wherein the vicinal-epoxyalkyl group contains from 2 to 4 carbon atoms and wherein the 2-alkenoate group contains from 2-6 carbon atoms; (c) the hydroxy(alkoxy) n alkyl 2-alkenoates wherein the alkyl and alkoxy groups contain from 2 to 4 carbon atoms, wherein n is an integer of from zero to 4, and wherein the 2-alkenoate group contains from 2 to 6 carbon atoms; (d) the alkoxy(alkoxy) n alkyl 2-alkenoates wherein the alkyl and alkoxy groups contain from 2 to 4 carbon atoms, with the proviso that the terminal alkoxy group contains from 1 to 4 carbon atoms, wherein n is an integer of from zero to 4, and wherein the 2-alkenoate group contains from 2 to 6 carbon atoms; (e) the dialkylaminoalkyl 2-alkenoates wherein the alkyl groups contain from 1 to 4 carbon atoms and wherein the 2-alkenoate group contains from 2 to 6 carbon atoms; and (f) N-vinylpyrrolidone.

Claim 11

The shape-retaining hydrogel of claim 8 wherein the components expressed as weight percent, based on the total weight of said components, are as follows: ______________________________________ COMPONENT WEIGHT PERCENT ______________________________________ Ethylenically Unsaturated Monomer <50 to ˜30 Solubilized Collagen 50 to ˜70 Modifier 0 to 35 Crosslinking Agent 0 to 5 ______________________________________ and wherein said hydrogel has a water content of from about 55 to about 95 weight percent.

Claim 12

The shape-retaining hydrogel of claim 8 wherein the components expressed as weight percent, based on the total weight of said components, are as follows: ______________________________________ COMPONENT WEIGHT PERCENT ______________________________________ Ethylenically Unsaturated Monomer <50 to ˜40 Solubilized Collagen 50 to ˜60 Modifier 0 to 20 Crosslinking Agent 0 to 2 ______________________________________ and wherein said hydrogel has a water content of from about 65 to about 90 weight percent.

Claim 13

The shape-retaining hydrogel of claim 8 in the form of a contact lens.

Claim 14

The shape-retaining hydrogel of claim 9 in the form of a contact lens.

Claim 15

The shape-retaining hydrogel of claim 10 in the form of a contact lens.

Claim 16

The shape-retaining hydrogel of claim 11 wherein said ethylenically unsaturated monomers are the unsubstituted, N-substituted and N,N-disubstituted 2-alkenamides wherein each N substituent is hydrogen or a (C 1 -C 6 )alkyl, and wherein the 2-alkenoyl group of the 2-alkenamide molecule contains from 2-6 carbon atoms.

Claim 17

The shape-retaining hydrogel of claim 11 wherein said ethylenically unsaturated monomers are the vicinal-epoxyalkyl 2-alkenoates wherein the vicinal-epoxyalkyl group contains from 2 to 4 carbon atoms and wherein the 2-alkenoate group contains from 2-6 carbon atoms.

Claim 18

The shape-retaining hydrogel of claim 11 wherein said ethylenically unsaturated monomers are the hydroxy(alkoxy) n alkyl 2-alkenoates wherein the alkyl and alkoxy groups contain from 2 to 4 carbon atoms, wherein n is an integer of from zero to 4, and wherein the 2-alkenoate group contains from 2 to 6 carbon atoms.

Claim 19

The shape-retaining hydrogel of claim 11 wherein said ethylenically unsaturated monomers are the alkoxy(alkoxy) n alkyl 2-alkenoates wherein the alkyl and alkoxy groups contain from 2 to 4 carbon atoms, with the proviso that the terminal alkoxy group contains from 1 to 4 carbon atoms, wherein n is an integer of from zero to 4, and wherein the 2-alkenoate group contains from 2 to 6 carbon atoms.

Claim 20

The shape-retaining hydrogel of claim 11 wherein said ethylenically unsaturated monomers are the dialkylaminoalkyl 2-alkenoates wherein the alkyl groups contain from 1 to 4 carbon atoms and wherein the 2-alkenoate group contains from 2 to 6 carbon atoms.

Claim 21

The shape-retaining hydrogel of claim 11 wherein said ethylenically unsaturated monomer is N,N-dimethylacrylamide.

Claim 22

The shape-retaining hydrogel of claim 12 wherein said ethylenically unsaturated monomer is N,N-dimethylacrylamide.

Claim 23

The shape-retaining hydrogel of claim 13 wherein said ethylenically unsaturated monomer is N,N-dimethylacrylamide.

Claim 24

A process for preparing shape-retaining hydrogels which comprises preparing an aqueous solution of reactants comprising (a) solubilized collagen; and (b) an ethylenically unsaturated monomer defined in claim 1; (c) said solution containing from 50 to about 70 percent of said collagen and less than 50 to about 30 weight percent of said ethylenically unsaturated compound, based on the total weight of the reactants; (d) effecting the polymerization reaction of said aqueous solution of reactants in a mold using cross-linking means of the group consisting of irradiation, polyethylenically unsaturated cross-linking compounds, and mixtures thereof; (e) for a period of time sufficient to produce shape-retaining hydrogel products; and (f) recovering said hydrogel product.

Claim 25

The process of claim 22 wherein said aqueous solution of reactants comprises a polyethylenically unsaturated cross-linking compound, and from about 0.5 to about 12 weight percent of said solubilized collagen.

Claim 26

The process of claim 23 wherein said cross-linking means comprises irradiation.

Claim 27

The process of claim 24 wherein said aqueous solution of reactants comprises an ethylenically unsaturated monomer defined in claim 4.

Claim 28

The process of claim 25 wherein said aqueous solution of reactants comprises an ethylenically unsaturated monomer defined in claim 14.

Claim 29

The process of claim 25 wherein said aqueous solution of reactants comprises an ethylenically unsaturated monomer defined in claim 16.

Claim 30

The process of claim 25 wherein said aqueous solution of reactants comprises an ethylenically unsaturated monomer defined in claim 19.

Claim 31

The process of claim 23 wherein said shape-retaining hydrogel products are in the form of contact lenses and are characterized by biocompatibility with living tissue, substantial non-biodegradability, high oxygen permeability, and high water content.