KR20250005635A - Polymeric compositions for oxygen permeable contact lenses - Google Patents

Abstract

Carboxylic acid esters having no exclusive hydrogen are homopolymerized or copolymerized with contact lens materials to produce desirable contact lens materials and contact lenses. These materials have favorable contact lens properties including a desired DK, hardness, machinability, and a desired refractive index of 1 or more.

Description

POLYMERIC COMPOSITIONS FOR OXYGEN PERMEABLE CONTACT LENSES

Composition for contact lenses

Siloxane-based materials are usually prepared by copolymerizing siloxanyl alkyl esters of methacrylic acid with other acrylate, methacrylate or itaconate monomers in various known blending recipes. Such compositions can exhibit excellent oxygen permeability due to the use of a large amount of siloxane material. In order to increase the oxygen permeability, it is desirable to increase the siloxane content. However, such an increase in the siloxane content often not only reduces hardness, but also sometimes presents difficulties with respect to machinability, dimensional stability and other usability.

It is known in the art that the introduction of fluorine-containing groups into polymers for contact lenses can significantly increase the oxygen permeability. These materials can have a hardness ranging from soft to semi-hard, but often require the use of specific wetting agents or surface treatment agents. On the other hand, while siloxanes increase the oxygen permeability, they sometimes have problems with biocompatibility and protein accumulation.

The contact lens material is prepared by free lycal polymerization of an organic material for contact lenses and a carboxylic acid ester having no beta hydrogen atom, wherein the carboxylic acid ester can have a Shore D hardness of 70 or more and a DK of 10 or more at a number average molecular weight of 50,000 or more when polymerized alone, and acts to prevent substantial reduction in the oxygen permeability of the organic material for contact lenses. In some cases, there is a reduction in the DK compared to the DK of the siloxane alone, but this reduction is substantially smaller than the reduction resulting from the use of a conventional curing agent such as methyl methacrylate.

The carboxylic acid esters can be copolymerized with other organic contact lens materials, or substantially homopolymerized by free radical polymerization, to produce homopolymers having acceptable contact lens values for DK and overall hardness, machinability and processing characteristics, including compatibility with the wearer's eye. Neopentyl itaconate and neopentyl methacrylate are preferred materials for use as homopolymer contact lenses, or for copolymerization with other organic contact lens monomers.

Other contact lenses based on telechelic perfluorinated polyethers are also known. These lenses may have good oxygen permeability, but are generally relatively soft and therefore difficult to machine using conventional mechanical techniques known in the art.

Another contact lens having good oxygen permeability is one made of various mixtures and copolymerized materials of organosiloxanes and fluorinated components, as described in U.S. Patent No. 4,433,125. However, on the other hand, these materials sometimes exhibit low levels of hardness.

In many of the above contact lens materials, methacrylates, acrylates and itaconates are used to increase hardness, but there are still problems in terms of optical properties essential for contact lenses.

In general, in conventional gas permeable hard contact lenses, the oxygen permeability is often increased by the addition of silicone and/or fluorine-containing materials, but a hardener is often required to maintain the desired hardness of the lens.

According to the present invention, a contact lens material is produced by free lycal polymerization of an organic material for a contact lens and a carboxylic acid ester having no beta hydrogen atom, wherein the carboxylic acid ester can have a Shore D hardness of 70 or more and a DK of 10 or more at a number average molecular weight of 50,000 or more when polymerized alone, and acts to prevent substantial reduction in the oxygen permeability of the organic material for a contact lens. In some cases, there is a reduction in DK compared to the DK of siloxane alone, but this reduction is substantially smaller than the reduction resulting from the use of a conventional curing agent such as methyl methacrylate.

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Claims (29)

Organic materials for contact lenses. A contact lens material having a Shore D hardness of 70 or more and a DK of 10 or more, prepared by free radical polymerizing a carboxylic acid ester having the following general formula derived from one or more alcohols not having a predetermined amount of beta hydrogen to provide the contact lens material with a predetermined hardness and oxygen permeability, wherein A is selected from the group consisting of mesaconic acid, itaconic acid, citraconic acid, methylene malonate, maleic acid, fumaric acid, ethylene tricarboxylic acid, acrylic acid and methacrylic acid, n is 1, 2 or 3, R1, R2 and R3 are the same or different and are each an alkyl, cycloalkyl or aryl group having 1 to 10 carbon atoms or an ether group having 2 to 10 carbon atoms, and when A is derived from a dibasic acid or a tribasic acid, the ester is a complete ester derived from one or more alcohols not having a beta hydrogen, It can be a half ester, a partial ester or a mixed ester.
In claim 1, the organic material for a contact lens is selected from the group consisting of the following (a) to (g): (a) an ethylenically unsaturated organosilicone having the following formula; [wherein, X is an ethylenically unsaturated group selected from the group consisting of vinyl, acryloxy, methacryloxy, vinyloxy, and carbovinyloxy, Y is a divalent group selected from the group consisting of methylene, ethylene, propylene, propenylene, butylene, cyclohexylene, and phenylene, a is an integer from 1 to 4, n is an integer from 4 to 20, b is an integer from 0 to 3, and may be the same or different in each i group, and R may be the same or different within each i residue and is selected from the group consisting of vinyl, methyl, ethyl, propyl, butyl, cyclohexyl, phenyl, 2-acetoxyethyl, Selected from the group consisting of 3-acetoxypropyl, 2-(carbomethoxy)ethyl, 3-(carbomethoxy)propyl, 3-hydroxypropyl, 4-hydroxybutyl, 3,3,3-trifluoropropyl, 3-(heptafluoroisopropoxy)propyl, pentafluorophenyl; (b) fluorosilicone acrylates; (c) fluoroacrylates; (d) fluoropolyethers; (e) hema type materials; (f) styrene polymers; and (g) mixtures thereof.
A contact lens material, wherein the carboxylic acid ester in the second paragraph is an ester having a predetermined hardness and a DK of 10 or more when homopolymerized into a polymer having a number average molecular weight of 50,000 or more by free radical polymerization.
A contact lens material in claim 3, wherein the ester is a monocarboxylic acid ester selected from the group consisting of acrylate, methacrylate, and mixtures thereof.
A contact lens material in claim 3, wherein the ester is a dicarboxylic acid ester selected from the group consisting of mesaconate, itaconate, citraconate, maleate, methylene malonate, and fumarate.
A contact lens material in claim 3, wherein the ester is a tribasic acid ester.
A contact lens substantially made of an ester which is a free radical polymerization product of a polymerizable carboxylic acid ester having the following general formula, and having a number average molecular weight of at least 50,000 and a Shore D hardness of at least 70 and at least 10, wherein A is selected from the group consisting of mesaconic acid, itaconic acid, citraconic acid, methylene malonate, maleic acid, fumaric acid, ethylene tricarboxylic acid, acrylic acid and methacrylic acid, n is 1, 2 or 3, R1, R2 and R3 are the same or different and are each an alkyl, cycloalkyl or aryl group having 1 to 10 carbon atoms or an ether group having 2 to 10 carbon atoms, and when A is derived from a dihydric or trihydric acid, the ester can be a complete ester, a half ester, a partial ester or a mixed ester derived from one or more alcohols having no beta hydrogen.
A contact lens according to claim 7, further comprising at least one modifier selected from the group consisting of a wetting agent, a crosslinking agent, a permeability enhancer, a property modifier, and a mixture thereof.
A contact lens having a DK of 15 or more in claim 7.
A contact lens in claim 7, wherein the ester is dineopentyl itaconate.
A contact lens in claim 7, wherein the ester is dineopentyl fumarate.
A contact lens in claim 7, wherein the ester is neopentyl methacrylate.
A contact lens in claim 7, wherein the ester is neopentyl acrylate.
A contact lens in claim 7, wherein the ester is dineopentyl maleate.
A contact lens in claim 7, wherein the ester is dineopentyl methylene malonate.
A contact lens in claim 7, wherein the ester is dineopentyl citraconate.
A contact lens according to claim 7, wherein the ester is dineopentyl mesaconate.
A polymerized contact lens material prepared by free radical polymerization of 1-10 wt% of a wetting agent, 0-60 wt% of silicone methacrylate, 0-30 wt% of a crosslinking agent and 10-80 wt% of dineopentyl itaconate.
A polymerized contact lens material prepared by free radical polymerization of methacrylic acid, n-vinyl pyrrolidone, methacryloyloxypropyl tris(trimethyl silyl)siloxane, tetraethylene glycol dimethacrylate, and dineopentyl itaconate.
A polymerized contact lens material prepared by free radical polymerization of 0-10 wt% of a wetting agent, 0-30 wt% of a crosslinking agent, 0-60 wt% of a fluorinated itaconate, 0-60 wt% of a fluorinated methacrylate, 0-60 wt% of a silicone methacrylate, and 10-80 wt% of a dineopentyl itaconate.
A polymerized contact lens material prepared by free radical polymerization of methacrylic acid, n-vinyl pyrrolidone, neopentyl glycol dimethacrylate, methacryloyloxypropyl tris(trimethylsilyl)siloxane, bis-hexafluoroisopropyl itaconate, hexafluoroisopropylmethycrylate and dineopentyl itaconate.
A polymerized contact lens material prepared by free radical polymerization of 0-10 wt% of a wetting agent, 10-80 wt% of dineopentyl iticonate, 0-60 wt% of a fluoroalkyl methacrylate, 0-60 wt% of a fluoroalkyl ataconate and 0-30 wt% of a crosslinking agent.
A polymerized contact lens material prepared by free radical polymerization of n-vinyl pyrrolidone, dineopentyl itaconate, hexafluoroisopropyl methacrylate, bis-hexafluoroisopropyl itaconate and neopentyl glycol dimethacrylate.
A method for modifying the hardness and DK value of a contact lens material, comprising mixing a carboxylic acid ester derived from one or more alcohols having no beta hydrogen and a contact lens material, and then polymerizing the ester under free radical conditions to copolymerize the material and the ester to obtain a predetermined hardness and oxygen permeability.
In claim 24, the ester is a compound having the following general formula, and the lens has a Shore D hardness of 70 or more and a DK of 10 or more. In the formula, A is selected from the group consisting of mesaconic acid, itaconic acid, citraconic acid, methylene malonate, maleic acid, fumaric acid, ethylene tracarboxylic acid, acrylic acid and methacrylic acid, n is 1, 2 or 3, R1, R2 and R3 are the same or different and are each an alkyl, cycloalkyl or aryl group having 1 to 10 carbon atoms or an ether group having 2 to 10 carbon atoms, and when A is derived from a dibasic acid or a tribasic acid, the ester can be a complete ester, a half ester, a partial ester or a mixed ester derived from one or more alcohols having no beta hydrogen.
A method according to claim 24, wherein the ester is dineopentyl itaconate.
A method in claim 24, wherein the ester is neopentyl ester.
A method in claim 24, wherein the ester is neopentyl fumarate.
A method in claim 24, wherein the ester is neopentyl maleate.