EP0044293A1 - Quaternäre ammoniumsalze in hydrogel-kontaktlinsen - Google Patents

Quaternäre ammoniumsalze in hydrogel-kontaktlinsen

Info

Publication number
EP0044293A1
EP0044293A1 EP19800900690 EP80900690A EP0044293A1 EP 0044293 A1 EP0044293 A1 EP 0044293A1 EP 19800900690 EP19800900690 EP 19800900690 EP 80900690 A EP80900690 A EP 80900690A EP 0044293 A1 EP0044293 A1 EP 0044293A1
Authority
EP
European Patent Office
Prior art keywords
group
methacrylate
drops
chemical company
witco chemical
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.)
Withdrawn
Application number
EP19800900690
Other languages
English (en)
French (fr)
Inventor
Jr. William M. Foley
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FOLEY WILLIAM M JUN
Original Assignee
FOLEY WILLIAM M JUN
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by FOLEY WILLIAM M JUN filed Critical FOLEY WILLIAM M JUN
Publication of EP0044293A1 publication Critical patent/EP0044293A1/de
Withdrawn legal-status Critical Current

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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

Definitions

  • This invention generally relates to soft contact lenses and particularly those well known in the art as hydrogel lenses.
  • the epithelium of the cornea required oxygen which is usually supplied from the oxygen dissolved in tears.
  • oxygen which is usually supplied from the oxygen dissolved in tears.
  • the flow of lacrimal fluid is greatly curtailed beneath the lens.
  • This reduction in fresh lacrimal fluid is not desirable as it substantially reduces the contact of the eye with oxygen. Therefore, it is extremely important that the lens material itself be gas permeable.
  • Hard lenses fail to admit sufficient oxygen and/or release sufficient carbon dioxide to maintain a healthy normal condition for the eye tissue and cornea covered, especially when the lens is worn continuously for extended periods of time. In other words, the conventional hard lenses cannot breathe sufficiently through the body of the lens.
  • the hydrogel soft contact lenses receive their flexibility from their capacity to absorb water. After machining and polishing the lenses, they are placed in a saline solution from which they absorb water and swell until equilibrium is obtained. This process allows hydrogel lenses to possess a high degree of hydration which is directly related to the mode of oxygen transport and the lenses are thereby able to provide the eye with sufficient oxygen.
  • the more water that the lens is able to absorb the higher the hydration percent and therefore, the better the oxygen permeability of the lens.
  • a problem associated with highly hydrated hydrogel lenses is that although they are able to obtain satisfactory oxygen transport levels, since they are used in the swollen state, the molecular materials of their composition are markedly reduced in mechanical strength and the resulting lenses are extremely fragile. Due to this fragileness, the thickness of the lens must be increased and, therefore, these pridr art soft lenses are ill-suited for the preparation of ultra-thin corneal lenses. By increasing the thickness of the lens, the gas permeability of the lens is thereby decreased forming a vicious cycle between gas permeability and strength. In making an ultra-thin lens, the greater the strength and the greater the refractive index of the material used, the better the resulting thin lens.
  • the disclosed invention obviates the above deficiency in the prior art by providing a co-monomer mixture suitable for producing hydrogel contact lenses which have a superiorly high strength and refractive index, which can withstand sterilization, and, in addition, offer superior gas permeability.
  • a further advantage of these materials, especially the more hydrophilic ones, lies in the fact that lenses made of these materials have a much lesser tendency to dehydrate while on the eye.
  • a group 3 monomer which is a cross-linking agent up to 10% of a group 3 monomer which is a cross-linking agent; and (d) the balance being a group 4 monomer which is a hydrophilic molecule selected from the group consisting of a hydroxy lower alkyl acrylate or methacrylate, a hydroxy lower alkoxy lower alkyl acrylate or methacrylate, or a lower alkoxy lower alkyl acrylate or methacrylate.
  • a group 5 monomer which is an unsaturated aliphatic monomeric acid having at least one carboxyl group in its molecule can be added.
  • soft contact lenses result which have hydration levels of 35% to 85%, exhibit excellent strength and possess good optics. and machineability.
  • the lens is prepared using conventional lens production techniques.
  • the disclosed invention is therefore, a contact lens possessing all of the following properties: (1) a lens with outstanding gas permeability due to its ability to tolerate a very high degree of hydration;
  • hydrogel contact lens of the disclosed invention is formed from co-polymerizing a group of several co-monomers.
  • the group 1 monomers which represent quaternary ammonium salts play a major role in producing the outstanding characteristics of the resulting lenses.
  • the quaternary ammonium salts permit extremely high levels of hydration, i.e., as high as 85%. These high hydration levels in turn permit the addition of group 2 monomers to the monomer mixture which provide outstanding strength to the resulting lens and yet do not reduce the hydration level to any significant degree, One would normally expect a significant drop in the hydration percentage when adding such materials as alkyl methacrylate monomers, however, the presence of the quaternary ammonium salts maintain these high levels of hydration.
  • the resulting lens therefore, possesses a combination of high hydration and strength not achieved by prior methods.
  • the amount of quaternary ammonium salt which can be added to the mixture is 5% to about 80%. Hydration levels will rise with higher percentages of the salt. At about 5% the hydration level will be about 35%.
  • a preferred amount of salt is 45% to 60% which provides hydration levels of about 60% to 85%.
  • X- is a negative ion such as halogen, preferably chloride and n is an integer of 1 or more.
  • R 1 and R 2 are not critical substituents. They may be alkyls such as ethyl, propyl, butyl, pentyl, heptyl, hexyl, etc., or alkoxy alkyls such as ethoxyethyl, methoxyethyl, propoxyethyl, butoxyethyl, pentoxyethyl, etc., or hydroxy alkyls such as hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, etc.
  • R 1 and R 2 may also be alicyclics such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl or aromatics such as phenyl or substituted phenyls.
  • the R 1 and/or R 2 group may be identical to hydrophilic R 3 substituent discussed hereinafter.
  • R 1 and R 2 may be part of a cyclic structure such as piperidine, morpholine or piperazine as shown in (2).
  • R 3 is a polymerizable vinyl group.
  • polymerizable vinyl group as used in this disclosure means a substituent providing a carbon-carbon double bond such that the molecule to which it is attached may be polymerized, such as vinyls per se, acrylates, methacrylates, acrylamides or methacrylamides.
  • reactants which form the vinyl per se functional group are vinyl ethers such as ethyl vinyl ether, propyl vinyl ether and analogs of the above including allyl, crotyl, etc., analogs.
  • Examples of reactants which form the acrylate functional group are dimethylaminoethyl acrylates, dimethylaminopropyl acrylate, dimethylaminobutyl acrylate and analogs of all of the above.
  • Examples of reactants which form the methacrylate functional group are dimethylamino methacrylate, dimethylaminopropyl acrylate and analogs of all of the above.
  • Examples of reactants which form the acrylamide functional group are dimethylaminoethyl acrylamides, dimethylaminopropyl acrylamide, and analogs of all of the above.
  • Examples of reactants which form the methacrylamide functional group are dimethylaminopropyl methacrylamide, dimethylaminoethyl methacrylamide, and the diethylamino and methylethylamino analogs of all of the above.
  • Difunctional methacrylamides are also contemplated such as aminoethyliminoethyl dimethacrylamide, aminopropyliminoethyl dimethacrylamide, etc., and aminopropylpiperazinepropyl dimethacrylamide.
  • R 4 represents a hydrophilic substituent.
  • Hydrophilic substituent is herein defined as a keto alkyl, carboxamide alkyl, carboxy alkyl, carbalkoxy alkyl, hydroxy alkyl, alkoxy alkyl, aryl alkyl, or aryloxy alkyl functional group and is intended to include mono, di and tri hydroxyl substituents.
  • the R 4 groups are formed from compounds such as 3-chloropropanediol-1, 2, propiolactone, chloroacetamide, 2-chloroethanol, 3-chloro 1-methoxy-2-hydroxypropane and 3-chloro-2-methoxy-1- hydroxypropane, etc.
  • the salts are formed from a Lewis acid and base as is well known in the art. Examples of these reactants and the formulations of the salts are as follows:
  • the propylimino unit may be repeated to form long chains.
  • the group 2 monomers are strength enhancing materials. These monomers which provide excellent durability to the lenses do not curtail hydration percentage due to the presence of the quaternary ammonium salt. The percentage of the group 2 monomer is about 1% to as high as 50%. Examples of the group 2 monomers are styrenes, alkyl acrylates or alkyl methacrylates, aryl acrylates or methacrylates and aryl vinyl ethers. These monomers are known to possess the desired strength enhancing property. As long as this property is present, the particular group 2 monomer which is chosen is not critical although styrene monomers have the added advantage of being gas permeable as well.
  • Styrene monomers are herein defined as any form of styrene or substituted styrenes such as alpha alkyl styrenes or vinyl toluene or a like alkylated or halogenated styrene.
  • Alkyl acrylates or methacrylates are well known in the art and include methyl acrylate, ethyl acrylate, isopropyl acrylate, propyl acrylate, butyl acrylate, sec. butyl acrylate, pentyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, sec. butyl methacrylate, pentyl methacrylate, and cyclohexyl methacrylate.
  • aryl acrylates and methacrylates are phenyl acrylate, phenyl methacrylate, etc.
  • An example of a phenyl vinyl ether is:
  • the group 3 monomer is a cross-linking agent which provides the desired strength and may be added up to 10% of the monomer mixture, preferably about 1%.
  • the cross-linking agents are well known to those in the art and are exemplified by diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylates, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, diethylene glycol bisallycarbonate, 2,3 epoxy propyl methacrylate, divinyl benzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene dimethacrylate,
  • These polyfunctional monomers are added to effect the stabilization of the polymer and the stabilization of the lens by forming a three-dimensional structure.
  • the cross-linking comonomer may also include quaternary ammonium salts in the molecule.
  • Applicant's application entitled SYMMETRIC HYDROGEL MATRIX FOR CONTACT LENSES, filed May 16, 1977, in part discloses a new type of cross-linker which enhances hydration since the chain of the hydrophilic glycol is lengthened thereby providing a more hydrophilic cross-linking agent and one which will not spacially restrict the hydration process.
  • the group 4 monomers represent a class of hydrophilic monomers which provide the principal co-monomer with the quaternary ammonium salt co-monomer. These hydrophilic monomers are well known to those in the art and generally represent the various hydrophilic acrylates and methacrylates which are conventionally used in the present hydrogel lenses. More specifically, these monomers are hydroxy lower alkyl acrylates. or methacrylates, hydroxy lower alkoxy lower alkyl acrylates or methacrylates, and alkoxy lower alkyl acrylates and methacrylates. A "lower alkyl” or “lower akloxy” is herein defined to mean an alkyl or alkoxy of about five carbon atoms or less.
  • the group 4 monomers include hydrophilic dihydroxy and trihydroxy alkyl acrylates and methacrylates such as 2,3 dihydroxypropyl methacrylates or 2,3 dihydroxybutyl methacrylates, etc.
  • Examples of other group 4 monomers are hydroxy substituted or alko-xy substituted methacrylates or acrylates.
  • the hydroxy substituted acrylates or methacrylates are generally disclosed and discussed in U.S. Patent 3,983,083 issued to Kaetsu et al, which is herewith incorporated by reference.
  • Other group 4 monomers are generally alkylene glycol monomethacrylates or acrylates. These are generally discussed in U.S. Patent 3,988,274 issued to Masuhara et al which is herewith incorporated by reference.
  • HEMA hydroxyethyl methacrylate
  • hydroxyethyl acrylate hydroxypropyl methacrylate
  • hydroxyproply acrylate butanedoil monomethacrylate
  • butanediol monoacrylate examples of these monomers are hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxyproply acrylate, butanedoil monomethacrylate, butanediol monoacrylate.
  • the most preferred monomers are the hydroxy alkyl acrylates and methacrylates, particularly 2-hydroxyethyl methacrylate.
  • the group 5 monomer can optionally be added to the polymerization mixture.
  • This monomer aids in hydration and facilitates machining and polishing by providing dry state hardness. It represents monomers having at least one carboxyl group in their molecule and are exemplified by acrylic acid, methacrylic acid and itaconic acid, but are not limited to these compounds so long as at least one carboxyl group is present. This component further increases the hydrationof the resulting lens. Up to 10% of this monomer may be added.
  • a polymerization catalyst or initiator can also be added to the monomer mixture in order to promote the polymerization.
  • These initiators are well known to those in the art and are for example, benzoyl peroxide, lauroyl peroxide, cumene hydro peroxide, di-tert-butyl peroxide, diisopropyl peroxycarbonate, azobisisobutyronitrole, t-butyl peroctoate, t-butyl perneodecanoate, t-butyl perpivalate, 2,5-dimethyl hexane 2, 5-diper-2-ethylhexoate or the like.
  • the monomers are mixed conventionally and placed in an oven to begin the polymerization (curing). Such polymerization is carried out conventionally between 40oC and 100oC.
  • the mixture is cured in the molds at about 65°C for about 1 to 4 hours to form cylindrical lens blanks.
  • the blanks are then annealed for several hours at approximately 85°C.
  • the lenses are then cut, polished and hydrated in saline solutionto form highly hydrated hydrogel soft contact lenses.
  • the following working examples are illustrative only and are not to be construed as limiting the. scope of the invention.
  • the lenses were prepared conventionally as outlined above unless otherwise specified. The experiments are summarized in Table 1 which follows the final example.
  • Example 1 (74% Hydration) Methoxyethyl Methacrylate 4.0Og
  • Example 3 (70.0% Hydration)
  • Ethylhexoate (U.S. Peroxygen Division, Witco Chemical Company, U.S.P. 245) 2 drops
  • the lens blanks had an equilibrium hydration level of 70.0%.
  • Methacrylic Acid 0.40g Triethyleneglycol Dimethacrylate 0.20g 2,5-Dimethyl Hexane-2, 5-diper-2- Ethylhexoate (U.S. Peroxygen Division,
  • the lens blanks had a hydration level of 75.6%.
  • Triethyleneglycol Dimethacrylate 0.20g 2,5-Dimethyl Hexane-2, 5-diper-2-
  • Methacrylic Acid 1.60g Triethyleneglycol Dimethacrylate 0.20g 2,5-Dimethyl Hexane-2, 5-diper-2-
  • Ethylhexoate (U.S. Peroxygen Division, Witco Chemical Company, U.S.P. 245) 2 drops
  • the lens blanks had a hydration level of 55.6%, with a slight haze.
  • Ethylhexoate (U.S. Peroxygen Division, Witco Chemical Company, U.S.P. 245) 2 drops
  • the above were blended and cured at 70-84°C for 1 hour and 20 minutes and 15 hours at 82-87°C.
  • the blanks had a hydration level of 80.7%.
  • Ethylhexoate (U.S. Peroxygen Division, Witco Chemical Company, U.S.P. 245) 2 drops
  • the above were blended and cured for one hour and 30 minutes at 68-87°C.
  • the lens blanks had a hardness of 85D and a hydration level of 35.7%.
  • Ethylhoxoate (U.S. Peroxygen Division, Witco Chemical Company, U.S.P. 245) 2 drops
  • the above were blended and cured at 69-84°C for one hour and 30 minutes.
  • the blanks had a hardness of
  • Ethylhexoate (U.S. Peroxygen Division, Witco Chemical Company, U.S.P. 245) 2 drops
  • buttons had a hardness at 83D.
  • Methoxyethyl Methacrylate 8.00g 2-Hydroxyethyl Methacrylate 10.00g Quaternary Salt of Dimethylaminoethyl Methacrylate and 3-Chloropropanediol-1,2 2.00g Triethyleneglycol Dimethacrylate 0.20g 2,5-Dimethyl Hexane-2, 5-diper-2- Ethylhexoate (U.S. Perosygen Division, Witco Chemical Company, U.S.P. 245) 2 drops Tertiarybutyl Perneodecanoate (U.S. Peroxygen Division, Witco Chemical Company, Esperox 33M) 2 drops The above were blended and cured at 63-86°C for two hours.
  • Ethylhexoate (U.S. Peroxygen Division, Witco Chemical Company, U.S.P. 245) 2 drops
  • Example 20 The above were blended and cured for 2 hours at 61-77°C and 15 hours and 30 minutes at 90°C.
  • Example 20 The above were blended and cured for 2 hours at 61-77°C and 15 hours and 30 minutes at 90°C.
  • the material was strong in the hydrated state, hydration level of 35.7%.
  • the material was strong enough to give a good soft lens with 0.078 mm center thickness in the hydrated state.
  • Ethylhexoate (U.S. Peroxygen Division, Witco Chemical Company, U.S.P. 245) 2 drops
  • Triethyleneglycol Dimethacrylate 0.20g 2,5-Dimethyl Haxane-2, 5-diper-2-
  • Ethylhexoate (U.S. Peroxygen Division, Witco Chemical Company, U.S.P. 245) 2 drops
  • the above were blended and cured at 64-80°C for 1 hours and 45 mintues and 16 hours at 92°C.
  • the lens blanks had a hydration level of 71.4%.
  • the above were blended and cured at 70-81°C for 3 hours and 45 minutes and 15 hours at 75-79°C.
  • the blanks had a hydration level of 33.7%.
  • Triethyleneglycol Dimethacrylate 0.20g 2,5-Dimethyl Hexane-2, 5-diper-2-

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP19800900690 1980-01-21 1980-01-21 Quaternäre ammoniumsalze in hydrogel-kontaktlinsen Withdrawn EP0044293A1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1980/000058 WO1981002136A1 (en) 1980-01-21 1980-01-21 Quaternary ammonium salts in hydrogel contact lenses

Publications (1)

Publication Number Publication Date
EP0044293A1 true EP0044293A1 (de) 1982-01-27

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ID=22154164

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19800900690 Withdrawn EP0044293A1 (de) 1980-01-21 1980-01-21 Quaternäre ammoniumsalze in hydrogel-kontaktlinsen

Country Status (2)

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EP (1) EP0044293A1 (de)
WO (1) WO1981002136A1 (de)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4926514B1 (de) * 1970-09-19 1974-07-09
US3947401A (en) * 1971-10-05 1976-03-30 Union Optics Corporation Hydrogels of unsaturated ester copolymers
US3965063A (en) * 1974-06-06 1976-06-22 Burton, Parsons And Company, Inc. Hydrophilic contact lenses and lens polymer
US4123407A (en) * 1976-11-26 1978-10-31 American Optical Corporation Hydrophilic contact lens

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8102136A1 *

Also Published As

Publication number Publication date
WO1981002136A1 (en) 1981-08-06

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