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
  • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• • 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
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/062—Polyethers

Definitions

• the conventional soft lenses are primarily hydrogels derived from a variety of hydrophilic monomers or polymers which have either been crosslinked or insolubilized in water by some other mechanism, such as by
• hydrophobic/hydrophilic properties normally contain approximately 38% water with a Dk value of 8-12 (x10 -11 cm 2 /sec) (ml O 2 /ml mmHg) at
• hydrophobic polymer system which is above its glass transition temperature, such as a silicone
• Such materials can have a high Dk value, but generally have a much poorer drape than hydrogel lenses.
• "Hard" lenses these were initially prepared from polymethyl methacrylate, but such systems lacked sufficient oxygen permeability to provide adequate oxygen levels to the cornea. Because of this difficulty, hard oxygen-permeable contact lens materials were introduced. Such materials have been prepared from either siloxanyl alkyl methacrylates or fluoromethacrylates, usually in copolymerization with other monomers to improve hardness, refractive index, and wettability.
• the extended wear hard gas permeable lenses normally provide greater visual acuity than hydrogel lenses, with a far greater rigidity to the lens material.
• Such hard lenses do not have the inherent comfort of a soft hydrogel lens and they also can develop marked surface deposits with time unless properly cleaned.
• Pat. No. 3,808,179 teaches that certain hard gas permeable contact lens materials containing a fluoroalkyl acrylate or methacrylate can be made inherently wettable.
• U.S. Pat. No. 3,542,461 teaches that solid oxygen permeable lenses of various fluoropolymers can be prepared that have indices of refraction similar to human tears.
• U.S. Pat. No. 3,940,207 teaches that soft, tough materials
• fluorine-containing contact lenses can be made, after surface treatment, which are wettable and have low oxygen permeability.
• U.S. Pat. No. 3,950,315 teaches that contact lenses containing less than 5% water can be made from a copolymer of methyl methacrylate and a fluoroester, said lens materials have a Dk of 2.5 (2,500 centibarrers).
• U.S. Pat. No. 4,433,111 teaches that a hydrogel polymer containing 5 to 10 mole % fluorine-containing monomer or precursor and another hydrophobic monomer has the ability to increase the protein repellency of the lens material in the presence of artificial tear fluid, with Dk values between 40-80 at 34°C.
• N-vinylpyrrolidone N-vinylpyrrolidone.
• a high oxygen permeability a high water of hydration and a high resistance to surface deposits in contact lens materials which can be obtained through a bulk polymerization reaction and utilized in a hydrogel form for either daily wear or extended wear applications.
• a hydrogel contact lens material is made from copolymerizing (a) from 0.1 wt% to 40 wt% of a linear, branched, cyclic or bicyclic fluorine-containing monomer with (b) 2-85 wt% of mono- or di-hydroxy alkyl ester or an alkylene oxide ester, of acrylic or methacrylic acid, and (c) 5-80 wt% of an N-vinyl lactam.
• one or more of the following monomers are further copolymerized with (a), (b) and (c); (d) 0-60% of other hydrophilic monomers, (e) 0-7% of a crosslinking agent and (f) 0-2 wt% of a uv absorbing monomer or polymer.
• Polymerization is either conducted by free radical initiation, by uv, x-ray, y-ray, electron beam or microwave polymerization.
• polymerization is carried out in bulk using a free radical initiator in a temperature range of 35°C to 90°C.
• Such polymerizations may also be conducted in a solvent such as glycerol.
• the Dk of the material is preferably at least 35 (x10 -11 cm 2 /sec) (ml O 2 /ml mm Hg) at 35°C and the material has a water of hydration of at least 30 weight percent.
• a clear hydrogel lens polymeric material has good surface resistance, high tensile and tear strength, high oxygen permeability, good optical clarity and consists essentially of the free radical
• polymerization product of (a) about 7 to about 25.0 part by weight of a fluorine-containing monomer, (b) about 2.5 to about 81.0 parts by weight of a
• the product has a Dk value of from at least 35 at 35°C and a wet water of hydration of at least 30 percent.
• solubility to the hydrogel and the hydroxyalkyl ester of acrylic or methacrylic acid (b) provides wettability and integrity to the gel network.
• the addition of the N-vinyl lactam (c) to (a) and (b) is critical to obtain clear bulk copolymers without any haze or opacity. Without the presence of (c), optically clear bulk polymers do not result.
• (c) also provides for wettability greater than that from utilizing only (b) in conjunction with (a).
• (c) is a compatibi l ity increasing agent or solubi l izing monomer capable of causing phase domain size of the hydrophobic moiety smaller than the wave length of light and this gives optical clarity.
• fluorosubstituents appear to increase the tear strength of the gel above that of a related hydrogel at the same water content but without the
• a uv-absorbing hydrogel contact lens such as for aphakic extended-wear patients
• a uv-absorbing monomer or polymer can be incorporated into the formulation such that uv absorption in the range of 300-410 nm is obtained.
• novel copolymers preferably have from 0.1 to 40 wt% of a linear, branched, cyclic or bicyclic fluorine-containing monomer with best results obtained with 10 to 25 wt% of (a).
• fluoromonomers useful in this invention have the following structures:
• R is selected from the class of hydrogen, methyl, fluoro and trifluqromethyl groups
• "a” is an integer from 1-4
• "b” is an integer from 0-4
• R 1 is selected from the class of hydrogen, methyl and trifluoromethyl groups
• R f is a straight or branched fluoroalkyl group preferably having from 1-18 carbon atoms, fluoroaryl group, or
• Fluorostyrenes having 1-24 fluorine atoms.
• R 2 is selected from the class of fluoro or R f groups
• R 3 is selected from the class of hydrogen or fluoro groups.
• R 4 is a substituent containing a polymerizable double bond.
• fluoro macromonomers they can be used in combination with conventional low molecular weight fluoromonomers to improve compatibilization.
• the macromonomers, if used, are preferably used at the low end of the 0.1 to 40% range and most preferably about 1 to about 5% by weight.
• R, R f are designated as above, and R 5 is selected from the class of hydrogen, alkyl or aryl substituents.
• fluoromonomers can either be used individually or in combination, with the fluoromethacrylates and the fluorostyrenes being the preferred materials.
• methacrylic acid which are of use, are preferably derived from 2-hydroxyethyl acrylate and
• methacrylates can be used without the above-noted hydroxyalkyl esters so long as optical clarity is maintained.
• 2-Hydroxyethyl methacrylate being the preferred material in concentration of 2 - 85 wt%, and preferably between 10 - 35%.
• N-vinyl lactam the preferred compound is N-vinylpyrrolidone, although other substituted vinylamides can be employed. It is important that this class of molecule be present, in concentrations from 5 - 80 wt%, and preferably from 40-60 wt%, in order to allow for compatibility and optical clarity for bulk polymerized formulations which include a fluoromonomer and a hydroxyalkyl ester. Outside of these limits it is usually difficult to obtain optically clear materials when the polymerization is conducted in the absence of solvent.
• crosslinking agents include polyfunctional derivatives of acrylic acid, methacrylic acid, acrylamide, methacrylamide and multi-vinyl substituted benzenes, including but not limited to the following: ethylene glycol
• diacrylate or dimethacrylate diethylene glycol diacrylate or dimethacrylate, triethylene glycol diacrylate or dimethacrylate, tetraethylene glycol diacrylate or dimethacrylate, polyethylene glycol diacrylate or dimethacrylate, trimethylolpropane triacrylate or trimethacrylate, Bisphenol A
• polysiloxanylbisalkyl acrylates and methacrylates polysiloxanylbisalkylglycerol acrylates and
• the additional hydrophilic monomers useful in the present invention include acrylic and
• vinylsulfonic acid and its salts vinylsulfonic acid and its salts, styrenesulfonic acid and its salts, 2-methacryloyloxyethyl sulfonic acid and its salts, 3-methacryloyloxypropyl sulfonic acid and its salts, allylsulfonic acid,
• 2-methacryloyloxyethane sulfonic acid is the preferred wetting agent.
• a uv absorbing material can be added to the above mixture of monomers if it is desired to reduce or eliminate uv radiation in the wavelength of
• benzophenone and benzotriazole families such as 2,2'-dihydroxy-4-methacryloyloxybenzophenone,
• benzophenone 1-,4-,5-,6-, or 7-vinylbenzotriazole 4-, 5-, 6-, or 7- methacryloyloxybenzotriazole, 1-methacryloylbenzotriazole, 4-, 5-, 6-, or 7- methacryloyloxy-2-hydroxypropoxybenzotriazole and 1-(methacryloyloxy-2-hydroxypropoxy)benzotriazole.
• copolymers described in this invention are preferentially prepared by radical polymerization utilizing a free radical initiator.
• the initiators are preferably either azo or peroxide families.
• Typical initiators include: 2,2'-azobis (2,4-dimethylpentanenitrile)(VAZO 52), 2,2'- azobisisobutyronitrile, 4,4'- azobis
• the monomer solutions containing 0.1 to 0.5 wt% initiator are flushed with either
• the samples which are in plastic cups, plastic or glass tubes, are then heated at 35°C for 24 hours, 50°C for three hours, 70°C for one hour and 90°C for three hours. After this cycle is completed, the samples are cooled and the
• contact lenses can be prepared directly as in spin casting.
• the material is prepared in button, rod, or disc form, or other desired shapes, which can then be machined.
• the resulting lenses are then hydrated in an isotonic buffered solution for one to two days at 35°C prior to use.
• isotonic buffered solution for one to two days at 35°C prior to use.
• N-vinylpyrrolidone either optically clear, hazy, or opaque polymeric materials are obtained. Under certain ratios, as described herein, optically clear, hard, machineable materials can be prepared.
• a hydrogel results, usually within 1 to 7 days.
• the hydrogels absorb between 30 wt.% to 93 wt.% of buffered isotonic saline solution.
• Such materials can have Dk values at 35°C ranging from 9 to 83.
• hydrogels have application in other biological materials such as surgical
• hydrophilic catheter coverings hydrophilic vascular grafts and hydrophilic burn dressings.
• the desired materials for fluorine-containing hydrogel lenses are obtained by mixing the desired monomers and initiator, filtering the homogeneous comonomer solution, and pouring said solution into previously dried reaction vessels.
• the vessels are then placed in a heating block or bath and flushed with argon for a period of 5 minutes, after which the vessels are heated at 35°C for 24 hours, 50°C for three hours, 70°C for one hour and 90°C for three hours.
• the heating block is cooled to room temperature and the vessels are removed.
• buttons or rods are then removed from their respective vessels.
• buttons are then cut into discs to determine water uptake by soaking in an isotonic buffered solution at pH 7.3 at 35°C for at least 100 hours or until maximum swelling has occurred.
• the % of water of hydration based on the dry disc is determined after drying the hydrated disc at 50°C under vacuum overnight.
• the oxygen permeability (Dk) was calculated by multiplying the cell constant with the inverse value of the slope obtained from the latter plot.
• the unit for Dk is 10 _11 (cm 2 /sec)(ml 0 2 /ml mm Hg) .
• Hydration 310 0.988Hydration 207 and the % dry hydration data were converted to an isotonic buffer by the equation:
• Table 1 illustrates the effect of variation of the hexafluoroisopropyl methacrylate (HFM) and
• HEMA 2-hydroxyethyl methacrylate contents
• NDP N-vinylpyrrolidone
• MA methacrylic acid
• Table 2 indicates the effect of varying the HEMA and MA contents, with constant contents of HFM and NVP.
• Table 3 illustrates the effect of varying the HEKA, NVP, and MA contents, with a constant content of HFM.
• Table 4 illustrates the effect of varying low content of HFM with varying contents of HEMA and MA at constant NVP content.
• Table 5 illustrates the effect of varying low content of PFS with varying contents of HEMA and MA at constant NVP content.
• Table 6 illustrates the effect of varying low content PFS with varying contents of HEMA, NVP, and MA. All measurements were obtained in a pH 7.3 buffer at 310 mos.
• Table 7 illustrates the effect of adding a styrenic derivative, t-butyl styrene (tBS).
• Table 8 illustrates the effect of adding a crosslinking agent, tetraethylene glycol dimethacrylate (TEGDM).
• TAGDM tetraethylene glycol dimethacrylate
• Table 9 illustrates the effect of adding a strengthening monomer, methyl methacrylate (MMA), to the hydrogel.
• MMA methyl methacrylate
• Table 10 illustrates the effect of variation of the pentafluorostyrene (PFS) and HEMA contents, with constant contents of NVP and MA.
• Table 11 illustrates the effect of combining different compositions of PFS and HFM, with varying content of HEMA and constant contents of NVP and MA,
• UV ultraviolet absorber
• Table 14 illustrates the use of a sulfonate monomer in its salt form as an added hydrophilic agent.
• HEMA, NVP and PFS were weighed into a beaker.
• SEM sulfoethyl methacrylate
• TAA triethanolamine
• Table 15 illustrates the use of p-fluorostyrene (pFS) as the fluoromonomer in conjunction with HEMA, NVP, and MA.
• pFS p-fluorostyrene
• Table 16 illustrates the use of glycerol as a solvent for the polymerization of PFS, HEMA, NVP, and MA. All reactions were thermally initiated with VAZO-52. The total monomer concentration was 85 wt.% and the glycerol concentration was 15 wt.%. Polymerization could be done in a stationary state or under spin casting conditions.
• Table 17 illustrates the use of glycerol as a solvent for the polymerization of PFS, HEMA, NVP, and the potassium salt of 3-sulfopropyl methacrylate (SPM). Reactions were initiated either thermally with VAZO-52 or by uv using benzoin methyl ether as the photoinitiator. The total monomer
• Table 18 illustrates the use of constant PFS with constant SEM.
• TEA as a function of increasing NVP and decreasing HEMA. All measurements were obtasined in a pH 7.3 buffer at 310 mos.
• Table 19 illustrates the use of glycerol as a solvent for the polymerization of pentafluorobenzyl methacrylate (PFMB), HEMA, NVP, and SPM. Reactions were initiated either thermally with VA70-52 or by uv using benzoin methyl ether as the photoinitiator,
• Table 20 illustrates the polymerization of PFBM, HEMA, NVP, and SEM.
• TEA All reactions were photoinitiated using benzoin methyl ether as the photoinitiator, either in the presence or absence of glycerol.
• hydrogel discs including fluorinated and non-fluorinated lens materials were soaked in the artificial tear solution at 35°C for two weeks.
• fluorinated lens materials containing from 0.2 to 25 wt.% fluoromonomer in accordance with this invention substantially less surface deposits were noted as compared to the non-fluorinated hydrogel lens materials, with the higher content fluoro material appearing to have less deposit formation.
• all fluoropolymer materials were readily cleaned by running water, a circumstance which was not possible with the non-fluorinated polymers. With the use of an enzyme cleaner, the surface deposits were also removed.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Eyeglasses (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=26695737

Family Applications (1)

Country Status (11)

Families Citing this family (68)

Citations (2)

Family Cites Families (20)

• 1987
  • 1987-03-05 US US07/022,270 patent/US4990582A/en not_active Expired - Lifetime
  • 1987-06-18 AT AT87305402T patent/ATE126357T1/de not_active IP Right Cessation
  • 1987-06-18 EP EP87305402A patent/EP0253515B1/en not_active Expired - Lifetime
  • 1987-06-18 DE DE3751441T patent/DE3751441T2/de not_active Expired - Fee Related
  • 1987-06-23 JP JP62154573A patent/JP2619245B2/ja not_active Expired - Lifetime
  • 1987-07-14 BR BR8703665A patent/BR8703665A/pt unknown
  • 1987-07-17 MX MX007414A patent/MX170196B/es unknown
  • 1987-07-17 AU AU75777/87A patent/AU7577787A/en not_active Abandoned
  • 1987-07-17 CA CA000542350A patent/CA1330141C/en not_active Expired - Fee Related
  • 1987-07-18 CN CN198787105002A patent/CN87105002A/zh active Pending
• 1990
  • 1990-12-21 WO PCT/US1990/007601 patent/WO1992011300A1/en not_active Ceased
  • 1990-12-21 EP EP91917407A patent/EP0563047A1/en not_active Withdrawn
• 1995
  • 1995-03-13 US US08/404,124 patent/US5684059A/en not_active Expired - Fee Related

Patent Citations (2)

Also Published As

Similar Documents

Legal Events