CN117460782A - Silicone hydrogel contact lenses - Google Patents

Silicone hydrogel contact lenses Download PDF

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Publication number
CN117460782A
CN117460782A CN202280011336.0A CN202280011336A CN117460782A CN 117460782 A CN117460782 A CN 117460782A CN 202280011336 A CN202280011336 A CN 202280011336A CN 117460782 A CN117460782 A CN 117460782A
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silicone hydrogel
weight
hydrogel contact
contact lens
silicon
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片承熙
罗未来
咸炯恩
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Interojo Inc
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Interojo Inc
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Priority claimed from PCT/KR2022/016455 external-priority patent/WO2023224184A1/en
Publication of CN117460782A publication Critical patent/CN117460782A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • 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
    • C08F290/068—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
    • G02C7/04—Contact lenses for the eyes
    • G02C7/049—Contact lenses having special fitting or structural features achieved by special materials or material structures

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Ophthalmology & Optometry (AREA)
  • General Health & Medical Sciences (AREA)
  • Eyeglasses (AREA)

Abstract

A silicone hydrogel contact lens is provided comprising a polymer composition prepared by polymerization of a composition for forming a silicone hydrogel contact lens comprising: about 10 to about 40 weight percent of a silicon-containing macromer, about 1 to about 20 weight percent of polyethylene glycol having a molecular weight of about 200g/mol to about 1,000g/mol, and a crosslinking agent or initiator, wherein the polymerization is conducted by thermal polymerization or UV photopolymerization at a temperature of about 100 ℃ to about 110 ℃ in a manner that removes at least about 95% of the polyethylene glycol from the polymer composition.

Description

Silicone hydrogel contact lenses
Technical Field
The present disclosure relates to compositions for forming silicone hydrogel contact lenses and silicone hydrogel contact lenses made from the compositions, and methods of making the compositions or the silicone hydrogel contact lenses.
Background
Contact lenses have been widely used for cosmetic purposes in addition to or separate from vision correction, and the market for cosmetic contact lenses continues to grow. Research efforts have been made to develop new cosmetic contact lenses, which create new products with different physical properties.
US 7,789,507 to Zanini et al describes an ophthalmic lens formed from a reaction mixture comprising: a high molecular weight hydrophilic polymer; an effective amount of a hydroxyl-functionalized silicon-containing monomer; and an amount of polyethylene glycol effective to facilitate release of the lens from the mold part in which the device is formed, wherein the polyethylene glycol comprises one or more of: PEG 2000, mPEG and PEG DME.
Disclosure of Invention
Technical problem
In one embodiment, a composition for making silicone hydrogel contact lenses is provided that exhibits high oxygen permeability (oxygen permeability) and high water content.
In another embodiment, a silicone hydrogel contact lens is provided that exhibits high oxygen permeability and high water content.
In yet another embodiment, methods of preparing compositions for making silicone hydrogel contact lenses and compositions described herein are provided.
Technical proposal
In one embodiment, a silicone hydrogel contact lens comprises a polymer composition prepared by polymerization of a composition for forming a silicone hydrogel contact lens comprising: about 10 to about 40 weight percent of a silicon-containing macromer, about 1 to about 20 weight percent of polyethylene glycol having a molecular weight of about 200g/mol to about 1,000g/mol, and a crosslinking agent or initiator, wherein the polymerization is conducted by thermal polymerization or UV photopolymerization at a temperature of about 100 ℃ to about 110 ℃ in a manner that removes at least about 95% of the polyethylene glycol from the polymer composition.
In one embodiment, a contact lens polymer composition prepared by polymerization of a composition for forming a silicone hydrogel contact lens comprises: about 10 to about 40 weight percent of a silicon-containing macromer, about 1 to about 20 weight percent of polyethylene glycol having a molecular weight of about 200g/mol to about 1,000g/mol, and a crosslinking agent or initiator, wherein the polymerization is conducted by thermal polymerization or UV photopolymerization at a temperature of about 100 ℃ to about 110 ℃ in a manner that removes at least about 95% of the polyethylene glycol from the polymer composition.
In one embodiment, a method of preparing a polymer composition includes polymerizing a composition for forming a silicone hydrogel contact lens comprising from about 10% to about 40% by weight of a silicon-containing macromer, from about 1% to about 20% by weight of polyethylene glycol having a molecular weight of from about 200g/mol to about 1,000g/mol, and a crosslinking agent or initiator, wherein the polymerization is conducted by thermal polymerization or UV photopolymerization at a temperature of from about 100 ℃ to about 110 ℃ to remove at least about 95% of the polyethylene glycol from the polymer composition.
The present disclosure is not limited to the above embodiments and includes other objects and advantages not mentioned. The present disclosure will be more clearly understood by embodiments thereof.
Additional aspects will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the presented embodiments.
Advantageous effects
In one embodiment, a composition for making silicone hydrogel contact lenses is provided that exhibits high oxygen permeability and high water content.
Detailed Description
Hereinafter, embodiments of the present disclosure will be described in detail in such a manner that one of ordinary skill in the art to which the present disclosure pertains can easily implement the present disclosure. The present disclosure may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
The cornea receives oxygen when in contact with oxygen dissolved in tears and oxygen in the air, while a contact lens located on the cornea can be a barrier to oxygen delivery. Thus, the oxygen permeability of contact lenses is an important consideration in developing new contact lenses, especially for improving eye health.
Furthermore, in the case of contact lens materials, a composition comprising a mixture of an initiator and a plurality of monomers is injected into a mold and then polymerized while a crosslinking reaction occurs by instantaneous energy. The polymeric material resulting from the polymerization reaction acts in the lens and the characteristics of the contact lens, such as refractive index, mechanical strength, wettability and oxygen permeability, are determined by the ingredients of the composition.
Definition of the definition
The term "hydrogel" as used herein refers to a crosslinked polymeric material that can hold at least 10% or more by weight of water in the matrix of the crosslinked polymer upon hydration.
The term "silicon-containing macromer" as used herein refers to a macromer having a weight average molecular weight of 500Da or greater as a monomer containing silicon and having an ethylenically unsaturated group.
As used in this specification, polyethylene glycol is of the formula H- (O-CH) 2 -CH 2 ) n -OH, wherein, typically, n has a value of 4 or greater.
The term "hydrophilic monomer" as used herein refers to monomers that: which has a polymerizable functional group such as an alkylene or acryl group and a hydrophilic functional group such as a hydroxyl, amine or pyrrolidone and has a molecular weight of less than 500 Da.
The term "silicon-containing monomer" as used herein refers to a monomer having a weight average molecular weight of less than 500Da that is a monomer containing silicon and having an ethylenically unsaturated group.
Silicone hydrogel contact lenses and polymer compositions
The present disclosure provides silicone hydrogel contact lenses comprising a polymer composition prepared by polymerization of a composition for forming a silicone hydrogel contact lens comprising: about 10 to about 40 weight percent of a silicon-containing macromer, about 1 to about 20 weight percent of polyethylene glycol having a molecular weight of about 200g/mol to about 1,000g/mol, and a crosslinking agent or initiator, wherein the polymerization is conducted by thermal polymerization or UV photopolymerization at a temperature of about 100 ℃ to about 110 ℃ in a manner that removes at least about 95% of the polyethylene glycol from the polymer composition.
The polyethylene glycol used in the silicone hydrogel contact lens-forming composition can be any PEG having a molecular weight of from about 200g/mol to about 1,000 g/mol. For the preparation of silicone hydrogel contact lenses, it is undesirable to use polyethylene glycols of high molecular weight (e.g., 2,000g/mol to 6,000 g/mol). Such high molecular weight PEG cannot be sufficiently removed from the composition during polymerization, and the resulting polymer cannot achieve desired characteristics such as high oxygen permeability and high water content. In one embodiment, the polyethylene glycol is selected from the group consisting of PEG 200, PEG 300, PEG 400, PEG 600, PEG 800, and PEG 1000. In a particular embodiment, the polyethylene glycol is PEG 200, PEG 400, or PEG 1000.
The polymer composition is prepared by polymerizing a composition for forming a silicone hydrogel contact lens. In one embodiment, the polymerization reaction is carried out by thermal polymerization at a temperature of about 100 ℃ to about 110 ℃. In another embodiment, the polymerization is carried out by UV photopolymerization.
In various embodiments, the polymerization step is performed in a manner that removes at least about 95% of the polyethylene glycol from the polymer composition. Here, the% removal of polyethylene glycol is measured based on the initial amount of polyethylene glycol contained in the composition prior to polymerization; in other words, PEG removal% = 100-remaining amount of PEG after polymerization/amount of PEG before polymerization x 100%. In some embodiments, the polymerization reaction is conducted to remove about 95%, 96%, or 97% of the polyethylene glycol from the composition.
In some embodiments, the silicone hydrogel contact lens has a moisture content of about 40% to about 65%. In various embodiments, the silicone hydrogel contact lens has a moisture content of about 40%, about 45%, about 50%, about 55%, about 60%, or about 65%.
In some embodiments, the silicone hydrogel contact lens has an oxygen permeability (Dk) of about 70 to about 120. In various embodiments, the silicone hydrogel contact lens has an oxygen permeability (Dk) of about 70, about 75, about 80, about 85, about 90, about 95, about 100, about 105, about 110, about 115, or about 120.
In some embodiments, a composition for forming a silicone hydrogel contact lens comprises:
from about 10% to about 40% by weight of a silicon-containing macromer,
about 1% to about 20% by weight of polyethylene glycol,
from about 10% to about 50% by weight of hydrophilic monomers,
about 10 to about 20 weight percent of a silicon-containing monomer, and
a crosslinking agent or an initiator.
The silicone hydrogel contact lenses described herein have a variety of improved characteristics, including improvements in both oxygen permeability and water content.
The morphology of the silicone hydrogel contact lens (which can be determined by adjusting the compatibility between monomers) can affect the physical properties of the silicone hydrogel contact lens while helping in terms of production efficiency and quality stability. The compatibility between monomers can be calculated by thermodynamic energy differences such as Flory-huggins. For more accurate calculation, compatibility can be calculated using three factors: dispersion, polarity, and hydrogen bonding, which may further increase the accuracy of the compatibility calculation. Thus, hansen solubility parameters have been used as tools for predicting compatibility.
Polymers containing silicon are known to have high oxygen permeability, and contact lenses made from silicone materials generally have high oxygen permeability. However, such contact lenses typically have a low water content due to the hydrophobic nature of the polymeric material. When the amount of hydrophilic monomer in the polymer is increased to increase the water content, the oxygen permeability is again reduced. Thus, conventional contact lenses using silicone materials exhibit a tradeoff relationship between oxygen permeability and moisture content. In other words, it is difficult to manufacture contact lenses that satisfy both high oxygen permeability and high water content.
Silicone hydrogel contact lenses of the present disclosure are prepared by polymerizing silicon-containing macromers, but still exhibit both satisfactory oxygen permeability and moisture content.
In one embodiment, a composition for forming a silicone hydrogel contact lens comprises a silicon-containing macromer and polyethylene glycol, wherein differences Δδd, Δδp, and Δδh between hansen solubility parameters of the silicon-containing macromer and the polyethylene glycol that determine hansen solubility parameters satisfy the following conditions:
-6.0MPa 1/2 ≤ΔδD≤1.0MPa 1/2 ；
1.5MPa 1/2 ≤ΔδP≤3.5MPa 1/2 the method comprises the steps of carrying out a first treatment on the surface of the And
4.0MPa 1/2 ≤ΔδH≤8.0MPa 1/2 。
a silicone hydrogel contact lens according to one embodiment of the present disclosure comprises a polymer obtained by polymerizing a composition for forming a silicone hydrogel contact lens, the composition comprising a silicon-containing macromer and polyethylene glycol, wherein differences Δδd, Δδp, and Δδh between hansen solubility parameters of the silicon-containing macromer and the polyethylene glycol, determining hansen solubility parameters, of a dispersive force (δd), a dipole attractive force (δp), and a hydrogen bonding force (δh), satisfy the following conditions:
-6.0MPa 1/2 ≤ΔδD≤1.0MPa 1/2 ；
1.5MPa 1/2 ≤ΔδP≤3.5MPa 1/2 the method comprises the steps of carrying out a first treatment on the surface of the And
4.0MPa 1/2 ≤ΔδH≤8.0MPa 1/2 。
polyethylene glycol is used as a processing aid during polymerization of silicone hydrogel contact lenses and thus acts such as dispersing, tackifying, and highly hardening depending on the type of material used to form the polymer. In addition, polyethylene glycol can greatly affect the characteristics of polymers formed according to the composition ratio of the composition. The radius of gyration and the size of the non-reactive polyethylene glycol vary from the beginning of the reaction depending on the compatibility with other components of the composition and, therefore, the compatibility between the polyethylene glycol and the polymer may vary. Subsequently, the non-reactive polyethylene glycol escapes through the hydration process and remains formed into a structure having a specific size and molecular arrangement through the radius of gyration. The structure formed by the radius of gyration affects the physical properties of the contact lens.
Thus, in compositions for forming silicone hydrogel contact lenses, polyethylene glycol participates in controlling the physical properties of the hydrogel by controlling the solubility of the silicon-containing macromer relative to the polyethylene glycol. Thus, silicone hydrogel contact lenses can achieve high oxygen permeability and high water content. The solubility of the silicon-containing macromer with respect to polyethylene glycol is controlled such that three controlling factors for determining hansen solubility parameters, namely, dispersion force (δd), dipole attraction force (δp), and hydrogen bonding force (δh), satisfy the above-described ranges.
Specifically, when the compatibility of polyethylene glycol with a polymer formed during polymerization of a composition for forming a silicone hydrogel contact lens is reduced, the polyethylene glycol undergoes phase separation, and after completion of the polymerization reaction, the polyethylene glycol is separated during hydration to form voids in the chains of the polymer, and these voids are filled with water, thereby achieving a high water content.
Polyethylene glycol is used to provide hydration sites that determine the water content by allowing the solubility between the silicon-containing macromer and polyethylene glycol to meet hansen solubility parameter conditions.
Accordingly, whereas existing silicone hydrogel contact lenses are made from polymers based on silicon-containing macromers, silicone hydrogel contact lenses have high oxygen permeability. Furthermore, as described above, the use of polyethylene glycol in the polymerization to increase the water content, silicone hydrogel contact lenses can achieve both high oxygen permeability and high water content.
Hansen solubility parameters (Hansen solubility parameter, HSP) consist of three parameters representing forces acting between molecules of a substance (dispersion force (δd), dipole attraction force (δp) and hydrogen bonding force (δh)) and can be calculated according to the method proposed by Charles Hansen in the literature entitled "Hansen Solubility Pa-rameters: a User's Handbook," second edition (2007) Boca Raton, fla.: CRC press ISBN 978-O-8493-7248-3.
The dispersive forces (δd) quantify the energy of the dispersive forces between molecules (i.e. van der waals forces), the dipole attraction (δp) represents the energy of the intermolecular dipole interactions, and the hydrogen bonding forces (δh) quantify the energy derived from the intermolecular hydrogen bonding, i.e. the ability to interact through hydrogen bonding.
Hansen Solubility Parameters (HSP) are vectors expressed as (δd, δp, δh), and are expressed by drawing with coordinate axes representing three parameters in a three-dimensional space (hansen space). Since there is a known information source such as a database of Hansen Solubility Parameters (HSP) of a general material, for example, the database can be referred to for obtaining Hansen Solubility Parameters (HSP) of a desired material. For materials whose Hansen Solubility Parameters (HSPs) are not registered in the database, hansen Solubility Parameters (HSPs) may be calculated from the chemical structure of the substance or by hansen solubility methods using computer program software such as Hansen Solubility Parameters in Practice (hsppi). Specifically, hansen solubility parameters for silicon-containing macromers can be calculated according to the Y-BM group contribution method (Y-BM Group Contribution method), and in the same manner, solubility parameters for other components of a composition for forming a silicone hydrogel contact lens (e.g., other single molecules such as polyethylene glycol, polymers, etc.) can be calculated and used.
In order to control the solubility of the silicon-containing macromer with respect to polyethylene glycol, i.e., in order for three parameters used to determine hansen solubility parameters, namely, dispersion force (δd), dipole attraction force (δp), and hydrogen bonding force (δh), to satisfy the following conditions: -6.0MPa 1/2 ≤ΔδD≤1.0MPa 1/2 ；1.5MPa 1/2 ≤ΔδP≤3.5MPa 1/2 The method comprises the steps of carrying out a first treatment on the surface of the 4.0MPa 1/2 ≤ΔδH≤8.0MPa 1 /2 The variables affecting the values of the dispersion force (δd), the dipole attraction force (δp), and the hydrogen bonding force (δh) can be controlled. For example, variables such as the formulation of the components and the amounts of the components, the structure and molecular weight of the silicon-containing macromer, and the molecular weight and content of polyethylene glycol of the compositions used to form silicone hydrogel contact lenses can complexly affect the conditions described above. Thus, the compositions for forming silicone hydrogel contact lenses can be designed to meet the above conditions by controlling these as variables.
In a silicone hydrogel contact lens according to another embodiment of the present invention, differences Δδd, Δδp, and Δδh between hansen solubility parameters of a silicon-containing macromer and polyethylene glycol, determining hansen solubility parameters, Δδd, dipolar attractive force (δp), and hydrogen bonding force (δh), may satisfy the following ranges:
-0.8MPa 1/2 ≤ΔδD≤0.3MPa 1/2 ；
2.0MPa 1/2 ≤ΔδP≤2.5MPa 1/2 the method comprises the steps of carrying out a first treatment on the surface of the And
4.5MPa 1/2 ≤ΔδH≤5.7MPa 1/2 。
in one embodiment, the silicon-containing macromer comprises at least a plurality of siloxane repeating units [ -Si-O- ], and comprises one or two acrylic functional groups.
In one embodiment, the weight average molecular weight of the silicon-containing macromer may be in the range of about 500Da to about 2,500 Da.
Specific examples of silicon-containing macromers include, but are not limited to: methacryloxypropyl tris (trimethylsiloxy) silane, monomethacryloxyalkyl-terminated polydimethylsiloxane, 3- { α - (trimethylsilyl) poly [ (oxo (dimethylsilylene) ] } propyl 2-methylpropan-2-enoate, monobutyl-terminated polydimethylsiloxane, methacryloxypropyl-terminated polydimethylsiloxane, monovinyl-terminated polydimethylsiloxane, bis (divinyl) -terminated polydimethylsiloxane, α -monovinyl-monophenyl- Ω -monohydride-terminated polymethylsiloxane, and the silicon-containing macromer may comprise at least one of these materials.
In one embodiment, the silicon-containing macromer may comprise at least one selected from the group consisting of a compound represented by the following formula 1, a compound represented by the following formula 2, a compound represented by the following formula 3, a compound represented by the following formula 4, and a combination thereof.
< 1>
Wherein, in the formula 1,
a is an integer from 1 to 30, b is an integer from 1 to 30, and c is an integer from 5 to 30, R 1 To R 4 Each independently is hydrogen or C1-C6 alkyl, and
R 5 is C1-C8 alkyl, tri (C1-C8) alkylsiloxy, phenyl, naphthyl, substituted C1-C8 alkyl, substituted phenyl, or substituted naphthyl, wherein the substituents of the alkyl groups are at least one selected from the group consisting of C1-C8 alkoxycarbonyl, C1-C8 alkyl, C1-C8 alkoxy, amide, halogen, hydroxy, carboxyl, C1-C8 alkylcarbonyl, and formyl, and the substituents of the phenyl and naphthyl groups are each selected fromFrom at least one of C1-C8 alkoxycarbonyl, C1-C8 alkyl, C1-C8 alkoxy, amide, halogen, hydroxy, carboxyl, C1-C8 alkylcarbonyl and formyl.
< 2>
Wherein, in the formula 2,
a is an integer from 1 to 27, and b is an integer from 3 to 27,
R 1 and R is 2 Each independently is hydrogen or C1-C8 alkyl, and
R 3 and R is 4 Each independently is hydrogen, C1-C6 alkyl, tri (C1-C6) alkylsiloxy, phenyl, naphthyl, substituted C1-C6 alkyl, substituted phenyl, or substituted naphthyl, wherein the substituent of the alkyl group is at least one selected from the group consisting of C1-C6 alkoxycarbonyl, C1-C6 alkyl, C1-C6 alkoxy, amide, halogen, hydroxy, carboxyl, C1-C6 alkylcarbonyl, and formyl, and the substituents of the phenyl and naphthyl groups are each at least one selected from the group consisting of C1-C6 alkoxycarbonyl, C1-C6 alkyl, C1-C6 alkoxy, amide, halogen, hydroxy, carboxyl, C1-C6 alkylcarbonyl, and formyl.
< 3>
Wherein, in the formula 3,
a is an integer from 1 to 27, and b is an integer from 3 to 27,
R 1 and R is 2 Each independently is hydrogen or C1-C8 alkyl, and
R 3 and R is 4 Each independently is hydrogen, C1-C6 alkyl, tri (C1-C6) alkylsiloxy, phenyl, naphthyl, substituted C1-C6 alkyl, substituted phenyl, or substituted naphthyl, wherein the substituents of the alkyl groups are selected from C1-C6 alkoxycarbonyl, C1-C6 alkyl, C1-C6 alkoxy, amide, halogen, hydroxyThe substituents of the group, carboxyl group, at least one of C1-C6 alkylcarbonyl and formyl group, and phenyl and naphthyl group are each at least one selected from C1-C6 alkoxycarbonyl, C1-C6 alkyl, C1-C6 alkoxy, amide, halogen, hydroxyl, carboxyl, C1-C6 alkylcarbonyl and formyl.
< 4>
Wherein, in the formula 4,
a is an integer from 1 to 8, and b is an integer from 3 to 10,
R 1 to R 4 Each independently is hydrogen or C1-C6 alkyl, and
R 5 is C1-C8 alkyl, tri (C1-C8) alkylsilyloxy, phenyl, naphthyl, substituted C1-C8 alkyl, substituted phenyl, or substituted naphthyl, wherein the substituent of the alkyl group is at least one selected from the group consisting of C1-C8 alkoxycarbonyl, C1-C8 alkyl, C1-C8 alkoxy, amide, halogen, hydroxy, carboxy, C1-C8 alkylcarbonyl, and formyl, and the substituents of the phenyl and naphthyl groups are each at least one selected from the group consisting of C1-C8 alkoxycarbonyl, C1-C8 alkyl, C1-C8 alkoxy, amide, halogen, hydroxy, carboxy, C1-C8 alkylcarbonyl, and formyl.
The type and amount of silicon-containing macromer can be freely determined within the range that satisfies hansen solubility parameters relative to polyethylene glycol.
The composition for forming a silicone hydrogel contact lens can comprise from about 21% to about 48% by weight of a silicon-containing macromer.
In one embodiment, the polyethylene glycol may have a weight average molecular weight in the range of about 200g/mol to about 1000 g/mol.
The amount of polyethylene glycol may be varied in accordance with the relationship with the silicon-containing macromer to meet hansen solubility parameter conditions relative to the macromer. For example, the composition for forming a silicone hydrogel contact lens can comprise about 4 parts by weight to about 96 parts by weight polyethylene glycol relative to 100 parts by weight of the silicon-containing macromer.
The type, molecular weight, content, etc. of polyethylene glycol can be freely determined within a range satisfying hansen solubility parameter conditions with respect to the silicon-containing macromer.
The physical characteristics of the final product (i.e., contact lens) are determined by how the composition of the components of the composition used to form the silicone hydrogel contact lens is designed. Three main factors, namely moisture content, oxygen permeability and durability, need to be considered in designing the physical properties of a contact lens, but other useful factors may be present. In this regard, in the case of durability, strength, elongation, and young's modulus may be different. In view of the physical characteristics of such contact lenses, the composition for forming a silicone hydrogel contact lens may also comprise other components in addition to the silicon-containing macromer and polyethylene glycol, so long as the composition meets predetermined hansen solubility parameter conditions.
In one embodiment, the composition for forming a silicone hydrogel contact lens can further comprise a hydrophilic monomer.
Hydrophilic monomers participate in free radical polymerization of compositions used to form silicone hydrogel contact lenses and structural units based on hydrophilic monomers are included in the polymer. The silicon-containing macromer and the hydrophilic monomer are polymerized by polymerization via free radical reactions initiated by heat or light to form a polymer.
The hydrophilic monomer may be, but is not limited to, for example, N-dimethylacrylamide, 2-hydroxyethyl methacrylate, glycerol monomethacrylate, 2-hydroxyethyl methacrylamide, polyethylene glycol monomethacrylate, methacrylic acid, acrylic acid, N-vinylpyrrolidone, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, and N-vinylformamide, and may contain at least one of these materials.
In one embodiment, the composition for forming a silicone hydrogel contact lens can comprise about 20 parts by weight to about 239 parts by weight hydrophilic monomer relative to 100 parts by weight silicon-containing macromer. In comparison to commercially available contact lenses, the compositions for forming silicone hydrogel contact lenses can achieve contact lenses having high moisture content while containing a non-relatively large amount of hydrophilic monomers within the above-described ranges.
In one embodiment, the composition for forming a silicone hydrogel contact lens can further comprise a silicon-containing monomer and a crosslinking agent.
In one embodiment, the silicon-containing monomer comprises at least a plurality of siloxane repeating units [ -Si-O- ], and comprises one or two acrylic functional groups.
The silicon-containing monomer has a weight average molecular weight of less than 500Da, is not a macromer, and is different from the silicon-containing macromer.
The silicon-containing monomer may be, but is not limited to, for example, alpha, omega-bis-methacryloxypropyl polydimethylsiloxane (SiGMA), 3-methacryloxypropyl TRIS (trimethylsiloxy) silane (TRIS), mono-methacryloxypropyl terminated polydimethylsiloxane, 3-methacryloxypropyl bis (trimethylsiloxy) methylsilane, and methacryloxypropyl pentamethyldisiloxane, and may comprise at least one of these materials.
In one embodiment, the composition for forming a silicone hydrogel contact lens can comprise about 23 parts by weight to about 143 parts by weight relative to 100 parts by weight of the silicon-containing macromer.
In one embodiment, the composition for forming a silicone hydrogel contact lens can further comprise a crosslinking agent.
The crosslinking agent may be, but is not limited to, for example, allyl Methacrylate (AMA), divinylbenzene (DVB), triethylene glycol dimethacrylate (TrEGDMA), triallyl isocyanurate (TAIC), ethylene Glycol Dimethacrylate (EGDMA), ethylenediamine dimethacrylate, and glycerol dimethacrylate, and may contain at least one of these materials.
In one embodiment, the composition for forming a silicone hydrogel contact lens can comprise about 1 to about 38 parts by weight of a crosslinker relative to 100 parts by weight of a silicon-containing macromer.
In one embodiment, the composition for forming a silicone hydrogel contact lens may further comprise an initiator. The initiator may be a thermal initiator or a photoinitiator that initiates a radical reaction by heat or light, such as infrared or ultraviolet light.
The initiator may comprise, for example, a compound such as lauryl peroxide, benzoyl peroxide, isopropyl percarbonate, or azobisisobutyronitrile, or a photoinitiator such as aromatic alpha-hydroxy ketone, alkoxybenzoin (alkoxoxybenzoin), acetophenone, t-butyl peroxyneodecanoate (tert-butyl peroxineadecanoate), acyl phosphine oxide, tertiary amine, diketone, or mixtures thereof. Examples of the photoinitiator may include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bis (2, 6-dimethoxybenzoyl) -2, 4-trimethylpentylphosphine oxide (DMBAPO), bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819), 2,4, 6-trimethylbenzyl diphenylphosphine oxide, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, benzoin methyl ester, camphorquinone, and ethyl 4- (N, N-dimethylamino) benzoate, and the photoinitiator may be used alone, or a combination of these materials may be used. Examples of commercially available visible light photoinitiators may include, but are not limited to, irgacure 819, irgacure 1700, irgacure 1800, irgacure 819, irgacure 1850 (manufacturer: ciba Specialty Chemicals), and Lucirin TPO initiators, and may include at least one of these materials.
In one embodiment, the composition for forming a silicone hydrogel contact lens can comprise about 1 to about 38 parts by weight of initiator relative to 100 parts by weight of the silicon-containing macromer.
In one embodiment, the composition for forming a silicone hydrogel contact lens may further comprise materials known as additives, such as UV blockers, pigments, antioxidants, plasticizers, wetting agents, lubricants, viscosity reducing agents, and compatibility enhancers, which may be added to the composition for making a contact lens.
The composition for forming a silicone hydrogel contact lens can be used to make a silicone hydrogel contact lens by generally known methods for making contact lenses.
For example, the composition for forming a silicone hydrogel contact lens obtained by mixing as described in detail above is injected into a mold, a lens is formed by polymerization using heat or light such as ultraviolet rays or infrared rays, and then the dried lens is separated from the mold and subjected to a hydration process, thereby completing the manufacture of the silicone hydrogel contact lens.
Silicone hydrogel contact lenses made using the composition for forming silicone hydrogel contact lenses as described in detail above exhibit physical properties that satisfy both high oxygen permeability and high water content.
In one embodiment, the silicone hydrogel contact lens has a moisture content of about 50% to about 60% and an oxygen permeability (Dk) of about 80 to about 120.
As noted above, it is desirable to properly formulate compositions for forming silicone hydrogel contact lenses to achieve the desired physical characteristics of the contact lenses to be manufactured. Thus, silicone hydrogel contact lenses having desirable durability such as strength, elongation and young's modulus, and improved moisture content and oxygen permeability can be obtained.
In one embodiment, the silicone hydrogel contact lens has a tensile strength of about 6kgf/mm 2 To about 8kgf/mm 2 . In one embodiment, the silicone hydrogel contact lens has an elongation of about 150% to about 200%. In one embodiment, the silicone hydrogel contact lens has a tensile modulus of about 0.3kgf/mm 2 To about 0.8kgf/mm 2 . In one embodiment, the silicone hydrogel contact lens has an oxygen permeability of about 80 x 10 -11 (cm 2 Per second) [ ml O 2 /(ml·mmHg)]To about 115X 10 -11 (cm 2 Per second) [ ml O 2 /(ml·mmHg)]. In one embodiment, the silicone hydrogel contact lens has a moisture content of about 50% to about 55%.
In some embodiments, various lens compositions prepared according to the description herein are provided, and non-limiting examples of such compositions include: (1) A composition comprising about 100 parts by weight of a silicon-containing macromer of formula 11, about 95 parts by weight of PEG 200, about 162 parts by weight of a hydrophilic monomer, about 108 parts by weight of a silicon-containing monomer, about 5 parts by weight of a crosslinker, and about 5 parts by weight of an initiator; (2) A composition comprising about 38 parts by weight of a silicon-containing macromer of formula 11, about 62 parts by weight of a silicon-containing macromer of formula 12, about 83 parts by weight of PEG 200, about 135 parts by weight of a hydrophilic monomer, about 90 parts by weight of a silicon-containing monomer, about 4 parts by weight of a crosslinking agent, and about 4 parts by weight of an initiator; (3) A composition comprising about 100 parts by weight of a silicon-containing macromer of formula 13, about 83 parts by weight of PEG 200, about 135 parts by weight of a hydrophilic monomer, about 90 parts by weight of a silicon-containing monomer, about 4 parts by weight of a cross-linking agent, and about 4 parts by weight of an initiator; (4) A composition comprising about 97 parts by weight of a silicon-containing macromer of formula 11, about 3 parts by weight of a silicon-containing macromer of formula 12, about 6 parts by weight of PEG 400, about 114 parts by weight of a hydrophilic monomer, about 76 parts by weight of a silicon-containing monomer, about 4 parts by weight of a crosslinking agent, and about 4 parts by weight of an initiator; (5) A composition comprising about 3 parts by weight of a silicon-containing macromer of formula 12, about 97 parts by weight of a silicon-containing macromer of formula 13, about 6 parts by weight of PEG 400, about 114 parts by weight of a hydrophilic monomer, about 76 parts by weight of a silicon-containing monomer, about 4 parts by weight of a crosslinking agent, and about 4 parts by weight of an initiator; (6) A composition comprising about 100 parts by weight of a silicon-containing macromer of formula 13, about 6 parts by weight of PEG 400, about 114 parts by weight of a hydrophilic monomer, about 76 parts by weight of a silicon-containing monomer, about 4 parts by weight of a crosslinker, and about 4 parts by weight of an initiator; (7) A composition comprising about 100 parts by weight of a silicon-containing macromer of formula 14, about 28 parts by weight of PEG 400, about 87 parts by weight of a hydrophilic monomer, about 58 parts by weight of a silicon-containing monomer, about 3 parts by weight of a crosslinker, and about 3 parts by weight of an initiator; (8) A composition comprising about 78 parts by weight of a silicon-containing macromer of formula 11, about 22 parts by weight of a silicon-containing macromer of formula 15, about 28 parts by weight of PEG 400, about 87 parts by weight of a hydrophilic monomer, about 58 parts by weight of a silicon-containing monomer, about 3 parts by weight of a crosslinking agent, and about 3 parts by weight of an initiator; (9) A composition comprising about 25 parts by weight of a silicon-containing macromer of formula 14, about 75 parts by weight of a silicon-containing macromer of formula 16, about 95 parts by weight of PEG 400, about 162 parts by weight of a hydrophilic monomer, about 108 parts by weight of a silicon-containing monomer, about 5 parts by weight of a crosslinking agent, and about 5 parts by weight of an initiator; (10) A composition comprising about 25 parts by weight of a silicon-containing macromer of formula 14, about 75 parts by weight of a silicon-containing macromer of formula 17, about 83 parts by weight of PEG 1000, about 135 parts by weight of a hydrophilic monomer, about 90 parts by weight of a silicon-containing monomer, about 4 parts by weight of a crosslinking agent, and about 4 parts by weight of an initiator; (11) A composition comprising about 3 parts by weight of a silicon-containing macromer of formula 15, about 97 parts by weight of a silicon-containing macromer of formula 18, about 95 parts by weight of PEG 1000, about 162 parts by weight of a hydrophilic monomer, about 108 parts by weight of a silicon-containing monomer, about 5 parts by weight of a crosslinking agent, and about 5 parts by weight of an initiator; (12) A composition comprising about 97 parts by weight of a silicon-containing macromer of formula 18, about 3 parts by weight of a silicon-containing macromer of formula 19, about 95 parts by weight of PEG 1000, about 162 parts by weight of a hydrophilic monomer, about 108 parts by weight of a silicon-containing monomer, about 5 parts by weight of a crosslinking agent, and about 5 parts by weight of an initiator; and (13) a composition comprising about 62 parts by weight of a silicon-containing macromer of formula 18, about 38 parts by weight of a silicon-containing macromer of formula 20, about 95 parts by weight of PEG 1000, about 162 parts by weight of a hydrophilic monomer, about 108 parts by weight of a silicon-containing monomer, about 5 parts by weight of a crosslinking agent, and about 5 parts by weight of an initiator. In various embodiments, the hydrophilic monomer is N-vinyl-2-pyrrolidone (NVP); the cross-linking agent is tri (glycol) dimethacrylate) (TEGDMA); the silicon-containing monomer is alpha, omega-dimethyl acryloxypropyl polydimethylsiloxane (SiGMA); and the initiator is 2,2' -Azobisisobutyronitrile (AIBN).
Hereinafter, examples and comparative examples of the present disclosure will be described. The following examples are merely embodiments of the present disclosure and are not intended to limit the present disclosure.
Examples
Example 1
100 parts by weight of a compound represented by the following formula 11 (weight average molecular weight: 1,000 Da) as a silicon-containing macromer, 162 parts by weight of N-vinyl-2-pyrrolidone (NVP) as a hydrophilic monomer, 95 parts by weight of polyethylene glycol (weight average molecular weight: 200 Da), 5 parts by weight of tri (ethylene glycol) dimethacrylate (TEGDMA) as a crosslinking agent, α, ω -bismethacryloxypropyl polydimethylsiloxane (SiGMA) as a silicon-containing monomer, and 2,2' -Azobisisobutyronitrile (AIBN) as a thermal initiator were mixed, thereby completing the preparation of a composition for forming a silicone hydrogel contact lens.
The composition for forming a silicone hydrogel contact lens is injected into a polypropylene mold and polymerized at 110 ℃ to make a lens, and the lens is dried and then separated from the mold. The separated lenses were combined with water in saline and sterilized at 120 ℃ to complete the manufacture of silicone hydrogel contact lenses.
< 11>
Wherein in formula 11, R 1 To R 4 Is methyl, R 5 Butyl, a=1, b=1, and c=15.
Example 2
The compound represented by formula 11 and the compound represented by formula 12 below were mixed in the amounts shown in table 1 below so that the amount of the silicon-containing macromer became 100 parts by weight, and 135 parts by weight of NVP as a hydrophilic monomer, 83 parts by weight of polyethylene glycol (weight average molecular weight of 200 Da), 4 parts by weight of TEGDMA as a crosslinking agent, siGMA as a silicon-containing monomer, and AIBN as a thermal initiator were mixed, thereby completing the preparation of the silicone hydrogel contact lens. Subsequently, a silicone hydrogel contact lens was produced in the same manner as in example 1.
< 12>
Wherein, in formula 12, R 1 To R 4 Methyl, a=1, and b=9.
Example 3
The compound represented by the following formula 13 was used so that the amount of the silicon-containing macromer became 100 parts by weight, and 135 parts by weight of NVP as a hydrophilic monomer, 83 parts by weight of polyethylene glycol (weight average molecular weight of 200 Da), 4 parts by weight of TEGDMA as a crosslinking agent, siGMA as a silicon-containing monomer, and AIBN as a thermal initiator were mixed, thereby completing the preparation of the composition for forming a silicone hydrogel contact lens. Subsequently, a silicone hydrogel contact lens was produced in the same manner as in example 1.
< 13>
Wherein in formula 13, R 1 To R 4 Is methyl, R 5 Butyl, a=3, and b=6.
Example 4
The compound represented by formula 11 and the compound represented by formula 12 were mixed in the amounts shown in the following table 1 so that the amount of the silicon-containing macromer became 100 parts by weight, and 114 parts by weight of NVP as a hydrophilic monomer, 6 parts by weight of polyethylene glycol (weight average molecular weight of 400 Da), 4 parts by weight of TEGDMA as a crosslinking agent, siGMA as a silicon-containing monomer, and AIBN as a thermal initiator were mixed, thereby completing the preparation of the composition for forming a silicone hydrogel contact lens. Subsequently, a silicone hydrogel contact lens was produced in the same manner as in example 1.
Example 5
The compound represented by formula 12 and the compound represented by formula 13 were mixed in the amounts shown in the following table 1 so that the amount of the silicon-containing macromer became 100 parts by weight, and 114 parts by weight of NVP as a hydrophilic monomer, 6 parts by weight of polyethylene glycol (weight average molecular weight of 400 Da), 4 parts by weight of TEGDMA as a crosslinking agent, siGMA as a silicon-containing monomer, and AIBN as a thermal initiator were mixed, thereby completing the preparation of the composition for forming a silicone hydrogel contact lens. Subsequently, a silicone hydrogel contact lens was produced in the same manner as in example 1.
Example 6
The compound represented by formula 13 was used so that the amount of the silicon-containing macromer became 100 parts by weight, and 114 parts by weight of NVP as a hydrophilic monomer, 6 parts by weight of polyethylene glycol (weight average molecular weight of 400 Da), 4 parts by weight of TEGDMA as a crosslinking agent, siGMA as a silicon-containing monomer, and AIBN as a thermal initiator were mixed, thereby completing the preparation of the composition for forming a silicone hydrogel contact lens. Subsequently, a silicone hydrogel contact lens was produced in the same manner as in example 1.
Example 7
The compound represented by the following formula 14 was used so that the amount of the silicon-containing macromer became 100 parts by weight, and 87 parts by weight of NVP as a hydrophilic monomer, 28 parts by weight of polyethylene glycol (weight average molecular weight of 200 Da), 3 parts by weight of TEGDMA as a crosslinking agent, siGMA as a silicon-containing monomer, and AIBN as a thermal initiator were mixed, thereby completing the preparation of the composition for forming a silicone hydrogel contact lens. Subsequently, a silicone hydrogel contact lens was produced in the same manner as in example 1.
< 14>
Wherein in formula 14, R 1 To R 4 Is methyl, R 5 Is a hydroxy-substituted butyl, a=6, and b=18.
Example 8
The compound represented by formula 11 and the compound represented by formula 15 below were mixed in amounts shown in table 1 below so that the amount of the silicon-containing macromer became 100 parts by weight, and 87 parts by weight of NVP as a hydrophilic monomer, 28 parts by weight of polyethylene glycol (weight average molecular weight of 400 Da), 3 parts by weight of TEGDMA as a crosslinking agent, siGMA as a silicon-containing monomer, and AIBN as a thermal initiator were mixed, thereby completing the preparation of the composition for forming a silicone hydrogel contact lens. Subsequently, a silicone hydrogel contact lens was produced in the same manner as in example 1.
< 15>
Wherein in formula 15, R 1 To R 4 Methyl, a=1, and b=9.
Example 9
The compound represented by formula 14 and the compound represented by formula 16 below were mixed in amounts shown in table 1 below so that the amount of the silicon-containing macromer became 100 parts by weight, and 162 parts by weight of NVP as a hydrophilic monomer, 95 parts by weight of polyethylene glycol (weight average molecular weight of 400 Da), 5 parts by weight of TEGDMA as a crosslinking agent, siGMA as a silicon-containing monomer, and AIBN as a thermal initiator were mixed, thereby completing the preparation of the composition for forming a silicone hydrogel contact lens. Subsequently, a silicone hydrogel contact lens was produced in the same manner as in example 1.
< 16>
Wherein, in formula 16, R 1 And R is 2 Is methyl, R 4 And R is 3 Is an amine-substituted methyl group, a=3, and b=13.
Example 10
The compound represented by formula 14 and the compound represented by formula 17 below were mixed in amounts shown in table 1 below so that the amount of the silicon-containing macromer became 100 parts by weight, and 135 parts by weight of NVP as a hydrophilic monomer, 83 parts by weight of polyethylene glycol (weight average molecular weight of 1000 Da), 4 parts by weight of TEGDMA as a crosslinking agent, siGMA as a silicon-containing monomer, and AIBN as a thermal initiator were mixed, thereby completing the preparation of the composition for forming a silicone hydrogel contact lens. Subsequently, a silicone hydrogel contact lens was produced in the same manner as in example 1.
< 17>
Wherein, in formula 17, R 1 To R 4 Is methyl, R 5 Is hexyl substituted with hydroxy, a=6, b=6, and c=20.
Example 11
The compound represented by formula 15 and the compound represented by formula 18 below were mixed in amounts shown in table 1 below so that the amount of the silicon-containing macromer became 100 parts by weight, and 162 parts by weight of NVP as a hydrophilic monomer, 95 parts by weight of polyethylene glycol (weight average molecular weight of 1000 Da), 5 parts by weight of TEGDMA as a crosslinking agent, siGMA as a silicon-containing monomer, and AIBN as a thermal initiator were mixed, thereby completing the preparation of the composition for forming a silicone hydrogel contact lens. Subsequently, a silicone hydrogel contact lens was produced in the same manner as in example 1.
< 18>
Wherein, in formula 18, R 1 To R 4 Is methyl, R 5 Is amide substituted hexyl, a=6, b=6, and c=18.
Example 12
The compound represented by the above formula 18 and the compound represented by the following formula 19 were mixed in amounts shown in table 1 below so that the amount of the silicon-containing macromer became 100 parts by weight, and 162 parts by weight of NVP as a hydrophilic monomer, 95 parts by weight of polyethylene glycol (weight average molecular weight of 1000 Da), 4 parts by weight of TEGDMA as a crosslinking agent, siGMA as a silicon-containing monomer, and AIBN as a thermal initiator were mixed, thereby completing the preparation of the composition for forming a silicone hydrogel contact lens. Subsequently, a silicone hydrogel contact lens was produced in the same manner as in example 1.
< 19>
Wherein in formula 19, R 1 To R 3 Is propyl, R 4 Is methyl substituted with hydroxy, a=6, and b=13.
Example 13
The compound represented by the above formula 18 and the compound represented by the following formula 20 were mixed in amounts shown in table 1 below so that the amount of the silicon-containing macromer became 100 parts by weight, and 162 parts by weight of NVP as a hydrophilic monomer, 95 parts by weight of polyethylene glycol (weight average molecular weight of 1000 Da), 4 parts by weight of TEGDMA as a crosslinking agent, siGMA as a silicon-containing monomer, and AIBN as a thermal initiator were mixed, thereby completing the preparation of the composition for forming a silicone hydrogel contact lens. Subsequently, a silicone hydrogel contact lens was produced in the same manner as in example 1.
< 20>
Wherein in formula 20, R 1 To R 3 Is propyl, R 4 Is methyl substituted with hydroxy, a=3, and b=13.
Comparative example 1
The compound represented by formula 13 was used so that the amount of the silicon-containing macromer became 100 parts by weight, and 114 parts by weight of NVP as a hydrophilic monomer, 6 parts by weight of polyethylene glycol (weight average molecular weight of 200 Da), 4 parts by weight of TEGDMA as a crosslinking agent, siGMA as a silicon-containing monomer, and AIBN as a thermal initiator were mixed, thereby completing the preparation of the composition for forming a silicone hydrogel contact lens. Subsequently, a silicone hydrogel contact lens was produced in the same manner as in example 1.
Comparative example 2
The compound represented by formula 12 and the compound represented by formula 13 were mixed in amounts shown in the following table 2 such that the amount of the silicon-containing macromer became 100 parts by weight, and 212 parts by weight of NVP as a hydrophilic monomer, 10 parts by weight of polyethylene glycol (weight average molecular weight of 400 Da), 7 parts by weight of TEGDMA as a crosslinking agent, siGMA as a silicon-containing monomer, and AIBN as a thermal initiator were mixed, thereby completing the preparation of the composition for forming a silicone hydrogel contact lens. Subsequently, a silicone hydrogel contact lens was produced in the same manner as in example 1.
Comparative example 3
The compound represented by formula 11 was used so that the amount of the silicon-containing macromer became 100 parts by weight, and 212 parts by weight of NVP as a hydrophilic monomer, 10 parts by weight of polyethylene glycol (weight average molecular weight of 400 Da), 7 parts by weight of TEGDMA as a crosslinking agent, siGMA as a silicon-containing monomer, and AIBN as a thermal initiator were mixed, thereby completing the preparation of the composition for forming a silicone hydrogel contact lens. Subsequently, a silicone hydrogel contact lens was produced in the same manner as in example 1.
Comparative example 4
The compound represented by formula 12 was used so that the amount of the silicon-containing macromer became 100 parts by weight, and 45 parts by weight of NVP as a hydrophilic monomer, 44 parts by weight of polyethylene glycol (weight average molecular weight of 1000 Da), 1 part by weight of TEGDMA as a crosslinking agent, siGMA as a silicon-containing monomer, and AIBN as a thermal initiator were mixed, thereby completing the preparation of the composition for forming a silicone hydrogel contact lens. Subsequently, a silicone hydrogel contact lens was produced in the same manner as in example 1.
Comparative example 5
The compound represented by formula 17 was used so that the amount of the silicon-containing macromer became 100 parts by weight, and 45 parts by weight of NVP as a hydrophilic monomer, 44 parts by weight of polyethylene glycol (weight average molecular weight of 1000 Da), 1 part by weight of TEGDMA as a crosslinking agent, siGMA as a silicon-containing monomer, and AIBN as a thermal initiator were mixed, thereby completing the preparation of the composition for forming a silicone hydrogel contact lens. Subsequently, a silicone hydrogel contact lens was produced in the same manner as in example 1.
Comparative example 6
The compound represented by formula 14 and the compound represented by formula 19 were mixed in the amounts shown in the following table 2 so that the amount of the silicon-containing macromer became 100 parts by weight, and 45 parts by weight of NVP as a hydrophilic monomer, 44 parts by weight of polyethylene glycol (weight average molecular weight of 1000 Da), 1 part by weight of TEGDMA as a crosslinking agent, siGMA as a silicon-containing monomer, and AIBN as a thermal initiator were mixed, thereby completing the preparation of the composition for forming a silicone hydrogel contact lens. Subsequently, a silicone hydrogel contact lens was produced in the same manner as in example 1.
Formulations of the compositions for forming silicone hydrogel contact lenses prepared according to examples 1 to 13 and comparative examples 1 to 6 are shown in tables 1 and 2 below.
TABLE 1
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TABLE 2
Evaluation example 1
The dispersion force (δd), dipole attraction force (δp), and hydrogen bonding force (δh) determining hansen solubility parameters of the silicon-containing macromer and polyethylene glycol in each of the compositions of examples 1 to 13 and comparative examples 1 to 6 were calculated using the Y-BM group contribution method, and the differences Δδd, Δδp, and Δδh therebetween were evaluated and are shown in table 3 below.
TABLE 3
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Evaluation example 2
The physical properties of each of the silicone hydrogel contact lenses manufactured according to examples 1 to 13 and comparative examples 1 to 6 were evaluated using the following methods and are shown in table 4.
(evaluation of Strength, elongation and Young's modulus)
Clamps for tensile testing are installed at both ends of the test specimen conforming to ASTM standards. After the installation is completed, a load is applied to the jig at a constant speed, and the mechanical properties of the sample are measured by deformation occurring in the sample. Depending on the characteristics of each specimen, deformation or fracture occurs depending on the applied force, and these are referred to as tensile strain and tensile stress, respectively. The property of tending to return to its original shape upon removal of a load after deformation occurs upon application of the load is called elasticity. The slope over the elastic region may be expressed as Young's modulus. Elongation is defined as epsilon = deltal/L0 as the ratio of the change deltal (change in length of the sample relative to the applied force) to the original mark length L0 of the sample (initial sample length before applying a force to the sample) and is typically expressed as a percentage.
(moisture content)
The water content of each lens was measured using a gravimetric method. Moisture was removed from the surface of the lens to measure weight. The weight is measured after drying at 100 ℃ to 110 ℃ (60 ℃ ±5 ℃ if the lens material is modified) until there is no change in weight. Lenses of 100mg to 300mg were used, and the weight was measured in units of 0.1 mg. The water content (W) was determined using the following expression H2O ) Calculated as a percentage.
( m1: weight of lens before drying, m2: weight of lens after drying )
(oxygen permeability)
The oxygen permeability (Dk) of a lens is represented by a diffusion coefficient (D), which is the ability to pass through a material, and a dissolution coefficient (k), which represents the degree of dissolution of oxygen in the material. In the present invention, oxygen permeability is measured according to ISO 18369 using polarography.
TABLE 4
As can be seen from the results shown in tables 3 and 4, the silicone hydrogel contact lenses of examples 1 to 13, which were determined to satisfy all conditions for determining hansen solubility parameters, had oxygen permeabilities (Dk) of 80 to 120 and achieved water contents of 50% to 60%, meaning that all predetermined criteria were all achieved. It was also determined that the silicone hydrogel contact lenses of examples 1-13 exhibited excellent durability evaluation results with respect to strength, elongation, and young's modulus.
As is apparent from the foregoing description, silicone hydrogel contact lenses according to the present disclosure exhibit higher oxygen permeability and higher moisture content when compared to comparative examples.
In addition to the effects described above, specific effects of the present disclosure will be described when specific details of implementing the disclosure are described.
Although the present disclosure has been described with reference to the embodiments described above, the embodiments set forth herein are not intended to limit the present disclosure, and it is apparent that various modifications can be made by one of ordinary skill in the art within the technical spirit of the present disclosure. Furthermore, although the effect of the configuration according to the present disclosure is not explicitly described in the detailed description of the foregoing embodiments, it is apparent that the predictable effect of the corresponding configuration should also be recognized.

Claims (20)

1. A silicone hydrogel contact lens comprising a polymer composition prepared by polymerization of a composition for forming a silicone hydrogel contact lens, the composition for forming a silicone hydrogel contact lens comprising:
from about 10% to about 40% by weight of a silicon-containing macromer,
about 1 to about 20 weight percent of polyethylene glycol having a molecular weight of about 200g/mol to about 1,000g/mol, and
a cross-linking agent or an initiator,
wherein the polymerization is carried out by thermal polymerization or UV photopolymerization at a temperature of about 100 ℃ to about 110 ℃ to remove at least about 95% of the polyethylene glycol from the polymer composition.
2. The silicone hydrogel contact lens of claim 1 wherein the polyethylene glycol is PEG 200, PEG 400, or PEG 1000.
3. The silicone hydrogel contact lens of claim 1 having a moisture content of from about 40% to about 65% and an oxygen permeability (Dk) of from about 70 to about 120.
4. The silicone hydrogel contact lens of claim 1, wherein the composition for forming a silicone hydrogel contact lens comprises:
from about 10% to about 40% by weight of the silicon-containing macromer,
about 1% to about 20% by weight of said polyethylene glycol,
from about 10% to about 50% by weight of hydrophilic monomers,
about 10 to about 20 weight percent of a silicon-containing monomer, and
a crosslinking agent or an initiator.
5. The silicone hydrogel contact lens of claim 1, wherein the dispersion force (δd), dipole attraction force (δp), and hydrogen bonding force (δh) of the silicone hydrogel contact lens satisfy the following conditions:
-6.0MPa 1/2 ≤ΔδD≤1.0MPa 1/2 ；
1.5MPa 1/2 ≤ΔδP≤3.5MPa 1/2 the method comprises the steps of carrying out a first treatment on the surface of the And
4.0MPa 1/2 ≤ΔδH≤8.0MPa 1/2 。
6. the silicone hydrogel contact lens of claim 1, wherein the silicone hydrogel contact lens has about 6kgf/mm 2 To about 8kgf/mm 2 From about 150% to about 200% elongation, about 0.3kgf/mm 2 To about 0.8kgf/mm 2 And/or a tensile modulus of about 80 x 10 -11 (cm 2 Per second) [ ml O 2 /(ml·mmHg)]To about 115X 10 -11 (cm 2 Per second) [ ml O 2 /(ml·mmHg)]Oxygen permeability of (2).
7. The silicone hydrogel contact lens of claim 1 wherein the silicon-containing macromer comprises a siloxane chain and has one or two acrylic functional groups.
8. The silicone hydrogel contact lens of claim 1 wherein the silicon-containing macromer has a weight average molecular weight of from about 500Da to about 2,500Da.
9. The silicone hydrogel contact lens of claim 1, wherein the composition for forming a silicone hydrogel contact lens comprises from about 21 wt% to about 48 wt% of the silicon-containing macromer.
10. The silicone hydrogel contact lens of claim 1, wherein the composition for forming a silicone hydrogel contact lens further comprises a hydrophilic monomer.
11. The silicone hydrogel contact lens of claim 10 wherein the hydrophilic monomer comprises at least one selected from the group consisting of: n, N-dimethylacrylamide, 2-hydroxyethyl methacrylate, glycerol monomethacrylate, 2-hydroxyethyl methacrylamide, polyethylene glycol monomethacrylate, methacrylic acid, acrylic acid, N-vinylpyrrolidone, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, N-vinylformamide, and combinations thereof.
12. The silicone hydrogel contact lens of claim 1 wherein said composition for forming a silicone hydrogel contact lens comprises from about 20 parts by weight to about 239 parts by weight of said hydrophilic monomer relative to 100 parts by weight of said silicon-containing macromer.
13. The silicone hydrogel contact lens of claim 1, wherein the composition for forming a silicone hydrogel contact lens further comprises a silicon-containing monomer.
14. The silicone hydrogel contact lens of claim 12 wherein the silicon-containing monomer comprises at least one selected from the group consisting of: alpha, omega-bis methacryloxypropyl polydimethylsiloxane (SiGMA), 3-methacryloxypropyl TRIS (trimethylsiloxy) silane (TRIS), mono methacryloxypropyl terminated polydimethylsiloxane, 3-methacryloxypropyl bis (trimethylsiloxy) methylsilane, methacryloxypropyl pentamethyldisiloxane, and combinations thereof.
15. The silicone hydrogel contact lens of claim 1 wherein the crosslinking agent comprises at least one selected from the group consisting of: allyl Methacrylate (AMA), divinylbenzene (DVB), triethylene glycol dimethacrylate (TrEGDMA), triallyl isocyanurate (TAIC), ethylene Glycol Dimethacrylate (EGDMA), ethylenediamine dimethacrylate, glycerol dimethacrylate, and combinations thereof.
16. The silicone hydrogel contact lens of claim 1 wherein the initiator comprises at least one selected from the group consisting of: lauryl peroxide, benzoyl peroxide, isopropyl percarbonate, azobisisobutyronitrile, aromatic alpha-hydroxy ketone, alkoxyoxybenzoin, acetophenone, t-butyl peroxyneodecanoate, acylphosphine oxide, tertiary amine, diketone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bis (2, 6-dimethoxybenzoyl) -2, 4-trimethylpentylphosphine oxide (DMBAPO), bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2,4, 6-trimethylbenzyl diphenyl phosphine oxide, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, benzoin methyl ester, camphorquinone, ethyl 4- (N, N-dimethylamino) benzoate, irgacure 819, irgacure 1800, irgacure 819, irgacure 1850, lucin initiator, and combinations thereof.
17. The silicone hydrogel contact lens of claim 1, wherein the composition for forming a silicone hydrogel contact lens further comprises at least one selected from the group consisting of UV blockers, pigments, diluents, and combinations thereof.
18. The silicone hydrogel contact lens of claim 1, which satisfies the following conditions:
-0.8MPa 1/2 ≤ΔδD≤0.3MPa 1/2 ；
2.0MPa 1/2 ≤ΔδP≤2.5MPa 1/2 The method comprises the steps of carrying out a first treatment on the surface of the And
4.5MPa 1/2 ≤ΔδH≤5.7MPa 1/2 。
19. a contact lens polymer composition prepared by polymerizing a composition for forming a silicone hydrogel contact lens, comprising:
from about 10% to about 40% by weight of a silicon-containing macromer,
about 1 to about 20 weight percent of polyethylene glycol having a molecular weight of about 200g/mol to about 1,000g/mol, and
a cross-linking agent or an initiator,
wherein the polymerization is carried out by thermal polymerization or UV photopolymerization at a temperature of about 100 ℃ to about 110 ℃ in a manner to remove at least about 95% of the polyethylene glycol from the polymer composition.
20. A method of preparing a polymer composition, the method comprising: polymerizing a silicone hydrogel contact lens-forming composition comprising from about 10% to about 40% by weight of a silicon-containing macromer, from about 1% to about 20% by weight of polyethylene glycol having a molecular weight of from about 200g/mol to about 1,000g/mol, and a crosslinking agent or initiator,
wherein the polymerization is carried out by thermal polymerization or UV photopolymerization at a temperature of about 100 ℃ to about 110 ℃ to remove at least about 95% of the polyethylene glycol from the polymer composition.
CN202280011336.0A 2022-05-20 2022-10-26 Silicone hydrogel contact lenses Pending CN117460782A (en)

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KR10-2022-0062008 2022-05-20
KR1020220079708A KR20240003019A (en) 2022-06-29 2022-06-29 Silicone hydrogel contact lenses
KR10-2022-0079708 2022-06-29
PCT/KR2022/016455 WO2023224184A1 (en) 2022-05-20 2022-10-26 Silicone hydrogel contact lenses

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