WO2023020346A1 - 隐形眼镜及其制造方法 - Google Patents

隐形眼镜及其制造方法 Download PDF

Info

Publication number
WO2023020346A1
WO2023020346A1 PCT/CN2022/111380 CN2022111380W WO2023020346A1 WO 2023020346 A1 WO2023020346 A1 WO 2023020346A1 CN 2022111380 W CN2022111380 W CN 2022111380W WO 2023020346 A1 WO2023020346 A1 WO 2023020346A1
Authority
WO
WIPO (PCT)
Prior art keywords
contact lens
groups
ions
solution
group
Prior art date
Application number
PCT/CN2022/111380
Other languages
English (en)
French (fr)
Inventor
邱显庭
林奕宏
黄盈蓁
Original Assignee
晶硕光学股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 晶硕光学股份有限公司 filed Critical 晶硕光学股份有限公司
Publication of WO2023020346A1 publication Critical patent/WO2023020346A1/zh

Links

Images

Classifications

    • 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/10—Filters, e.g. for facilitating adaptation of the eyes to the dark; Sunglasses
    • G02C7/108—Colouring materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals

Definitions

  • the present disclosure is about contact lenses and methods of making the same. More specifically, the present disclosure relates to contact lenses with blue light blocking capabilities and methods of making the same.
  • DES digital eye strain
  • contact lenses that block specific wavelengths of blue light and have enhanced wettability are proposed as a promising strategy to alleviate the syndrome.
  • short-wavelength blue light in the range of approximately 400nm to 450nm is more likely to cause photochemical damage due to the accumulation of lipofuscin component A2E pigment or age-related damage caused by light-responsive proteins (such as cytochrome oxidase and porphyrin). macular degeneration.
  • an ophthalmic device such as a contact lens, that not only exhibits effective blue light blocking and a relatively less yellow appearance, but also has enhanced surface hydrophilicity, water retention, and lubricity of the device.
  • contact lenses are provided.
  • the contact lens includes a contact lens body and a blue light blocking material.
  • a blue light blocking material covers the contact lens body.
  • the blue blocking material includes a plurality of metal particles dispersed on the body of the contact lens.
  • the plurality of metal particles includes silver, gold, cobalt, manganese, nickel, copper, zinc, platinum, palladium, cadmium, indium, potassium, calcium, iron, or combinations thereof.
  • the contact lens includes from about 1 wt% to about 20 wt% blue light blocking material, based on the total weight of the contact lens.
  • the plurality of metal particles has a diameter of about 1 nm to 10000 nm.
  • contact lenses exhibit tunable plasmon resonances under visible light in the range of 380nm to 800nm.
  • the contact lenses suppress blue light by about 5% to about 99% at wavelengths ranging from 380 nm to about 480 nm.
  • the contact lenses have an average water contact angle of about 30 degrees to 70 degrees.
  • the contact lenses have an average hysteresis of about 0.1 degrees to 35 degrees.
  • the contact lens body comprises a hydrogel contact lens or a silicone hydrogel contact lens.
  • the contact lens body includes carboxyl, amine, hydroxyl, or pyrrolidone structures.
  • a method of making a contact lens is provided.
  • Contact lens bodies are provided.
  • the contact lens body is then flooded with the reaction solution to form a contact lens having a blue light blocking material covering the contact lens body.
  • the reaction solution includes a first solvent, at least one compound, and at least one reducing agent.
  • Compounds include metal ions.
  • the reducing agent reduces metal ions to metal particles.
  • the first solvent includes a water-soluble solvent.
  • the metal ions include silver ions, gold ions, cobalt ions, manganese ions, nickel ions, copper ions, zinc ions, platinum ions, palladium ions, cadmium ions, indium ions, potassium ions, calcium ions , iron ions, or combinations thereof.
  • the reducing agent includes at least one functional group including carboxyl group, amine group, thiol group, sulfide group, aldehyde group, hydroxyl group, alkoxide group, N - a heterocyclic group, a pyrrolidone group, a borohydride group or a combination thereof.
  • the reaction solution further includes carboxyl groups, amine groups, thiol groups, sulfide groups, aldehyde groups, hydroxyl groups, acrylamides, alkoxide groups, N-heterocyclic group, pyrrolidone group, ethylene glycol group or a combination thereof to functionalize at least one hydrophilicity enhancing molecule.
  • the method further includes packaging the contact lens with a packaging solution, wherein the packaging solution includes at least one hydrophilicity enhancing molecule; and performing a sterilization process.
  • the method further includes performing a heating process at a temperature in the range of 25°C to 135°C while immersing the contact lens body with the reaction solution.
  • the heating process includes heating the container containing the contact lens body and the reaction solution in an incubator for about 20 minutes to about 24 hours.
  • the incubator includes an oven, an autoclave, or a water bath incubator.
  • the method further includes preparing a heated reaction solution at a temperature below the lower critical solution temperature, wherein the heated reaction solution includes a polymer dissolved in a second solvent; using the heated reaction solution to immersing the contact lens; and heating the thermally reactive solution to form at least one hydrophobic moiety on the contact lens body.
  • the polymer is formed with carboxyl groups, amine groups, thiol groups, sulfide groups, aldehyde groups, hydroxyl groups, acrylamides, alkoxide groups, N-heterocyclic groups groups, pyrrolidone groups, ethylene glycol groups, or combinations thereof.
  • At least one hydrophobic moiety consists of carbon chains having alkane, alkene or alkyne linkages.
  • the carbon chain is present in a linear form or a non-linear form including branched or cyclic.
  • the method further includes extracting the contact lens with an extraction solution; performing a hydration process with a hydration solution; and performing a sterilization process with a packaging solution, wherein at least one of the extraction solution, the hydration solution, and the packaging solution One includes at least one hydrophilicity enhancing molecule.
  • FIG. 1 is a flowchart illustrating a method of making a contact lens according to some embodiments of the present disclosure.
  • FIGS. 2A and 2B are schematic diagrams illustrating various intermediate stages in a method of making a contact lens according to some embodiments of the present disclosure.
  • 3 and 4 are digital images of contact lenses according to some embodiments of the present disclosure.
  • UV-Vis ultraviolet-visible
  • 6A-6C are digital images of contact lenses according to some embodiments of the present disclosure.
  • FIG. 7A shows blue light transmission of contact lenses according to some embodiments of the present disclosure.
  • Figure 7B shows the UV-Vis transmission spectrum of a silicone hydrogel contact lens/hydrogel contact lens according to some embodiments of the present disclosure.
  • FIG. 1 is a flowchart illustrating a method of making a contact lens according to some embodiments of the present disclosure. As shown in FIG. 1 , the method 10 includes operation 12 and operation 14 . Note that the method described in FIG. 1 is an example only, and is not intended to limit the present disclosure. Accordingly, additional operations may be performed before, during, and/or after the method described in FIG. 1 , and some other operations may only be briefly described herein.
  • a contact lens body is provided.
  • the contact lens body can be a hydrogel contact lens body or a silicone hydrogel contact lens body.
  • Contact lens bodies can be manufactured by suitable methods.
  • the contact lens body includes carboxyl, amine, hydroxyl, or pyrrolidone structures.
  • the contact lens body can have carboxyl groups, amine groups (eg, primary, secondary, or tertiary amines), hydroxyl groups, pyrrolidone groups, thiol groups, or combinations thereof.
  • Such functional groups on and/or near its surface can react with compounds including metal ions of the subsequently prepared reaction solution.
  • contact lens body 100 is flooded with reaction solution 110 to form a contact lens having a blue-blocking material covering contact lens body 100 .
  • the contact lens body 100 and the reaction solution 110 can be placed in the container 200 , and the contact lens body 100 is completely immersed in the reaction solution 110 .
  • container 200 comprises polypropylene or glass.
  • the reaction solution 110 may include a solvent, at least one compound including metal ions, and at least one reducing agent for reducing the metal ions to metal particles.
  • the solvent includes a water-soluble solvent.
  • the solvent can be deionized water.
  • the metal ions include silver ions, gold ions, cobalt ions, manganese ions, nickel ions, copper ions, zinc ions, platinum ions, palladium ions, cadmium ions, indium ions, potassium ions, calcium ions, iron ions or a combination thereof.
  • the metal ion-containing compound can be silver nitrate.
  • the reducing agent includes at least one functional group including carboxyl group, amine group, thiol group, sulfide group, aldehyde group, hydroxyl group, alkoxide group, N-heterocycle group, pyrrolidone group, borohydride group, or a combination thereof.
  • preferred classes of reducing agents include chemicals containing carboxyl groups, amine groups, or thiols.
  • the reducing agent can be poly(acrylamide-co-acrylic acid), trisodium citrate, sodium tetrahydroborate, or combinations thereof.
  • the reducing agent has a molecular weight between about 37 and about 1,000,000 Daltons.
  • the reaction solution 110 further includes at least one hydrophilicity enhancing molecule, a stabilizer, or a combination thereof.
  • the hydrophilicity enhancing molecule is made of carboxyl group, amine group, thiol group, sulfide group, aldehyde group, hydroxyl group, acrylamide, alkoxide group, N-heterocyclic group groups, pyrrolidone groups, ethylene glycol groups, or combinations thereof.
  • hydrophilicity enhancing molecules such as poly(acrylic acid), polyvinylpyrrolidone (PVP), hyaluronic acid (HA), micro-hyaluronic acid, carboxymethylcellulose, hydroxypropylmethyl Hydroxypropyl methylcellulose (HPMC) or the like may also have the ability to reduce metal ions to metal particles.
  • the hydrophilicity enhancing molecule can be different from the reducing agent.
  • the addition of hydrophilicity-enhancing molecules can improve the blue-light blocking efficacy and surface properties of contact lenses.
  • the stabilizer can be any suitable dispersant and/or surfactant.
  • Stabilizers can interact with the metal particles.
  • stabilizers include ionic, nonionic, zwitterionic surfactants, ammonium salts, sodium salts, the like, or combinations thereof.
  • contact lens body 100 is flooded with all components of reaction solution 110 in one step.
  • each component of reaction solution 110 may be mixed with contact lens body 100 individually.
  • contact lens body 100 may first be flooded with a solution comprising a reducing agent, and then a compound comprising metal ions is added to the solution.
  • contact lens body 100 is immersed in reaction solution 110 for about 30 minutes at room temperature.
  • the method further includes performing a heating process at a temperature ranging from 25° C. to 135° C. while immersing the contact lens body 100 with the reaction solution 110 .
  • the temperature may be about 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125 , 130 or 135°C.
  • contact lens body 100 is heated from a pH of about 3.0 to about 11.0.
  • the container 200 containing the contact lens body 100 and the reaction solution 110 may be placed in an incubator 300 for performing a heating process, as shown in FIGS. 2A and 2B .
  • the incubator 300 comprises a water bath incubator (e.g., the incubator 300 shown in FIG. 2A includes water 310 therein), an oven (e.g., the incubator 300 shown in FIG. 2B ), or an autoclave (not shown).
  • the heating process includes heating the vessel 200 in the incubator 300 for about 20 minutes to about 24 hours.
  • container 200 may be heated for 20 minutes, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 or 24 hours.
  • the heating process may speed up modification of the blue-blocking material covering the contact lens body 100 .
  • the method further comprises preparing a thermally reactive solution at a temperature below a lower critical solution temperature (LCST); immersing the contact lens with the thermally reactive solution; and heating the thermally reactive solution to form at least one hydrophobic portion on the contact lens body.
  • LCST critical solution temperature
  • the heated reaction solution includes a polymer dissolved in a solvent.
  • the polymer is made with carboxyl groups, amine groups, thiol groups, sulfide groups, aldehyde groups, hydroxyl groups, acrylamides, alkoxide groups, N-heterocyclic groups, pyrrole functionalized with pyridone groups, ethylene glycol groups, or combinations thereof.
  • the polymer can be hyaluronic acid (hyaluronic acid; HA), micro-hyaluronic acid (micro-HA), hydroxypropylmethylcellulose (HPMC) and carboxymethylcellulose (carboxymethylcellulose; CMC), polyvinylpyrrolidone (polyvinylpyrrolidone; PVP).
  • the solvent includes deionized water.
  • the hot reaction solution is heated to or above the LCST point. Specifically, upon heating of the thermal reactive solution, the hydrophobic portion of the polymer is revealed, thereby creating a relatively hydrophobic surface on and/or adjacent to the contact lens body. Hydrophobic surfaces can cause contact lenses not to exhibit an intact water film.
  • at least one hydrophobic moiety consists of carbon chains with alkane, alkene, or alkyne linkages. In some embodiments, the carbon chain is present in a linear form or a non-linear form including branched or cyclic.
  • the hydrophobic moiety on the body of the contact lens can be bonded to the hydrophobic moiety of the hydrophilicity-enhancing molecule used in solution during any subsequent extraction, hydration, and/or sterilization processes, such that the hydrophilicity-enhancing molecule is hydrophilic
  • the sexual portion is exposed, and the surface of the contact lens body exhibits hydrophilicity.
  • the surface hydrophilicity, wettability and/or lubricity properties of the contact lens can be improved.
  • the method further includes extracting the contact lens with the extraction solution. The extraction process may be performed after flooding the contact lens body with the reactive solution and/or flooding the contact lens with the heated reactive solution.
  • the extraction solution when the contact lens body is a silicone hydrogel contact lens, can be isopropanol and 50% v/v isopropanol. In other embodiments, when the contact lens body is a hydrogel contact lens, the extraction solution can be borate buffered saline. In some embodiments, the extraction solution further includes at least one hydrophilicity enhancing molecule.
  • the hydrophilicity enhancing molecule includes at least one functional group, the functional group includes carboxyl group, amine group, thiol group, sulfide group, aldehyde group, hydroxyl group, alkoxide group, N - a heterocyclic group, a pyrrolidone group, a borohydride group or a combination thereof.
  • preferred classes of hydrophilicity enhancing molecules include carboxylic, amine or thiol containing chemicals.
  • the hydrophilicity enhancing molecule may be poly(acrylamide-co-acrylic acid), poly(acrylic acid), polyvinylpyrrolidone (PVP), hyaluronic acid (HA), microtransparent Hyaluronic acid (micro HA), carboxymethylcellulose (carboxymethylcellulose; CMC), hydroxypropylmethylcellulose (hydroxypropylmethylcellulose; HPMC), surfactant or a combination thereof.
  • the hydrophilicity enhancing molecule can be the same as the polymer of the thermally reactive solution. In some embodiments, the hydrophilicity enhancing molecule may be different from the polymer of the thermally reactive solution.
  • the method further includes performing a hydration process.
  • the contact lenses are hydrated with a hydration solution such as borate buffered saline.
  • the hydration solution may further include hydrophilicity enhancing molecules as described above.
  • the hydrophilicity enhancing molecule can be the same as the polymer of the thermally reactive solution.
  • the hydrophilicity enhancing molecule may be different from the polymer of the thermally reactive solution. Hydrophilicity enhancing molecules can have LCST properties.
  • the method further includes performing a sterilization process.
  • the contact lenses are packaged with a packaging solution prior to performing the sterilization process.
  • the packaging solution includes borate buffered saline.
  • the packaging solution further includes at least one hydrophilicity enhancing molecule, such as hyaluronic acid, micro-hyaluronic acid, carboxymethylcellulose, hydroxypropylmethylcellulose, a surfactant, or a combination thereof.
  • the hydrophilicity enhancing molecule can be the same as the polymer of the thermally reactive solution.
  • the hydrophilicity enhancing molecule may be different from the polymer of the thermally reactive solution.
  • the contact lenses are sterilized at about 121°C for about 20 minutes.
  • the contact lens includes a contact lens body and a blue light blocking material covering the contact lens body, wherein the blue light blocking material includes a plurality of metal particles dispersed on the contact lens body.
  • the contact lens body comprises a hydrogel contact lens or a silicone hydrogel contact lens.
  • the contact lens body includes carboxyl, amine, hydroxyl, or pyrrolidone structures.
  • the contact lens body can have carboxyl groups, amine groups (eg, primary, secondary, or tertiary amines), hydroxyl groups, pyrrolidone groups, thiol groups, or combinations thereof.
  • the plurality of metal particles includes silver, gold, cobalt, manganese, nickel, copper, zinc, platinum, palladium, cadmium, indium, potassium, calcium, iron, or combinations thereof.
  • the plurality of metal particles has a diameter of about 1 nm to 10000 nm.
  • the diameter of the metal particles is preferably 1 nm to 1000 nm, or more preferably 1 nm to 200 nm.
  • the metal particles can be particles separated from each other, clusters, or a combination thereof.
  • the metal particles are substantially uniformly dispersed throughout the contact lens body.
  • the contact lens includes from about 1 wt% to about 20 wt% blue blocking material, based on the total weight of the contact lens. With only a small amount of blue light blocking material, the contact lenses of the present disclosure can achieve good blue light blocking efficiency.
  • the contact lens exhibits tunable plasmon resonances under visible light in the range of 380nm to 800nm. In some embodiments, the contact lens exhibits tunable plasmon resonances under visible light, preferably in the range of 380nm to 500nm. In some embodiments, the contact lens exhibits tunable plasmon resonance at visible light in the range of 380nm to 450nm, more preferably. In some embodiments, the contact lenses inhibit blue light from about 5% to about 99% at wavelengths ranging from 380nm to about 480nm, while having a light blocking efficacy of 14% to 98% at 480nm to 800nm. In some embodiments, the contact lenses have an average water contact angle of about 30 degrees to 70 degrees. In some embodiments, the contact lenses have an average retardation of about 0.1 degrees to 35 degrees.
  • 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate; HEMA) and methacrylic acid are mixed with crosslinking agents ethylene glycol dimethacrylate and trimethylol propyl acrylate to form a mixture.
  • the mixture was used to dissolve the remaining powders including reactive blue dye, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IRGACURE 819) and 2-[2-hydroxy- 5-[2-(Methacryloyloxy)ethyl]phenyl]-2H-benzotriazole until all powder is dissolved in the mixture.
  • the reaction mixture thus prepared was added and cast in a front-to-back curved mold made of polypropylene and irradiated at 5 mW/cm 2 for 20 minutes in air.
  • the resulting hydrogel contact lenses in dry state were released and then extracted twice by borate buffered saline at 60° C. for 1 hour.
  • the resulting hydrogel contact lenses were placed in blister packs filled with borate buffered saline and sterilized.
  • the resulting hydrogel contact lens has a water content of about 58%, an oxygen permeability of about 20 DK to 25 DK, a modulus of about 0.3 to 0.4, and a blue light blocking efficacy of about 1% to 3%.
  • N-vinylpyrrolidone N-vinyl pyrrolidone
  • NVP 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate
  • HEMA 2-hydroxyethyl methacrylate
  • methacrylic acid and N,N-dimethylaniline N,N
  • the hydrophilic component of -dimethylaniline; DMA is first mixed with the silica gel material (3-methacryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, and then Mix with crosslinking agent ethylene glycol dimethacrylate and triallyl-s-triazine-2,4,6(1H.3H,5H)-trione.
  • the reaction mixture thus prepared was added and cast in a front-to-back curved mold made of polypropylene and irradiated for 30 minutes at 5 mW/cm 2 in air.
  • the resulting silicone hydrogel contact lens was released in a dry state.
  • the dried silicone hydrogel contact lenses were extracted with isopropanol and 50% v/v isopropanol for 1 hour at 50°C, and then washed twice with borate buffered saline at 25°C for 10 minutes. Hydrated silicone hydrogel contact lenses were placed in blister packs filled with borate buffered saline and sterilized.
  • the resulting silicone hydrogel contact lenses have a water content of about 48% to 52%, an oxygen permeability of about 120 DK, a modulus of about 0.6 to 0.7, and a blue light blocking efficacy of about 5% to 7%.
  • the same reaction mixture was prepared except that methacrylic acid was replaced by the same amount of 2-hydroxyethyl methacrylate. Subsequent manufacturing process is the same as above.
  • the resulting silicone hydrogel contact lenses without methacrylic acid addition exhibited a water content of about 46% to 50%, an oxygen permeability of about 120 DK, a modulus of about 0.6 to 0.7, and a blue light blocking efficacy of about 8% to 10%.
  • Stock solutions were prepared via deionized water to dissolve powders of poly(acrylamide-co-acrylic acid) and trisodium citrate at final concentrations of 0.5 mg/ml and 0.1 M, respectively.
  • 600 ⁇ L of the stock solution was added to a container made of polypropylene.
  • the dry release silicone hydrogel contact lens or hydrogel contact lens ie, the contact lens body
  • 300 ⁇ L of 20 mM, 1.62 mM and 0.41 mM silver nitrate solutions were added to the container and mixed with the stock solutions.
  • 900 ⁇ L of deionized water was added to the container.
  • the resulting mixture ie, reaction solution
  • the final concentrations of silver nitrate for the three reaction mixtures were about 566.7 ppm, 45.9 ppm, and 11.6 ppm, respectively.
  • the silicone hydrogel contact lenses or hydrogel contact lenses in the container were incubated with the reaction solution for 30 minutes at room temperature.
  • the container was then heated in an oven for 2 hours at a temperature ranging from 25°C to 85°C.
  • the contact lenses were washed twice with deionized water in order to remove unreacted reaction solution.
  • the silicone hydrogel contact lenses were extracted by isopropanol and 50% v/v isopropanol for 1 hour at 50°C, respectively, and then hydrated by borate buffered saline at 25°C Twice, for 10 minutes.
  • it was then extracted twice by borate buffered saline at 60°C for 1 hour. All contact lenses were finally placed in borate buffered saline prior to any further experimentation.
  • the final contact lens exhibited a positive temperature-dependent response to dispersing the blue blocking material on the contact lens body.
  • 3 and 4 are digital images of silicone hydrogel contact lenses and hydrogel contact lenses, respectively. As shown in Figures 3 and 4, when the incubation temperature was increased, enhanced blue light blocking efficacy of the resulting contact lenses was observed (ie, the contact lenses were darker in color).
  • UV-Vis ultraviolet-visible light
  • Figure 5A and Figure 5B silicon Hydrogel contact lenses (Fig. 5B) are more reactive to blue light blocking materials.
  • the corresponding blue light blocking efficacy of the resulting silicone hydrogel contact lenses achieves a blue light blocking efficacy of from about 8% to about 100%. This is attributed to the higher fraction of effective functional groups such as carboxyl and pyrrolidone groups in silicone hydrogel contact lenses.
  • Silicone hydrogel contact lenses without the methacrylic acid component showed little reactivity in terms of sterilization, as shown in Figure 6A.
  • Silicone hydrogel contact lenses (SiHy) with a methacrylic acid component were reactive in both 24 h room temperature incubation and sterilization at 121 °C, as shown in Figure 6B.
  • the hydrogel contact lens (Hy) reacted with the reaction solution only when the sterilization was continued, as shown in Figure 6C.
  • silicone hydrogel contact lenses As evidenced by the results in Examples 1 and 2, the data in the Examples reinforce the conclusion that, compared to silicone hydrogel contact lenses or hydrogel contact lenses without methacrylic acid addition, more functional groups (e.g., pyrrolidone groups, and methacrylic acid groups) silicone hydrogel contact lenses proved to be more effective in blocking blue light.
  • more functional groups e.g., pyrrolidone groups, and methacrylic acid groups
  • PAA represents poly(acrylamide-co-acrylic acid)
  • TSC is an abbreviation for trisodium citrate.
  • Blue light blocking refers to blue light blocking efficacy at wavelengths from 380nm to 480nm.
  • a 96 ml stock solution was first prepared by dissolving both powders of poly(acrylamide-co-acrylic acid) and trisodium citrate using deionized water at room temperature under a magnetic stir bar for 1 hour. The final concentrations of poly(acrylamide-co-acrylic acid) and trisodium citrate were 0.5 mg/ml and 0.1 M, respectively. Then, under stirring, 176 ml of deionized water and 16 ml of silver nitrate solution were added to the stock solution for another 1 hour to form a reaction solution. The final concentration of silver nitrate was 15 ppm.
  • Example 3 demonstrate that the modification of blue-blocking materials on contact lenses is temperature-dependent, it is believed that the more efficient heat transfer in water vapor than in air explains the results in Example 6, indicating that the temperature-dependent reactions are In other words, water vapor emerging from a water bath is relatively more efficient than an oven. Therefore, all following experiments were applied via water vapor.
  • PA poly(acrylic acid); acid; another material of hyaluronic acid
  • micro HA micro hyaluronic acid
  • CMC carboxymethyl cellulose
  • Each of the containers houses a dry hydrogel contact lens. Then, 1.8 ml of the reaction solution thus prepared was added to the vessel for 30 minutes. All containers were then incubated in water vapor at 85°C for 2 hours. After incubation, all contact lenses were placed in new containers loaded with 2ml of fresh deionized water. All samples were recorded via a digital video camera and the resulting images were processed for analysis by means of the Palette add-on from a computer program or Image J software. Effect poly(acrylamide-co-acrylic acid) or other additional auxiliary materials are shown in Table 3.
  • PAA denotes poly(acrylamide-co-acrylic acid); PA denotes poly(acrylic acid) having a molecular weight of about 2000 Daltons; TSC denotes trisodium citrate; PVP denotes polyvinylpyrrolidone; Hyaluronic acid having a molecular weight of about 1,000,000 Daltons; micro-HA means micro-hyaluronic acid having a molecular weight of less than about 10,000 Daltons; CMC means carboxymethylcellulose having a molecular weight of about 250,000 Daltons; and CL means contact lens. Marking * indicates that the range of blue light blocking material is unevenly distributed on the contact lens. Color change ( ⁇ C): The yellow color (255, 255, 0) served as a control group for further comparison.
  • Example 8 containing functional chemicals such as hyaluronic acid (hyaluronic acid; HA), micro hyaluronic acid (micro HA), carboxymethyl cellulose (carboxymethyl cellulose; CMC), and hydroxypropyl methyl cellulose (hydroxypropyl methylcellulose; HPMC) to further adjust the blue light blocking material modification.
  • HA hyaluronic acid
  • micro hyaluronic acid micro HA
  • carboxymethyl cellulose carboxymethyl cellulose
  • CMC carboxymethyl cellulose
  • HPMC hydroxypropyl methyl cellulose
  • Contact lenses were first prepared according to the method described in #21 (Example 7). After 2 hours of blue light blocking material modification, the contact lenses were washed twice with deionized water and incubated in a solution, alternatively deionized water, 0.1 wt% HA in a water bath heated for an additional 1 hour at 85°C , 0.1wt% micro-HA, 0.5wt% CMC, 0.3wt% HPMC (hydroxypropyl methylcellulose; 80cp to 120cp) or 0.1wt% HPMC (hydroxypropyl methylcellulose, 2600cp to 5600cp) . Contact lenses were then hydrated three times in borate-buffered saline at 60°C for 0.5 hours.
  • contact lenses were packaged in glass containers with 3 ml of packaging solution, optionally borate buffered saline, 0.1 wt% hyaluronic acid, 0.1 wt% micro hyaluronic acid, 0.5 wt% carboxymethylcellulose, 0.3 wt% hydroxypropyl methylcellulose (80cp to 120cp) or 0.1 wt% hydroxypropylmethylcellulose (2600cp to 5600cp). Then, the packaged contact lenses were sent to process at 121°C for an average of 20 minutes in the sterilization process. All results are shown in Table 4 and Table 5.
  • HA represents hyaluronic acid with a molecular weight of about 1,000,000 Daltons
  • micro HA represents micro hyaluronic acid with a molecular weight of less than about 10,000 Daltons
  • HPMC a represents hyaluronic acid with a molecular weight of 80 cp to 120 cp of hydroxypropylmethylcellulose
  • HPMC b denotes hydroxypropylmethylcellulose with 2600cp to 5600cp
  • CMC denotes carboxymethylcellulose with a molecular weight of about 250000 Daltons.
  • the lubricity score is a qualitative rating scheme in which a scale of 0 to 6 is used, with 0 or lower numbers indicating better lubricity.
  • a mixture of 84 ml was first prepared by dissolving poly(acrylamide-co-acrylic acid) and trisodium citrate using deionized water under sonication for about 3 minutes.
  • the final concentrations of poly(acrylamide-co-acrylic acid) and trisodium citrate were 0.5 mg/ml and 0.1 M, respectively.
  • a magnetic stir bar was placed in the mixture and held steady at about 300 rpm to 400 rpm.
  • 126 ml of silver nitrate solution with two different concentrations was slowly added to the mixture.
  • 42 ml of 0.1 wt% PVP was then added to the mixture and stirred for another 20 minutes.
  • the resulting reaction solutions were obtained with final concentrations of 15 ppm and 22.5 ppm silver nitrate.
  • the dry-releasing hydrogel contact lens was immersed in 1.8 ml of the reaction solution thus prepared in the container for 30 minutes. All containers were then incubated for 2 hours at 85°C in steam. Afterwards, all contact lenses were washed twice with deionized water. Then, within 1 hour at 85°C, soak the contact lens in an incubator for 300s via water bath incubation, wherein the reactive solutions are 0.3wt% HPMC (80cp to 120cp), and 0.1wt% HPMC (80cp to 120cp) ) with 0.1wt% PVP.
  • the contact lenses were hydrated three times in borate buffered saline at 60°C for 0.5 hours and filled with 1 ml of 0.1 wt% micro-HA with 0.1 wt% HA, 0.2 wt% micro-HA, 0.2 wt% HA, 0.1 wt% HA With 0.5wt% CMC, 0.1wt% micro-HA and 0.5wt% CMC, surfactant 9217 or 0.1wt% HA and 0.5wt% CMC and surfactant 9217, surfactant 9217 contains 0.1wt% polyethylene glycol 200 , 0.01 wt% Tween 80, and 2 wt% 2-(methacryloyloxy)ethyl 2-(trimethylammonium)ethylphosphate-n-butyl methacrylate copolymer.
  • Example 6 The surface properties of the control hydrogel contact lens obtained via Example 1 and the commercial product DAYILIED TOTAL 1 contact lens are listed in Table 6.
  • WBUT represents water break-up time.
  • Table 7 summarizes the resulting contact lenses after various conditions adjusted via the hydration process or packaging solution.
  • HA means hyaluronic acid having a molecular weight of about 1,000,000 Daltons
  • micro HA means micro hyaluronic acid having a molecular weight of less than about 10,000 Daltons
  • HPMC means hydroxypropyl methylcellulose
  • CMC means carboxymethylcellulose with a molecular weight of about 250000 Daltons.
  • BLB means the blue light blocking efficacy at the wavelength of 380nm to 480nm.
  • Het. refers to the uneven distribution of blue light blocking material on a contact lens.
  • WBUT refers to water break-up time.
  • the sign # indicates that the packaging solution of the contact lens after sterilization showed a yellowish color.
  • a mark * indicates that one or more of the resulting contact lenses failed to initially display a complete water film.
  • the packaging solution was added by CMC, and the resulting contact lenses exhibited blue light blocking efficacy of about 18% to 37% when silver nitrate was added at concentrations of 15 ppm and 22.5 ppm.
  • the blue light blocking efficacy and water retention of the resulting contact lenses were significantly reduced. This result can be attributed to a cooperative effect between the two polymers on dissolution and stabilization in the surface microstructure of the contact lens.
  • contact lenses hydrated with HPMC exhibited approximately 15° to 35° reduction in advancing contact angle and hysteresis with increased water retention capacity (20% to 55% reduction in water rupture area after 3 minutes), indicating that as compared to control contact lenses The resulting hydrophilic properties of contact lenses are improved in comparison.
  • contact lenses filled with borate buffered saline exhibited a significant reduction in the first time point of water breakup time. Specifically, for those with a 22.5 ppm silver nitrate response, more than 80% of the contact lenses were not able to perform a fully intact water film at the beginning of the inspection.
  • Sample 1 sample 2, and sample 3 were collected from Example 9, corresponding to packaging solutions of borate buffered saline, surfactant 9217, and surfactant 9217 with 0.5 wt% CMC and 0.1 wt% HA, respectively.
  • Samples 1-3 were recorded via a digital video camera and the resulting images were analyzed by processing with the Palette add-on from a computer program or Image J software, as shown in FIG. 9 . Each product was then examined with respect to UV-Vis spectroscopy. Calculate the blue light blocking efficacy from 380nm to 480nm. Table 8 summarizes the results for Samples 1-3 and two commercial products.
  • the contact lens includes a plurality of blue-blocking materials dispersed over the body of the contact lens.
  • the contact lenses of the present disclosure have good blue light blocking properties and exhibit relatively less yellowish appearance.
  • the contact lenses of the present disclosure have good surface hydrophilicity, water retention properties and lubricity.

Landscapes

  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Ophthalmology & Optometry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Health & Medical Sciences (AREA)
  • Eyeglasses (AREA)

Abstract

提供隐形眼镜及其制造方法（10），隐形眼镜包括隐形眼镜主体（100）及蓝光阻挡材料，蓝光阻挡材料覆盖隐形眼镜主体（100），蓝光阻挡材料包括分散在隐形眼镜主体（100）上的多个金属颗粒，隐形眼镜具有良好蓝光阻挡功效及表面性质。

Description

隐形眼镜及其制造方法 技术领域
本揭露是关于隐形眼镜及其制造方法。更具体而言，本揭露是关于具有阻挡蓝光能力的隐形眼镜及其制造方法。
背景技术
近十年来，数位眼疲劳(digital eye strain；DES)，亦称为电脑视觉症候群，为重大公共卫生挑战。它表示与长期使用数位设备，以及对于眼睛的其他直接或间接环境压力相关的一系列视觉障碍、干燥或不适症候群。对于在此等情况下的一般隐形眼镜使用者，提出阻挡特定波长的蓝光并且润湿性增强的隐形眼镜为缓解症候群的有希望策略。尤其对于老年人，大约在400nm至450nm范围内的短波长蓝光由于脂褐质成分A2E色素积累而导致光化学损伤的可能性更高或光响应蛋白(如细胞色素氧化酶及卟啉)导致年龄相关黄斑变性。
传统阻挡蓝光眼镜经由添加化学颜料或染料来应用的。然而，为了更高蓝光阻挡效率，强烈黄色或琥珀色在外观方面通常不合乎需要。虽然另外与显示不同颜色的其他染料混合会抵消外观，但蓝光阻挡效率会因此降低。此外，涵盖500nm的染料吸收会干扰正常颜色感知，并削弱整体透光率及视觉效果，尤其对于暗视。此等非所欲缺点反过来可能对一般用户对隐形眼镜的偏好产生负面影响。
因此，仍然需要制造一种眼科装置，例如隐形眼镜，其不仅表现出有效蓝光阻挡及相对较少黄色外观，而且增强了表面亲水性、保水性以及装置的润滑性。
发明内容
根据本揭露的态样，提供隐形眼镜。隐形眼镜包括隐形眼镜主体及蓝光阻挡材料。蓝光阻挡材料覆盖隐形眼镜主体。蓝光阻挡材料包括分散在隐形眼镜主体上的多个金属颗粒。
根据本揭示案的一些实施例，多个金属颗粒包括银、金、钴、锰、镍、铜、锌、铂、钯、镉、铟、钾、钙、铁或其组合。
根据本揭示案的一些实施例，以隐形眼镜的总重量计，隐形眼镜包括 约1wt％至约20wt％的蓝光阻挡材料。
根据本揭示案的一些实施例，多个金属颗粒具有约1nm至10000nm的直径。
根据本揭示案的一些实施例，隐形眼镜在380nm至800nm范围内的可见光下，表现出可调谐等离子体子共振。
根据本揭示案的一些实施例，隐形眼镜在380nm至约480nm范围内的波长下，抑制约5％至约99％的蓝光。
根据本揭示案的一些实施例，隐形眼镜具有约30度至70度的平均水接触角。
根据本揭示案的一些实施例，隐形眼镜具有约0.1度至35度的平均迟滞现象。
根据本揭示案的一些实施例，隐形眼镜主体包括水凝胶隐形眼镜或硅水凝胶隐形眼镜。
根据本揭示案的一些实施例，隐形眼镜主体包括羧基、胺基、羟基或吡咯啶酮结构。
根据本揭示案的另一态样，提供制造隐形眼镜的方法。提供隐形眼镜主体。然后，隐形眼镜主体用反应溶液浸没以形成具有覆盖隐形眼镜主体的蓝光阻挡材料的隐形眼镜。反应溶液包括第一溶剂、至少一种化合物、及至少一种还原剂。化合物包括金属离子。还原剂将金属离子还原成金属颗粒。
根据本揭示案的一些实施例，第一溶剂包括水溶性溶剂。
根据本揭示案的一些实施例，金属离子包括银离子、金离子、钴离子、锰离子、镍离子、铜离子、锌离子、铂离子、钯离子、镉离子、铟离子、钾离子、钙离子、铁离子或其组合。
根据本揭示案的一些实施例，还原剂包括至少一个官能基，官能基包括羧基团、胺基团、硫醇基团、硫化物基团、醛基团、羟基团、醇盐基团、N-杂环基团、吡咯啶酮基团、硼氢化物基团或其组合。
根据本揭示案的一些实施例，反应溶液进一步包括用羧基团、胺基团、硫醇基团、硫化物基团、醛基团、羟基团、丙烯酰胺、醇盐基团、N-杂环基团、吡咯啶酮基团、乙二醇基团或其组合来官能化的至少一种亲水性增强分子。
根据本揭示案的一些实施例，该方法进一步包括用包装溶液来包装隐形眼镜，其中包装溶液包括至少一种亲水性增强分子；及执行灭菌过程。
根据本揭示案的一些实施例，该方法进一步包括当用反应溶液来浸没隐形眼镜主体时，在25℃至135℃范围内的温度下执行加热过程。
根据本揭示案的一些实施例，加热过程包括在恒温箱中，加热容纳隐形眼镜主体及反应溶液的容器约20分钟至约24小时。
根据本揭示案的一些实施例，恒温箱包括烘箱、高压蒸汽杀菌器或水浴恒温箱。
根据本揭示案的一些实施例，该方法进一步包括在低于较低临界溶液温度的温度下，制备热反应溶液，其中热反应溶液包括溶解于第二溶剂中的聚合物；用热反应溶液来浸没隐形眼镜；及将热反应溶液加热以在隐形眼镜主体上形成至少一个疏水性部分。
根据本揭示案的一些实施例，聚合物是用羧基团、胺基团、硫醇基团、硫化物基团、醛基团、羟基团、丙烯酰胺、醇盐基团、N-杂环基团、吡咯啶酮基团、乙二醇基团或其组合来官能化。
根据本揭示案的一些实施例，至少一个疏水性部分由具有烷烃、烯烃或炔烃键的碳链组成。
根据本揭示案的一些实施例，碳链为以直链形式或包括支链或环状的非直链形式呈现。
根据本揭示案的一些实施例，该方法进一步包括用萃取溶液来萃取隐形眼镜；用水合溶液来执行水合过程；及用包装溶液执行灭菌过程，其中萃取溶液、水合溶液及包装溶液中的至少一者包括至少一个亲水性增强分子。
应了解前面一般描述及以下详细描述举例说明，并且意欲提供如请求保护的本揭露的进一步解释。
附图的简要说明
本揭露的态样根据与随附图式一起阅读的以下详细描述来最佳理解。注意，根据行业中的标准作法，各个特征未按比例绘制。事实上，为了论述清晰，可以任意增加或减少各种特征的尺寸。
图1为例示根据本揭示案的一些实施例的制造隐形眼镜的方法的流程图。
图2A及图2B为例示根据本揭示案的一些实施例的制造隐形眼镜的方法中的各个中间阶段的略图。
图3及图4为根据本揭示案的一些实施例中的隐形眼镜的数位影像。
图5A及图5B分别示出根据本揭示案的一些实施例的硅水凝胶隐形眼 镜及水凝胶隐形眼镜的紫外光-可见光(UV-Vis)光谱。
图6A至图6C为根据本揭示案的一些实施例的隐形眼镜的数位影像。
图7A示出根据本揭示案的一些实施例的隐形眼镜的蓝光透射率。
图7B示出根据本揭示案的一些实施例的硅水凝胶隐形眼镜/水凝胶隐形眼镜的UV-Vis透射光谱。
图8至图9为根据本揭示案的一些实施例的隐形眼镜的数位影像。
【主要元件符号说明】
10：方法                     12：操作
14：操作                     100：隐形眼镜主体
110：反应溶液                200：容器
300：恒温箱                  310：水
实现发明的最佳方式
现将详细参考本揭露的某些实施例，其实例在附图中说明。在可能的情况下，在附图及描述中使用相同参考数字来指代相同或相似部分。
为了使本揭示案的描述更加详细及完整，下面对本揭示案的实施态样及具体实施例进行说明性描述；然而，此并非实施或利用本揭示案的具体实施例的唯一形式。以下揭示的实施例可以有利方式彼此组合或替换，并且在没有进一步记录或描述的情况下，其他实施例可添加至实施例。在以下描述中，详细描述许多特定细节以使得读者能够完全理解以下实施例。然而，本揭露的实施例可在没有此等特定细节的情况下实施。
图1为例示根据本揭示案的一些实施例的制造隐形眼镜的方法的流程图。如图1所示，该方法10包括操作12及操作14。注意图1描述的方法仅为实例，并且不意欲限制本揭露。因此，额外操作可在图1描述的方法之前、期间、及/或之后执行，并且一些其他操作仅可在本文中简短描述。
参考图1。在图1的操作12中，提供隐形眼镜主体。在一些实施例中，隐形眼镜主体可为水凝胶隐形眼镜主体或硅水凝胶隐形眼镜主体。隐形眼镜主体可借由合适方法来制造。在一些实施例中，隐形眼镜主体包括羧基、胺基、羟基或吡咯啶酮结构。例如，隐形眼镜主体可具有羧基、胺基(例如，一级胺、二级胺或三级胺)、羟基、吡咯啶酮基团、硫醇基或其组合。其表面上及/或附近的此等官能基可与包括随后制备的反应溶液的金属离子的化合物反应。
参考图1及图2A至图2B。在图1的操作14中，隐形眼镜主体100用 反应溶液110浸没以形成具有覆盖隐形眼镜主体100的蓝光阻挡材料的隐形眼镜。如图2A及图2B所示，隐形眼镜主体100及反应溶液110可安置于容器200中，并且隐形眼镜主体100完全浸泡于反应溶液110中。在一些实施例中，容器200包括聚丙烯或玻璃。
反应溶液110可包括溶剂、包含金属离子的至少一种化合物及用于将金属离子还原至金属颗粒的至少一种还原剂。在一些实施例中，溶剂包括水溶性溶剂。在一些实例中，溶剂可为去离子水。
在一些实施例中，金属离子包括银离子、金离子、钴离子、锰离子、镍离子、铜离子、锌离子、铂离子、钯离子、镉离子、铟离子、钾离子、钙离子、铁离子或其组合。在一些实例中，包含金属离子的化合物可以是硝酸银。
在一些实施例中，还原剂包括至少一个官能基，官能基包括羧基团、胺基团、硫醇基团、硫化物基团、醛基团、羟基团、醇盐基团、N-杂环基团、吡咯啶酮基团、硼氢化物基团或其组合。在一些实例中，较佳类别的还原剂包括含有羧基、胺基或硫醇的化学品。例如，还原剂可为聚(丙烯酰胺-共-丙烯酸)、柠檬酸三钠、四氢硼酸钠或其组合。在一些实施例中，还原剂具有约37至约1000000道尔顿之间的分子量。
在一些实施例中，反应溶液110进一步包括至少一种亲水性增强分子、稳定剂或其组合。在一些实施例中，亲水性增强分子是用羧基团、胺基团、硫醇基团、硫化物基团、醛基团、羟基团、丙烯酰胺、醇盐基团、N-杂环基团、吡咯啶酮基团、乙二醇基团或其组合来官能化。注意一些亲水性增强分子，诸如聚(丙烯酸)、聚乙烯吡咯啶酮(polyvinylpyrrolidone；PVP)、透明质酸(hyaluronic acid；HA)、微型透明质酸、羧甲基纤维素、羟基丙基甲基纤维素(hydroxypropyl methylcellulose；HPMC)或类似物亦可具有将金属离子还原至金属颗粒的能力。在一些实施例中，亲水性增强分子可不同于还原剂。添加亲水性增强分子可改良隐形眼镜的蓝光阻挡功效及表面性质。
在一些实施例中，稳定剂可为任何合适分散剂及/或界面活性剂。稳定剂可与金属颗粒相互作用。在一些实施例中，稳定剂包括离子、非离子、两性离子界面活性剂、铵盐、钠盐、类似者或其组合。
在一些实施例中，在一个步骤中，隐形眼镜主体100用反应溶液110的所有组分来浸没。在其他实施例中，反应溶液110的各组分可个别地与隐形眼镜主体100混合。例如，隐形眼镜主体100可首先用包含还原剂的 溶液来浸没，并且然后将包含金属离子的化合物添加至溶液。在一些实施例中，在室温下，将隐形眼镜主体100浸没于反应溶液110中约30分钟。
在一些实施例中，该方法进一步包括当用反应溶液110来浸没隐形眼镜主体100时，在25℃至135℃范围内的温度下执行加热过程。在一些实例中，温度可为约25、30、35、40、45、50、55、60、65、70、75、80、85、90、95、100、105、110、115、120、125、130或135℃。在一些实施例中，将隐形眼镜主体100自约3.0的pH值加热至约11.0。容纳隐形眼镜主体100及反应溶液110的容器200可安置于用于执行加热过程的恒温箱300中，如图2A及图2B中示出。在一些实施例中，恒温箱300包括水浴恒温箱(例如，图2A所示的恒温箱300包括其中的水310)、烘箱(例如，图2B所示的恒温箱300)或高压蒸汽杀菌器(未绘示)。在一些实施例中，加热过程包括将恒温箱300中的容器200加热约20分钟至约24小时。在一些实例中，容器200可加热20分钟、0.5、1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23或24小时。加热过程可加速覆盖隐形眼镜主体100的蓝光阻挡材料的修饰。
在一些实施例中，该方法进一步包括在低于较低临界溶液温度(lower critical solution temperature；LCST)的温度下，制备热反应溶液；用热反应溶液来浸没隐形眼镜；及将热反应溶液加热以在隐形眼镜主体上形成至少一个疏水性部分。
在一些实施例中，热反应溶液包括溶解于溶剂中的聚合物。在一些实施例中，聚合物是用羧基团、胺基团、硫醇基团、硫化物基团、醛基团、羟基团、丙烯酰胺、醇盐基团、N-杂环基团、吡咯啶酮基团、乙二醇基团或其组合来官能化。在一些实例中，聚合物可为透明质酸(hyaluronic acid；HA)、微型透明质酸(微型HA)、羟基丙基甲基纤维素(hydroxypropylmethylcellulose；HPMC)及羧甲基纤维素(carboxymethyl cellulose；CMC)、聚乙烯吡咯啶酮(polyvinylpyrrolidone；PVP)。在一些实例中，溶剂包含去离子水。
在一些实施例中，热反应溶液加热达到或超过LCST点。具体而言，在将热反应溶液加热之后，聚合物的疏水性部分显露出来，由此产生隐形眼镜主体上及/或附近的相对疏水表面。疏水表面可导致隐形眼镜不能展示完整水膜。在一些实施例中，至少一个疏水性部分由具有烷烃、烯烃或炔烃键的碳链组成。在一些实施例中，碳链为以直链形式或包括支链或环状的非直链形式呈现。隐形眼镜主体上的疏水性部分可键合至用于任何随后萃 取、水合、及/或灭菌过程中的溶液的亲水性增强分子的疏水性部分，以使得亲水性增强分子的亲水性部分得以暴露，并且隐形眼镜主体的表面展现亲水性。因此，隐形眼镜的表面亲水性、湿润性及/或润滑性性质可得以改良。在一些实施例中，该方法进一步包括用萃取溶液来萃取隐形眼镜。在用反应溶液来浸没隐形眼镜主体及/或用热反应溶液来浸没隐形眼镜之后，可执行萃取过程。
在一些实施例中，当隐形眼镜主体为硅水凝胶隐形眼镜，萃取溶液可为异丙醇及50％v/v异丙醇。在其他实施例中，当隐形眼镜主体为水凝胶隐形眼镜时，萃取溶液可为硼酸盐缓冲盐水。在一些实施例中，萃取溶液进一步包括至少一种亲水性增强分子。在一些实施例中，亲水性增强分子包括至少一个官能基，官能基包括羧基团、胺基团、硫醇基团、硫化物基团、醛基团、羟基团、醇盐基团、N-杂环基团、吡咯啶酮基团、硼氢化物基团或其组合。在一些实例中，较佳类别的亲水性增强分子包括含有羧基、胺基或硫醇的化学品。在一些实例中，亲水性增强分子可为聚(丙烯酰胺-共-丙烯酸)、聚(丙烯酸)、聚乙烯吡咯啶酮(polyvinylpyrrolidone；PVP)、透明质酸(hyaluronic acid；HA)、微型透明质酸(微型HA)、羧甲基纤维素(carboxymethyl cellulose；CMC)、羟基丙基甲基纤维素(hydroxypropylmethylcellulose；HPMC)、界面活性剂或其组合。在一些实施例中，亲水性增强分子可与热反应溶液的聚合物相同。在一些实施例中，亲水性增强分子可不同于热反应溶液的聚合物。
该方法进一步包括执行水合过程。在一些实施例中，隐形眼镜借由水合溶液诸如硼酸盐缓冲盐水来水合。在一些实施例中，水合溶液可进一步包括如上所述亲水性增强分子。在一些实施例中，亲水性增强分子可与热反应溶液的聚合物相同。在一些实施例中，亲水性增强分子可不同于热反应溶液的聚合物。亲水性增强分子可具有LCST性质。
该方法进一步包括执行灭菌过程。在一些实施例中，在执行灭菌过程之前，隐形眼镜用包装溶液来包装。在一些实施例中，包装溶液包括硼酸盐缓冲液盐水。在一些实施例中，包装溶液进一步包括至少一种亲水性增强分子，诸如透明质酸、微型透明质酸、羧甲基纤维素、羟基丙基甲基纤维素、界面活性剂或其组合。在一些实施例中，亲水性增强分子可与热反应溶液的聚合物相同。在一些实施例中，亲水性增强分子可不同于热反应溶液的聚合物。在一些实施例中，隐形眼镜在约121℃下灭菌约20分钟。
本揭露的另一态样提供隐形眼镜。隐形眼镜包括隐形眼镜主体及覆盖 隐形眼镜主体的蓝光阻挡材料，其中蓝光阻挡材料包括分散在隐形眼镜主体上的多个金属颗粒。
在一些实施例中，隐形眼镜主体包括水凝胶隐形眼镜或硅水凝胶隐形眼镜。在一些实施例中，隐形眼镜主体包括羧基、胺基、羟基或吡咯啶酮结构。例如，隐形眼镜主体可具有羧基、胺基(例如，一级胺、二级胺或三级胺)、羟基、吡咯啶酮基团、硫醇基或其组合。
在一些实施例中，多个金属颗粒包括银、金、钴、锰、镍、铜、锌、铂、钯、镉、铟、钾、钙、铁或其组合。在一些实施例中，多个金属颗粒具有约1nm至10000nm的直径。在一些实施例中，金属颗粒的直径较佳为1nm至1000nm，或更佳1nm至200nm。在一些实施例中，金属颗粒可为彼此分离的颗粒、丛集或其组合。在一些实施例中，金属颗粒实质上均匀地在隐形眼镜主体中散开。在一些实施例中，以隐形眼镜的总重量计，隐形眼镜包括约1wt％至约20wt％蓝光阻挡材料。仅以少许量蓝光阻挡材料，本揭露的隐形眼镜可达成良好蓝光阻挡效率。
在一些实施例中，隐形眼镜在380nm至800nm范围内的可见光下，表现出可调谐等离子体子共振。在一些实施例中，隐形眼镜较佳在380nm至500nm范围内的可见光下，表现出可调谐等离子体子共振。在一些实施例中，隐形眼镜更佳在380nm至450nm范围内的可见光下，表现出可调谐等离子体子共振。在一些实施例中，隐形眼镜在380nm至约480nm范围内的波长下，抑制约5％至约99％的蓝光，同时480nm至800nm下的光阻挡功效为14％至98％。在一些实施例中，隐形眼镜具有约30度至70度的平均水接触角。在一些实施例中，隐形眼镜具有约0.1度至35度的平均延迟现象。
<实例1：制备水凝胶隐形眼镜>
2-羟乙基甲基丙烯酸酯(2-hydroxyethyl methacrylate；HEMA)及甲基丙烯酸与交联剂乙二醇二甲基丙烯酸酯及三羟甲基丙基丙烯酸三甲酯混合以形成混合物。混合物用于在磁搅拌棒搅拌下，溶解其余粉末包括活性蓝染料、双(2,4,6-三甲基苯甲酰基)-苯基氧化膦(IRGACURE 819)及2-[2-羟基-5-[2-(甲基丙烯酰氧基)乙基]苯基]-2H-苯并三唑，直到所有粉末溶解于混合物中为止。
添加如此制备的反应混合物并且在由聚丙烯制成的前后弯曲模具中铸造并且在空气中，在5mW/cm 2下照射20分钟。将干燥状态下的所得水凝胶隐形眼镜释放，然后在60℃下，借由硼酸盐缓冲盐水来萃取两次，持续1小时。将所得水凝胶隐形眼镜安置于填充有硼酸盐缓冲盐水的泡罩包装中 并且灭菌。所得水凝胶隐形眼镜具有约58％的水含量、约20DK至25DK的氧渗透性、约0.3至0.4的模数、及约1％至3％的蓝光阻挡功效。
<实例2：制备硅水凝胶隐形眼镜>
N-乙烯基吡咯啶酮(N-vinyl pyrrolidone；NVP)、2-羟乙基甲基丙烯酸酯(2-hydroxyethyl methacrylate；HEMA)、甲基丙烯酸及N,N-二甲基苯胺(N,N-dimethylanilline；DMA)的亲水性组分首先与硅胶材料(3-甲基丙烯酰氧基-2-羟基丙氧基)丙基双(三甲基甲硅烷氧基)甲基硅烷混合，然后与交联剂乙二醇二甲基丙烯酸酯及三烯丙基-s-三嗪-2,4,6(1H.3H,5H)-三酮混合。最后，混合物用于在磁搅拌棒搅拌下，溶解其余粉末包括活性蓝染料、双(2,4,6-三甲基苯甲酰基)-苯基氧化膦(IRGACURE 819)及2-[2-羟基-5-[2-(甲基丙烯酰氧基)乙基]苯基]-2H-苯并三唑，直到所有粉末溶解于混合物中为止。
添加如此制备的反应混合物并且在由聚丙烯制成的前后弯曲模具中铸造并且在空气中，在5mW/cm 2下照射30分钟。将干燥状态下的所得硅水凝胶隐形眼镜释放。随后，在50℃下，分别将干燥硅水凝胶隐形眼镜用异丙醇及50％v/v异丙醇萃取1小时，然后在25℃下，用硼酸盐缓冲盐水洗涤两次，持续10分钟。将水合硅水凝胶隐形眼镜安置于填充有硼酸盐缓冲盐水的泡罩包装中并且灭菌。所得硅水凝胶隐形眼镜具有约48％至52％的水含量、约120DK的氧渗透性、约0.6至0.7的模数、及约5％至7％的蓝光阻挡功效。
为了进一步理解隐形眼镜与蓝光阻挡材料之间的反应的细节，制备相同反应混合物，除了将甲基丙烯酸置换为相同量的2-羟乙基甲基丙烯酸酯。随后制造过程与如上所述相同。没有甲基丙烯酸添加的所得硅水凝胶隐形眼镜展示约46％至50％的水含量、约120DK的氧渗透性、约0.6至0.7的模数及约8％至10％的蓝光阻挡功效。
<实例3>
储备溶液经由去离子水来制备以便溶解聚(丙烯酰胺-共-丙烯酸)及柠檬酸三钠的粉末，最终浓度分别为0.5mg/ml及0.1M。将600μL储备溶液添加于由聚丙烯制成的容器中。然后，干燥释放硅水凝胶隐形眼镜或水凝胶隐形眼镜(亦即，隐形眼镜主体)安置于容器中并且浸没至储备溶液中。将300μL的20mM、1.62mM及0.41mM硝酸银溶液添加至容器中并且与储备溶液混合。约5分钟之后，为了确保混合物浸没隐形眼镜，将900μL的去离子水添加至容器中。所得混合物(亦即，反应溶液)为透明的。三个反应 混合物的硝酸银的最终浓度分别为约566.7ppm、45.9ppm、及11.6ppm。
接下来，在室温下，将容器中的硅水凝胶隐形眼镜或水凝胶隐形眼镜用反应溶液培育30分钟。然后，以25℃至85℃的范围温度，容器在烘箱中加热2小时。之后，隐形眼镜用去离子水洗涤两次以便移除未反应的反应溶液。培育过程之后，在50℃下，硅水凝胶隐形眼镜分别借由异丙醇及50％v/v异丙醇来萃取1小时，然后在25℃下，借由硼酸盐缓冲盐水来水合两次，持续10分钟。对于水凝胶隐形眼镜，其接着在60℃下，借由硼酸盐缓冲盐水来萃取两次，持续1小时。在任何进一步实验之前，所有隐形眼镜最终安置于硼酸盐缓冲盐水中。
在各种条件下的反应概述于表1中。在表1中，SiHy表示硅水凝胶隐形眼镜，并且Hy表示水凝胶隐形眼镜。标记X表示380nm至480nm蓝光阻挡功效少于10％，并且标记O表示380nm至480nm蓝光阻挡功效大于10％。
如表1所示。最终隐形眼镜展示将蓝光阻挡材料分散于隐形眼镜主体上的反应为与温度正相关的。图3及图4分别为硅水凝胶隐形眼镜及水凝胶隐形眼镜的数位影像。如图3及图4所示，当培育温度增加时，观察到所得隐形眼镜的增强蓝光阻挡功效(亦即，隐形眼镜的颜色较暗)。另外，借由计算图5A及图5B所示的380nm至480nm下的紫外光-可见光(UV-Vis)光谱概况，在相同条件下，如与水凝胶隐形眼镜(图5A)相比，硅水凝胶隐形眼镜(图5B)对于蓝光阻挡材料更具有反应性。所得硅水凝胶隐形眼镜的对应蓝光阻挡功效达成约8％至约100％的蓝光阻挡功效。此归因于硅水凝胶隐形眼镜具有更高部分的有效官能基，诸如羧基及吡咯啶酮基团。
表1
Figure PCTCN2022111380-appb-000001
<实例4>
遵循如在实例1及2中描述的相同方案，将干燥硅水凝胶隐形眼镜(具有或不具有甲基丙烯酸组分)及水凝胶隐形眼镜浸没于反应溶液中30分钟。 之后，在室温下将隐形眼镜继续在反应溶液中浸泡额外24小时，或密封于玻璃容器中以便在121℃下进行平均20分钟灭菌。最后，在任何进一步实验之前，将隐形眼镜安置于硼酸盐缓冲盐水中。
结果显示于表1及图6A至图6C中。没有甲基丙烯酸组分的硅水凝胶隐形眼镜在灭菌方面几乎没有反应性，如图6A所示。具有甲基丙烯酸组分的硅水凝胶隐形眼镜(SiHy)在24h室温培育及121℃下的灭菌方面均具有反应性，如图6B所示。另一方面，仅在继续进行灭菌时，水凝胶隐形眼镜(Hy)与反应溶液反应，如图6C展示。
如在实例1及2中的结果来证明，实例中的资料加强以下结论：与没有甲基丙烯酸添加的硅水凝胶隐形眼镜或水凝胶隐形眼镜相比，具有更多官能基(例如，吡咯啶酮基团、及甲基丙烯酸基团)的硅水凝胶隐形眼镜在蓝光阻挡方面证明更有效。
<实例5>
借由遵循如在实例1及2中描述的反应溶液方案及示意性制造说明，执行一系列实验来研究蓝光阻挡材料修饰中的聚(丙烯酰胺-共-丙烯酸)及柠檬酸三钠对于硅水凝胶隐形眼镜的效应。在任何其他检查之前，全部所得隐形眼镜转移至硼酸盐缓冲盐水。
实验条件及结果显示于表2及图7A至图7B。在表2中，PAA表示聚(丙烯酰胺-共-丙烯酸)，并且TSC为柠檬酸三钠的缩写。蓝光阻挡涉及380nm至480nm波长下的蓝光阻挡功效。
另外，借由#6制造的所得隐形眼镜的稳定性借由另外在50℃下培育隐形眼镜1个月来进一步测试，其显示于#7中。图7B显示隐形眼镜#6及#7的UV-Vis透射光谱。如与#6中的结果相比，UV-Vis吸收概况、对应蓝光阻挡功效都不显著改变。
表2
Figure PCTCN2022111380-appb-000002
<实例6>
首先借由使用去离子水在室温下、在磁搅拌棒下溶解聚(丙烯酰胺-共-丙烯酸)及柠檬酸三钠的两种粉末1小时，制备96ml的储备溶液。聚(丙烯酰胺-共-丙烯酸)及柠檬酸三钠的最终浓度分别为0.5mg/ml及0.1M。然后，在搅拌下，将176ml的去离子水及16ml硝酸银溶液添加至储备溶液另外1小时以形成反应溶液。硝酸银的最终浓度为15ppm。
各容器添加借由1.8ml反应溶液。然后将各容器负载一个水凝胶隐形眼镜，将其浸没于反应溶液中。然后，所有容器划分成两组，如图2A及图2B示出。将一组安置于图2A展示的水蒸气的水浴中。另一组在图2B展示的烘箱中培育。两种培育条件在85℃下控制2小时。
结果展示于图8中。自图8，可以看出在烘箱中培育的隐形眼镜对于蓝光阻挡材料修饰而言为无效的，蓝光阻挡功效为约25％并且隐形眼镜的颜色为最淡的。另一方面，在水蒸气的水浴中培育的彼等容器展示约45％蓝光阻挡效率。当将由聚丙烯制成的容器替换成有助于热量转导的玻璃材料时，观察到蓝光阻挡功效增加约10％。萃取、水合及灭菌之后，具有水蒸气中的反应的隐形眼镜展示约15％的蓝光阻挡功效。由于实例3中的结果证明隐形眼镜上的蓝光阻挡材料的修饰与温度有关，咸信在水蒸气中比在空气中更有效的热量转导解释实例6中的结果，表明对于与温度有关反应而言，与烘箱相比，由水浴显现的水蒸气相对更有效。因此，所有以下实验都经由水蒸气来应用。
<实例7>
进行一系列实验来研究一旦移除初始组分聚(丙烯酰胺-共-丙烯酸)或添加额外辅助材料，水凝胶隐形眼镜上的蓝光阻挡材料反应。为了制备用于比较的一系列反应溶液，#14、#15、#18及#19中的实验用与实例6类似的方法来制备。关于#16-#17及#20-#24中的实验，首先制备含有聚(丙烯酰胺-共-丙烯酸)及柠檬酸三钠的96ml混合物。然后，在搅拌下将128ml去离子水及16ml硝酸银溶液添加至混合物中另外5分钟。最终，在搅拌下，将具有48ml 31.3μM PA(poly(acrylic acid)；聚(丙烯酸))、0.1wt％PVP(polyvinylpyrrolidone；聚乙烯吡咯啶酮，29000道尔顿)、0.1wt％HA(hyaluronic acid；透明质酸)、0.1wt％微型HA(微型透明质酸)或0.5wt％CMC(carboxymethyl cellulose；羧甲基纤维素)的另一种材料选择性添加至混合物另外20分钟。硝酸银的最终浓度为15ppm。
容器中的每一者安置有一个干燥水凝胶隐形眼镜。然后，将1.8ml如此制备的反应溶液添加至容器30分钟。然后，将所有容器在水蒸气中在85℃ 下培育2小时。培育之后，所有隐形眼镜安置于负载有2ml新鲜去离子水的新容器中。所有样品经由数位摄影机来记录，并且所得影像借由来自电脑程序的调色板附件或影像J软件，经由处理来分析。效应聚(丙烯酰胺-共-丙烯酸)或其他额外辅助材料显示于表3中。
在表3中，PAA表示聚(丙烯酰胺-共-丙烯酸)；PA表示具有约2000道尔顿的分子量的聚(丙烯酸)；TSC表示柠檬酸三钠；PVP表示聚乙烯吡咯啶酮；HA表示具有约1000000道尔顿的分子量的透明质酸；微型HA表示具有少于约10000道尔顿的分子量的微型透明质酸；CMC表示具有约250000道尔顿的分子量的羧甲基纤维素；并且CL表示隐形眼镜。标记*表示蓝光阻挡材料范围不均匀地分布于隐形眼镜上。颜色变化(△C)：黄颜色(255，255，0)充当用于进一步比较的对照组。
表3
Figure PCTCN2022111380-appb-000003
<实例8>
如实例8示出，含有功能化学品诸如透明质酸(hyaluronic acid；HA)、 微型透明质酸(微型HA)、羧甲基纤维素(carboxymethyl cellulose；CMC)、及羟基丙基甲基纤维素(hydroxypropyl methylcellulose；HPMC)的额外溶液进一步调节蓝光阻挡材料修饰。此等功能化学品有助于改良医疗装置的表面性质。因此，为了最大改良表面性质及平衡蓝光阻挡功效，在水合、灭菌或其组合的过程中运作的功能化学品在一系列检查中予以测试。
隐形眼镜首先根据#21描述的方法(实例7)来制备。蓝光阻挡材料修饰2小时之后，隐形眼镜用去离子水洗涤两次并且在额外加热1小时的水浴中，在85℃下，在溶液中培育，该溶液替代地为去离子水，0.1wt％HA、0.1wt％微型HA、0.5wt％CMC、0.3wt％HPMC(hydroxypropyl methylcellulose；羟基丙基甲基纤维素，80cp至120cp)或0.1wt％HPMC(羟基丙基甲基纤维素，2600cp至5600cp)。然后，隐形眼镜在硼酸盐缓冲液盐水中在60℃下水合0.5小时三次。最终，隐形眼镜包装于具有3ml包装溶液的玻璃容器，该溶液视情况为硼酸盐缓冲液盐水、0.1wt％透明质酸、0.1wt％微型透明质酸、0.5wt％羧甲基纤维素、0.3wt％羟基丙基甲基纤维素(80cp至120cp)或0.1wt％羟基丙基甲基纤维素(2600cp至5600cp)。然后，将包装隐形眼镜发送至在121℃下、在灭菌过程中处理平均20分钟。所有结果显示于表4及表5中。
在表4及表5中，HA表示具有约1000000道尔顿的分子重量的透明质酸；微型HA表示具有少于约10000道尔顿的分子重量的微型透明质酸；HPMC a表示具有80cp至120cp的羟基丙基甲基纤维素；HPMC b表示具有2600cp至5600cp的羟基丙基甲基纤维素；并且CMC表示具有约250000道尔顿的分子重量的羧甲基纤维素。润滑性评分为定性分级方案，其中使用0至6的量表，并且0或较低数字指示更好润滑性。样品用过量去离子水冲洗至少三次，然后在评估之前，转移至磷酸盐缓冲生理盐水(Phosphate buffered saline，PBS)。评估之前，手用肥皂液冲洗，用去离子水广泛冲洗，然后用
Figure PCTCN2022111380-appb-000004
毛巾干燥。没有借由功能化学品来进一步修饰的水凝胶隐形眼镜的润滑性定义为2级。对于一致性，所有评分借由相同两个操作者来独立地收集以避免偏差并且迄今为止的资料在评估中展现很好定性一致性及相容性。
在水合、灭菌或其组合的过程中运作的功能化学品适用于调节蓝光阻挡功效(表4所示)及表面润滑性(表5所示)。如表4所示。总体上，除了在反应溶液中添加更多银以外，与在硼酸盐缓冲液盐水中相比，在微型HA、HA或HPMC中灭菌的水凝胶隐形眼镜在蓝光阻挡方面，在约1％至约16％的范围内增加显著。
如在表5中所示。对于在硼酸盐缓冲液盐水、HA、HPMC或CMC中灭菌的所有所得隐形眼镜而言，与其他条件比较，为了额外水合而在0.3wt％HPMC(80cp至120cp，估计26000道尔顿)中培育的隐形眼镜执行经增强的表面润滑性水准。另外，将HA及HPMC添加至灭菌过程亦足以增加获自不同水合条件的所有水凝胶隐形眼镜的润滑性。
表4
Figure PCTCN2022111380-appb-000005
表5
Figure PCTCN2022111380-appb-000006
<实例9>
首先借由在约3分钟音波处理下，借由使用去离子水来溶解聚(丙烯酰胺-共-丙烯酸)及柠檬酸三钠，制备84ml混合物。聚(丙烯酰胺-共-丙烯酸)及柠檬酸三钠的最终浓度分别为0.5mg/ml及0.1M。然后，将磁搅拌棒安置在混合物中并且保持稳定约300rpm至400rpm。随后将具有两个不同浓度的 126ml硝酸银溶液缓慢添加至混合物。15分钟之后，然后将42ml的0.1wt％PVP添加至混合物，另外搅拌20分钟。获得具有15ppm及22.5ppm硝酸银的最终浓度的所得反应溶液。
然后，将干燥释放水凝胶隐形眼镜浸没于容器中的1.8ml如此制备反应溶液中30分钟。然后，所有容器在水蒸气中在85℃下培育2小时。之后，所有隐形眼镜用去离子水洗涤两次。然后，在85℃下，在1小时内，经由水浴培育，将隐形眼镜浸泡至恒温箱300s，其中反应性溶液分别为0.3wt％HPMC(80cp至120cp)、及0.1wt％HPMC(80cp至120cp)与0.1wt％PVP。之后，将隐形眼镜在硼酸盐缓冲盐水中在60℃下水合0.5小时三次并且填充1ml的0.1wt％微型HA与0.1wt％HA、0.2wt％微型HA、0.2wt％HA、0.1wt％HA与0.5wt％CMC、0.1wt％微型HA与0.5wt％CMC、界面活性剂9217或0.1wt％HA与0.5wt％CMC及界面活性剂9217，界面活性剂9217含有0.1wt％聚乙二醇200、0.01wt％吐温80、及2wt％2-(甲基丙烯酰氧基)乙基2-(三甲基铵)乙基磷酸盐-n-甲基丙烯酸丁酯共聚物。
经由实例1获得的对照水凝胶隐形眼镜及商业产品DAYILIED TOTAL 1隐形眼镜的表面性质在表6中列出。在表6中，WBUT表示水破裂时间。
表6
Figure PCTCN2022111380-appb-000007
表7总结经由水合过程或包装溶液来调节的各种条件之后的所得隐形眼镜。在表7中，HA表示具有约1000000道尔顿的分子量的透明质酸；微型HA表示具有少于约10000道尔顿的分子量的微型透明质酸；HPMC表示羟基丙基甲基纤维素，并且CMC表示具有约250000道尔顿的分子量的羧甲基纤维素。BLB表示380nm至480nm的波长下的蓝光阻挡功效。Het.是指隐形眼镜上的蓝光阻挡材料的不均匀分布。WBUT是指水破裂时间。标记#表示在灭菌之后的隐形眼镜的包装溶液显示淡黄色。标记*表示一个或一个以上所得隐形眼镜不能在开始时显示完整水膜。
在0.3wt％HPMC中水合之后，借由CMC来添加包装溶液，当硝酸银的添加浓度为15ppm及22.5ppm时，所得隐形眼镜展示约18％至37％的蓝光阻 挡功效。然而，当HPMC的部分替换成PVP时，所得隐形眼镜的蓝光阻挡功效及保水性显著减少。此结果可归因于两种聚合物之间对于隐形眼镜的表面微观结构中的溶解及稳定性的合作效应。
总体上，用HPMC水合的隐形眼镜展示前进接触角的约15°至35°减少及迟滞现象与增加保水能力(3分钟之后，水破裂区域减少20％至55％)，表明如与对照隐形眼镜相比，隐形眼镜的所得亲水性质得以改良。然而，填充有硼酸盐缓冲盐水的隐形眼镜在水破裂时间的第一时点处展示显著减少。具体而言，对于具有22.5ppm硝酸银反应之，超过80％的隐形眼镜在检查开始时不能够执行完全完整水膜。此归因于在超过转变温度(例如，较低临界溶液温度)的温度下用HPMC来培育时，分布于隐形眼镜上的疏水性区域增加。观察到当在包装溶液中添加的潮湿化学品诸如HA、微型HA、CMC、及界面活性剂逐渐地增加时，水破裂时间及水破裂区域改良，包装溶液中的潮湿化学品的浓度增加0.2wt％、0.6wt％及超过1wt％。在选定潮湿化学品之中，相对小分子诸如微型HA及界面活性剂9217更有效地覆盖隐形眼镜的疏水性部分，导致延长及保持所得隐形眼镜上的水膜及表面润滑性。总之，此结论指示考虑到表面亲水性及湿润性，与商业产品DAILIES TOTAL 1隐形眼镜比较，本揭示案的蓝光阻挡隐形眼镜为相容的。
表7
Figure PCTCN2022111380-appb-000008
Figure PCTCN2022111380-appb-000009
<实例10>
自实例9收集样品1、样品2及样品3，对应包装溶液分别为硼酸盐缓冲盐水、界面活性剂9217及具有0.5wt％CMC及0.1wt％HA的界面活性剂9217。样品1-3经由数位摄影机来记录，并且所得影像借由来自电脑程序的调色板附件或影像J软件，经由处理来分析，如图9所示。然后，关于UV-Vis光谱，检查每一种产物。计算380nm至480nm的蓝光阻挡功效。表8概述样品1-3及两个商业产品的结果。
在表8中，黄颜色(255，255，0)充当用于颜色变化(△C)的进一步比较的对照组。所有样品1-3显示超过其他两种商业产品的约30％至35％蓝光阻挡，同时与仅具有大约14％的Miacare相比，其以黄色显示的颜色为更少微黄色的。以荧光绿色呈现的Freshkon Daily不适合于颜色比较，但是仅约10.6％的蓝光阻挡几乎不足以眼睛保护。
表8
Figure PCTCN2022111380-appb-000010
如上所述，根据本揭露的实施例，提供隐形眼镜及其制造方法。隐形眼镜包括分散在隐形眼镜主体上的多个蓝光阻挡材料。与商业隐形眼镜比较，本揭示案的隐形眼镜具有良好蓝光阻挡性质并且展现相对更少微黄色外观。另外，本揭示案的隐形眼镜具有良好表面亲水性、保水性质与润滑 性。
虽然本揭露相当详细地参考其某些实施例来描述，但是其他实施例为可能的。因此，随附权利要求的精神及范围不应限于本文包含的实施例的描述。
熟习此项技术者显而易知本揭露的结构可产生各种修改及变化而不脱离本揭露的范围或精神。鉴于前述，规定本揭露涵盖本揭露的修改及变化，只要其属于权利要求的范围内。

Claims (24)

  1. 一种隐形眼镜，其特征在于，包括：
    隐形眼镜主体；及
    蓝光阻挡材料，覆盖该隐形眼镜主体，其中该蓝光阻挡材料包含分散于该隐形眼镜主体上的多个金属颗粒。
  2. 根据权利要求1所述的隐形眼镜，其特征在于，所述金属颗粒包含银、金、钴、锰、镍、铜、锌、铂、钯、镉、铟、钾、钙、铁或其组合。
  3. 根据权利要求1所述的隐形眼镜，其特征在于，以该隐形眼镜的总重量计，该隐形眼镜包含1wt％至20wt％的该蓝光阻挡材料。
  4. 根据权利要求1所述的隐形眼镜，其特征在于，所述金属颗粒具有1nm至10000nm的直径。
  5. 根据权利要求1所述的隐形眼镜，其特征在于，该隐形眼镜在380nm至800nm范围内的可见光下，表现出可调谐等离子体子共振。
  6. 根据权利要求1所述的隐形眼镜，其特征在于，该隐形眼镜在380nm至480nm范围内的波长下，抑制5％至99％的蓝光。
  7. 根据权利要求1所述的隐形眼镜，其特征在于，该隐形眼镜具有30度至70度的平均水接触角。
  8. 根据权利要求1所述的隐形眼镜，其特征在于，该隐形眼镜具有0.1度至35度的平均迟滞现象。
  9. 根据权利要求1所述的隐形眼镜，其特征在于，该隐形眼镜主体包含水凝胶隐形眼镜或硅水凝胶隐形眼镜。
  10. 根据权利要求1所述的隐形眼镜，其特征在于，该隐形眼镜主体包含羧基、胺基、羟基或吡咯啶酮结构。
  11. 一种制造隐形眼镜的方法，其特征在于，包括以下步骤：
    提供隐形眼镜主体；及
    用反应溶液来浸没该隐形眼镜主体，以形成具有覆盖该隐形眼镜主体的蓝光阻挡材料的隐形眼镜，其中该反应溶液包含：
    第一溶剂；
    包含金属离子的至少一种化合物；及
    用于将该金属离子还原至金属颗粒的至少一种还原剂。
  12. 根据权利要求11所述的方法，其特征在于，该第一溶剂包含水溶性溶剂。
  13. 根据权利要求11所述的方法，其特征在于，该金属离子包括银离子、金离子、钴离子、锰离子、镍离子、铜离子、锌离子、铂离子、钯离子、镉离子、铟离子、钾离子、钙离子、铁离子或其组合。
  14. 根据权利要求11所述的方法，其特征在于，该还原剂包含至少一个官能基，该官能基包括羧基团、胺基团、硫醇基团、硫化物基团、醛基团、羟基团、醇盐基团、N-杂环基团、吡咯啶酮基团、硼氢化物基团或其组合。
  15. 根据权利要求11所述的方法，其特征在于，该反应溶液进一步包括用羧基团、胺基团、硫醇基团、硫化物基团、醛基团、羟基团、丙烯酰胺、醇盐基团、N-杂环基团、吡咯啶酮基团、乙二醇基团或其组合来官能化的至少一种亲水性增强分子。
  16. 根据权利要求11所述的方法，其特征在于，进一步包括以下步骤：
    用包装溶液来包装该隐形眼镜，其中该包装溶液包括至少一种亲水性增强分子；及
    执行灭菌过程。
  17. 根据权利要求11所述的方法，其特征在于，进一步包括以下步骤：当用该反应溶液来浸没该隐形眼镜主体时，在25℃至135℃范围内的温度下执行加热过程。
  18. 根据权利要求17所述的方法，其特征在于，该加热过程包括在恒温箱中，加热容纳该隐形眼镜主体及该反应溶液的容器20分钟至24小时。
  19. 根据权利要求18所述的方法，其特征在于，该恒温箱包含烘箱、高压蒸汽杀菌器或水浴恒温箱。
  20. 根据权利要求11所述的方法，其特征在于，进一步包括以下步骤：
    在低于较低临界溶液温度的温度下，制备热反应溶液，其中该热反应溶液包括溶解于第二溶剂中的聚合物；
    用该热反应溶液来浸没该隐形眼镜；及
    将该热反应溶液加热以在该隐形眼镜主体上形成至少一个疏水性部分。
  21. 根据权利要求20所述的方法，其特征在于，该聚合物是用羧基团、胺基团、硫醇基团、硫化物基团、醛基团、羟基团、丙烯酰胺、醇盐基团、N-杂环基团、吡咯啶酮基团、乙二醇基团或其组合来官能化。
  22. 根据权利要求20所述的方法，其特征在于，该至少一个疏水性部分由具有烷烃、烯烃或炔烃键的碳链组成。
  23. 根据权利要求22所述的方法，其特征在于，该碳链为以直链形式或包括支链或环状的非直链形式呈现。
  24. 根据权利要求20所述的方法，其特征在于，进一步包括以下步骤：
    用萃取溶液来萃取该隐形眼镜；
    用水合溶液来执行水合过程；及
    用包装溶液来执行灭菌过程，其中该萃取溶液、该水合溶液及该包装溶液中的至少一者包括至少一种亲水性增强分子。
PCT/CN2022/111380 2020-08-21 2022-08-10 隐形眼镜及其制造方法 WO2023020346A1 (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US202063068383P 2020-08-21 2020-08-21
US17/445,313 2021-08-18
US17/445,313 US20220057653A1 (en) 2020-08-21 2021-08-18 Contact lens and method of manufacturing the same

Publications (1)

Publication Number Publication Date
WO2023020346A1 true WO2023020346A1 (zh) 2023-02-23

Family

ID=80270686

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/CN2022/111380 WO2023020346A1 (zh) 2020-08-21 2022-08-10 隐形眼镜及其制造方法
PCT/CN2022/112744 WO2023020478A1 (zh) 2020-08-21 2022-08-16 隐形眼镜及其制造方法

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/112744 WO2023020478A1 (zh) 2020-08-21 2022-08-16 隐形眼镜及其制造方法

Country Status (3)

Country Link
US (3) US20220057653A1 (zh)
TW (2) TWI833300B (zh)
WO (2) WO2023020346A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019229725A2 (en) * 2018-06-02 2019-12-05 BODDEDA, Apparao A smart contact lens for performing wireless operations and a method of producing the same
US20220057653A1 (en) * 2020-08-21 2022-02-24 Pegavision Corporation Contact lens and method of manufacturing the same
CN114671974A (zh) * 2022-03-31 2022-06-28 华诺森（武汉）生物医药技术有限公司 一种硅水凝胶隐形眼镜及其配方与制备方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030149187A1 (en) * 2002-01-25 2003-08-07 Fuji Photo Film Co., Ltd. Thin-layer metal film
US20070298242A1 (en) * 2006-06-26 2007-12-27 University Of Central Florida Research Foundation, Inc. Lenses having dispersed metal nanoparticles for optical filtering including sunglasses
JP2008133535A (ja) * 2006-10-26 2008-06-12 Ube Nitto Kasei Co Ltd 金属ナノ粒子付着基材の製造方法、基材付着性金属ナノ粒子形成用組成物、金属層被覆基材の製造方法、無電解めっき前処理方法、無電解めっき前処理用組成物および無電解めっき品
US20150362757A1 (en) * 2014-06-12 2015-12-17 Smart Performer Co., Ltd. Colored contact lens provided with blue light filtering and anti-uv functions
CN109212777A (zh) * 2017-07-05 2019-01-15 晶硕光学股份有限公司 具有表面修饰的隐形眼镜及其制备方法
CN210323641U (zh) * 2019-09-30 2020-04-14 江苏视准医疗器械有限公司 一种抗蓝光隐形眼镜
WO2021006411A1 (ko) * 2019-07-09 2021-01-14 주식회사 인터로조 블루라이트 차단 콘택트렌즈 및 이의 제조 방법
CN213122489U (zh) * 2020-08-26 2021-05-04 江苏汇鼎光学眼镜有限公司 一种防蓝光效果好的偏光镜片
US20220057653A1 (en) * 2020-08-21 2022-02-24 Pegavision Corporation Contact lens and method of manufacturing the same

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8707731D0 (en) * 1987-04-01 1987-05-07 Coopervision Optics Forming opaque coloured areas in contact lenses
US6524379B2 (en) * 1997-08-15 2003-02-25 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
JP2002131704A (ja) * 2000-10-20 2002-05-09 Masayuki Kuzuu メタリックコンタクトレンズ
US8882267B2 (en) * 2006-03-20 2014-11-11 High Performance Optics, Inc. High energy visible light filter systems with yellowness index values
JP2010052985A (ja) * 2008-08-28 2010-03-11 Fujifilm Corp 金属酸化物微粒子分散液及び成形体
TW201544867A (zh) * 2014-05-27 2015-12-01 Metal Ind Res & Dev Ct 隱形眼鏡及其製造方法
CN104793349B (zh) * 2015-01-29 2017-09-19 广州琦安琦视觉科技有限公司 一种具有防紫外线、衍射光及蓝光多功能隐形眼镜
EP3173826B1 (en) * 2015-11-27 2019-02-13 Pegavision Corporation Hydrogel composition and hydrogel contact lenses made of the composition
CN106810640B (zh) * 2015-11-27 2019-03-22 晶硕光学股份有限公司 水胶组成物及水胶镜片
US20210132416A1 (en) * 2019-10-31 2021-05-06 Menicon Singapore Pte Ltd. Contact lens with selective wavelength transmittance
TWI725719B (zh) * 2020-01-21 2021-04-21 天辰創新材料科技股份有限公司 用以抗藍光之眼鏡鏡片材料、眼鏡鏡片及其製程

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030149187A1 (en) * 2002-01-25 2003-08-07 Fuji Photo Film Co., Ltd. Thin-layer metal film
US20070298242A1 (en) * 2006-06-26 2007-12-27 University Of Central Florida Research Foundation, Inc. Lenses having dispersed metal nanoparticles for optical filtering including sunglasses
JP2008133535A (ja) * 2006-10-26 2008-06-12 Ube Nitto Kasei Co Ltd 金属ナノ粒子付着基材の製造方法、基材付着性金属ナノ粒子形成用組成物、金属層被覆基材の製造方法、無電解めっき前処理方法、無電解めっき前処理用組成物および無電解めっき品
US20150362757A1 (en) * 2014-06-12 2015-12-17 Smart Performer Co., Ltd. Colored contact lens provided with blue light filtering and anti-uv functions
CN109212777A (zh) * 2017-07-05 2019-01-15 晶硕光学股份有限公司 具有表面修饰的隐形眼镜及其制备方法
WO2021006411A1 (ko) * 2019-07-09 2021-01-14 주식회사 인터로조 블루라이트 차단 콘택트렌즈 및 이의 제조 방법
CN210323641U (zh) * 2019-09-30 2020-04-14 江苏视准医疗器械有限公司 一种抗蓝光隐形眼镜
US20220057653A1 (en) * 2020-08-21 2022-02-24 Pegavision Corporation Contact lens and method of manufacturing the same
US20220057655A1 (en) * 2020-08-21 2022-02-24 Pegavision Corporation Contact lens and method of manufacturing the same
CN213122489U (zh) * 2020-08-26 2021-05-04 江苏汇鼎光学眼镜有限公司 一种防蓝光效果好的偏光镜片

Also Published As

Publication number Publication date
TWI833300B (zh) 2024-02-21
TWI833307B (zh) 2024-02-21
TW202309611A (zh) 2023-03-01
US20220057655A1 (en) 2022-02-24
TW202309612A (zh) 2023-03-01
WO2023020478A1 (zh) 2023-02-23
US20240085726A1 (en) 2024-03-14
US20220057653A1 (en) 2022-02-24

Similar Documents

Publication Publication Date Title
WO2023020346A1 (zh) 隐形眼镜及其制造方法
JP6982640B2 (ja) 架橋親水性コーティングを備えるシリコーンヒドロゲルレンズ
CN104144972B (zh) 离子有机硅水凝胶
RU2621721C2 (ru) Силиконовые полимеры, содержащие сульфокислотные группы
CN107255839B (zh) 具有亲水层的接触透镜
CN103777254B (zh) 制造软性硅氧烷水凝胶接触透镜的方法
CN101971057B (zh) 眼用透镜涂覆方法
CN104114612B (zh) 包含所需的水含量和透氧度的有机硅水凝胶
US8647699B2 (en) Method for coating silicone hydrogels
EP2101838B1 (en) Process for the coating of contact lenses
EP2109784B2 (en) Antimicrobial medical devices including silver nanoparticles
JP5689418B2 (ja) 改善された加水分解安定性を有するイオン性シリコーンヒドロゲル
AU2017306270A1 (en) Polymer compositions containing grafted polymeric networks and processes for their preparation and use
TW201030034A (en) Silicone hydrogel materials with chemically bound wetting agents
TW201209079A (en) Method for making UV-absorbing ophthalmic lenses
KR20110014672A (ko) 감소된 단백질 흡수를 나타내는 실리콘 하이드로젤 콘택트 렌즈
AU2021399237A1 (en) Photostable mimics of macular pigment
KR101963513B1 (ko) 세리아 입자를 포함한 콘택트렌즈 및 이의 제조 방법
CN105008115B (zh) 具有在表面上的减少量的硅的含硅氧烷接触镜片
TWI551616B (zh) 一種應用於眼科物件之矽水凝膠的製造方法
US20210301088A1 (en) Ophthalmic devices containing transition metal complexes as high energy visible light filters
TW202317596A (zh) 作為可見光吸收劑之過渡金屬錯合物
TW202336496A (zh) 含有光吸收區之隱形眼鏡及其製備方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22857658

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE