WO2023082166A1 - 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
WO2023082166A1
WO2023082166A1 PCT/CN2021/130237 CN2021130237W WO2023082166A1 WO 2023082166 A1 WO2023082166 A1 WO 2023082166A1 CN 2021130237 W CN2021130237 W CN 2021130237W WO 2023082166 A1 WO2023082166 A1 WO 2023082166A1
Authority
WO
WIPO (PCT)
Prior art keywords
lens
hydrophilic
initiator
methacrylate
monomer
Prior art date
Application number
PCT/CN2021/130237
Other languages
English (en)
French (fr)
Inventor
郑秀宜
李坤灿
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
Priority to US17/772,147 priority Critical patent/US20240168200A1/en
Priority to CN202180005076.1A priority patent/CN116438252A/zh
Priority to PCT/CN2021/130237 priority patent/WO2023082166A1/zh
Priority to TW111101158A priority patent/TWI820572B/zh
Publication of WO2023082166A1 publication Critical patent/WO2023082166A1/zh

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G02B1/043—Contact lenses
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • 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
    • 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
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/12—Optical coatings produced by application to, or surface treatment of, optical elements by surface treatment, e.g. by irradiation
    • 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
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • 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
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
    • G02B2207/109—Sols, gels, sol-gel materials

Definitions

  • the present disclosure relates to a contact lens and a method of manufacturing the same.
  • silicone hydrogel contact lenses Due to the high oxygen permeability of silicone hydrogel contact lenses, oxygen can pass through the lens to reach the cornea, thereby reducing dry eyes and red eyes. Silicone hydrogel has become the mainstream of the contact lens market in recent years. However, silicone hydrogel contact lenses have some disadvantages. For example, the hydrophobicity of the silicone main material will cause discomfort and dryness to the lens and eyes, and the surface of the lens is prone to protein adsorption and deposition.
  • lens surface modification technology can be used to improve wearing comfort.
  • conventional surface modification techniques have some disadvantages.
  • plasma treatment can be used to modify the surface of contact lenses.
  • contact lenses usually must be dried before plasma treatment, and plasma treatment equipment is expensive. Therefore, plasma treatment will increase the cost of manufacturing contact lenses. cost.
  • surface modification can be achieved by grafting hydrophilic polymers onto contact lenses.
  • this method is only applicable to some types of hydrogel contact lens materials, which must have specific functional groups.
  • contact lenses can be made by adding wetting agents to the lens formulations used to manufacture silicone hydrogel contact lenses, however, wetting agents may not be compatible with the silicone component of the lens formulation and cause the lens to cloud , adversely affect the properties of the lens.
  • wetting agents may not be compatible with the silicone component of the lens formulation and cause the lens to cloud , adversely affect the properties of the lens.
  • the present disclosure provides a contact lens comprising a lens and a hydrophilic polymer layer.
  • the hydrophilic polymer layer intertwines with the lens.
  • the hydrophilic polymer layer and the lens form an interpenetrating polymer network (Interpenetrating polymer network, IPN) or a semi-interpenetrating polymer network (Semi-interpenetrating polymer network, Semi-IPN).
  • IPN interpenetrating polymer network
  • Semi-IPN semi-interpenetrating polymer network
  • the hydrophilic polymer layer is formed by polymerizing the initiator adsorbed on the lens and at least one hydrophilic vinylic monomer.
  • the initiator includes potassium persulfate (Potassium persulfate, KPS), azobisisobutyronitrile (AIBN), 2,2'-azobisisobutylamidine dihydrochloride (2 ,2'-Azobis[2-methylpropionamidine]dihydrochloride, AAPH), 2,2'-Azo-bis-(2-methylbutyronitrile) (2,2'-Azobis-(2-methybutyronitrile), AMBN), 2,2'-Azo-bis-(2,4-dimethylvaleronitrile) (2,2'-Azobis(2,4-dimethyl)valeronitrile, ADVN), 4,4'-Azo-4- Cyanovaleric acid (4,4'-Azobis (4-cyanovaleric acid), ACVA), tert-butanol peroxide (2-Methylpropane-2-peroxol, TBHP), azobisiso
  • KPS
  • At least one hydrophilic vinylic monomer includes acrylic acid, methacrylic acid, acrylamide (Acrylamide), methacrylamide, N,N-dimethylacrylamide (N,N-Dimethylacrylamide, DMA ), N,N-Dimethylmethacrylamide (N,N-Dimethyl-2-propenamide, DMMA), N,N-Dimethylmethacrylamide, N-Hydroxyethylacrylamide (N-Hydroxyethylacrylamide , NHEMAA), N-[tris(hydroxymethyl)methyl]-acrylamide, 2,3-dihydroxypropyl methacrylate (2,3-Dihydroxypropyl methacrylate; Glycerol monomethacrylate, GMMA), hydroxymethacrylate Ethyl ester (HEMA), 2-acrylamido-2-methyl-1-propanesulfonic acid, N-vinylpyrrolidone, methyl methacrylate (Methyl methacrylate, MA
  • At least one hydrophilic vinylic monomer comprises a first hydrophilic vinylic monomer and a second hydrophilic vinylic monomer, the first hydrophilic vinylic monomer and the second hydrophilic vinylic monomer
  • the weight ratio of the hydrophilic vinylic monomers is 20:1 to 1:1.
  • the at least one hydrophilic vinylic monomer comprises different first hydrophilic vinylic monomers, second hydrophilic vinylic monomers, and third hydrophilic vinylic monomers.
  • the lenses comprise hydrogel lenses or silicone hydrogel lenses.
  • the present disclosure provides a method of manufacturing a contact lens comprising the following operations. Allow the lens to absorb the initiator.
  • the initiator adsorbed on the lens is polymerized with at least one hydrophilic vinyl monomer to form a hydrophilic polymer layer intertwined with the lens, wherein the hydrophilic polymer layer and the lens form interpenetrating polymerization network of things or semi-interpenetrating polymer network.
  • allowing the lens to absorb the initiator comprises: soaking the lens in an initiator solution containing the initiator.
  • the concentration of the initiator in the initiator solution is 0.1 wt% to 10 wt%.
  • polymerizing the initiator adsorbed on the lens with at least one hydrophilic vinylic monomer includes the following operations.
  • the lens absorbing the initiator is soaked in a monomer solution containing at least one hydrophilic vinylic monomer. Heating lens and monomer solution.
  • the lens and monomer solution are heated to a temperature of 60°C to 130°C.
  • the lens and monomer solution are heated for 0.5 minutes to 140 minutes.
  • the lens and monomer solution are heated for 30 minutes to 120 minutes.
  • the initiator includes potassium persulfate (KPS), azobisisobutyronitrile (AIBN), 2,2'-azobisisobutylamidine dihydrochloride (AAPH), 2,2 '-Azo-bis-(2-methylbutyronitrile) (AMBN), 2,2'-Azo-bis-(2,4-dimethylvaleronitrile) (ADVN), 4,4'-azo Nitrogen-4-cyanovaleric acid (ACVA), tert-butanol peroxide (TBHP), azobisisobutylimidazoline hydrochloride, cumene hydroperoxide, ditertiary butyl peroxide (DTBP), Benzoyl peroxide or a combination thereof.
  • KPS potassium persulfate
  • AIBN azobisisobutyronitrile
  • AAPH 2,2'-azobisisobutylamidine dihydrochloride
  • AMBN 2,2 '-Azo-bis-(2-methyl
  • At least one hydrophilic vinylic monomer comprises acrylic acid, methacrylic acid, acrylamide, methacrylamide, N,N-dimethylacrylamide (DMA), N,N-dimethyl Methacrylamide (DMMA), N,N-dimethylmethacrylamide, N-hydroxyethylacrylamide (NHEMAA), N-[tris(hydroxymethyl)methyl]-acrylamide, 2,3 -Dihydroxypropyl methacrylate (GMMA), hydroxyethyl methacrylate (HEMA), 2-acrylamido-2-methyl-1-propanesulfonic acid, N-vinylpyrrolidone, methyl methacrylate Acrylate (MAA), Ethylene Glycol Diacrylate, Hydroxypropyl Acrylate, Hydroxypropyl Methacrylate, Trimethylammonium Methacrylate 2-Hydroxypropyl Methacrylate Hydrochloride, Aminopropyl Methacrylate Ester hydrochloride, dimethylamin
  • a range indicated by "one value to another value” is a general representation which avoids enumerating all values in the range in the specification. Therefore, the description of a specific numerical range covers any numerical value in the numerical range and the smaller numerical range bounded by any numerical value in the numerical range, as if the arbitrary numerical value and the smaller numerical value are expressly written in the specification. same range.
  • “about,” “approximately,” “essentially,” or “essentially” includes the stated value and averages within acceptable deviations from the particular value as determined by one of ordinary skill in the art, taking into account the The measurement in question and the specific amount of error associated with the measurement (ie, limitations of the measurement system). For example, “about” can mean within one or more standard deviations of the stated value, or for example within ⁇ 30%, ⁇ 20%, ⁇ 15%, ⁇ 10%, ⁇ 5%. Furthermore, “about”, “approximately”, “essentially” or “substantially” used herein can select a more acceptable range of deviation or standard deviation according to measurement properties, coating properties or other properties, and can be Not one standard deviation applies to all properties.
  • the present disclosure provides a contact lens comprising a lens and a hydrophilic polymer layer.
  • the hydrophilic polymer layer intertwines with the lens.
  • the hydrophilic polymer layer forms an interpenetrating polymer network or a semi-interpenetrating polymer network with the lens.
  • the hydrophilic polymer layer is formed by polymerizing the initiator adsorbed on the lens and at least one hydrophilic vinylic monomer.
  • the hydrophilic polymer layer is a hydrophilic polymer network.
  • the initiator since the contact lens has a network structure, the initiator will be adsorbed on the surface of the contact lens, and will also enter the interior of the network structure. Therefore, when the initiator generates free radicals and undergoes a polymerization reaction with the hydrophilic vinyl monomer, a staggered structure in which the network of the hydrophilic polymer layer and the network structure of the contact lens are entangled will be formed, thereby improving surface of the lens.
  • the hydrophilic polymer layer is not covalently bonded to the lens. In some embodiments, no covalent bond is formed between the hydrophilic polymer layer and the lens.
  • the surface properties of the lens can be modified by the hydrophilic polymer layer to have good hydrophilicity.
  • the hysteresis angle of the contact lens is between 4 degrees and 63 degrees.
  • the hysteresis angle is 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 30, 40, 50, 60 or 63 Spend.
  • the initiator includes potassium persulfate (KPS), azobisisobutyronitrile (AIBN), 2,2'-azobisisobutylamidine dihydrochloride (AAPH), 2,2 '-Azo-bis-(2-methylbutyronitrile) (AMBN), 2,2'-Azo-bis-(2,4-dimethylvaleronitrile) (ADVN), 4,4'-azo Nitrogen-4-cyanovaleric acid (ACVA), tert-butanol peroxide (TBHP), azobisisobutylimidazoline hydrochloride, cumene hydroperoxide, ditertiary butyl peroxide (DTBP), Benzoyl peroxide or a combination thereof.
  • KPS potassium persulfate
  • AIBN azobisisobutyronitrile
  • AAPH 2,2'-azobisisobutylamidine dihydrochloride
  • AMBN 2,2 '-Azo-bis-(2-methyl
  • At least one hydrophilic vinylic monomer comprises acrylic acid, methacrylic acid, acrylamide, methacrylamide, N,N-dimethylacrylamide (DMA), N,N-dimethyl Methacrylamide (DMMA), N,N-dimethylmethacrylamide, N-hydroxyethylacrylamide (NHEMAA), N-[tris(hydroxymethyl)methyl]-acrylamide, 2,3 -Dihydroxypropyl methacrylate (GMMA), hydroxyethyl methacrylate (HEMA), 2-acrylamido-2-methyl-1-propanesulfonic acid, N-vinylpyrrolidone, methyl methacrylate Acrylate (MAA), Ethylene Glycol Diacrylate, Hydroxypropyl Acrylate, Hydroxypropyl Methacrylate, Trimethylammonium Methacrylate 2-Hydroxypropyl Methacrylate Hydrochloride, Aminopropyl Methacrylate Ester hydrochloride, dimethylamin
  • the present disclosure can simultaneously use two different hydrophilic vinylic monomers to react with the initiator. Compared with reacting a single hydrophilic vinylic monomer with an initiator, using two hydrophilic vinylic monomers can make the contact lens have better hydrophilicity and wettability.
  • the type and weight ratio of the hydrophilic vinyl monomer can be adjusted according to the design requirements of the lens.
  • the at least one hydrophilic vinylic monomer comprises different first and second hydrophilic vinylic monomers.
  • the first hydrophilic vinylic monomer has an amine group and the second hydrophilic vinylic monomer has a hydroxyl group.
  • the first hydrophilic vinylic monomer is N,N-dimethylacrylamide (DMA)
  • the second hydrophilic vinylic monomer is 2,3-dihydroxypropyl methacrylate ( GMMA).
  • the weight ratio of the first hydrophilic vinylic monomer to the second hydrophilic vinylic monomer is 20:1 to 1:1.
  • the contact lens can have good hydrophilicity and wettability.
  • the present disclosure can simultaneously use three or more different hydrophilic vinylic monomers to react with the initiator. Compared with reacting a single hydrophilic vinylic monomer with an initiator, the use of three hydrophilic vinylic monomers can make the contact lens have better hydrophilicity and wettability.
  • the type and weight ratio of the hydrophilic vinyl monomer can be adjusted according to the design requirements of the lens.
  • the at least one hydrophilic vinylic monomer comprises different first hydrophilic vinylic monomers, second hydrophilic vinylic monomers, and third hydrophilic vinylic monomers.
  • the first hydrophilic vinylic monomer has an amine group
  • the second hydrophilic vinylic monomer has a hydroxyl group
  • the third hydrophilic vinylic monomer has a group
  • the first hydrophilic vinylic monomer is N,N-dimethylacrylamide (DMA)
  • the second hydrophilic vinylic monomer is 2,3-dihydroxypropyl methacrylate ( GMMA)
  • the third hydrophilic vinylic monomer is (NVP).
  • the lenses comprise hydrogel lenses or silicone hydrogel lenses.
  • the hydrogel lens is made of a non-silicon-containing hydrogel material, and the non-silicon-containing hydrogel material includes at least one hydroxyl vinyl monomer, a hydrophilic monomer, a crosslinking monomer, and an initiator.
  • the silicone hydrogel lens is made of a silicone hydrogel material, which includes at least one polysiloxane monomer, a hydrophilic monomer, a crosslinking monomer, and an initiator. Lenses of various materials can be surface-modified by the manufacturing method of the disclosure, so the manufacturing method has wide applicability.
  • the present disclosure provides a method of manufacturing a contact lens comprising the following operations.
  • (a) The lens is made to adsorb the initiator.
  • the hydrophilic vinyl monomer and the lens reference may be made to the foregoing embodiments, and details are not repeated here.
  • the manufacturing method of the present disclosure can form a hydrophilic polymer layer on the lens through one modification, which can effectively improve the comfort of wearing the contact lens.
  • the manufacturing process is simple, and the manufacturing efficiency can be improved.
  • the manufacturing method of the disclosure uses low equipment cost, which can reduce the manufacturing cost.
  • the manufacturing method of the present disclosure can be applied to modify the surface of hydrogel lenses or silicone hydrogel lenses, so it has a wide range of applications.
  • allowing the lens to absorb the initiator comprises: soaking the lens in an initiator solution containing the initiator.
  • the concentration of the initiator in the initiator solution is 0.1 wt% to 10 wt%.
  • the concentration is 0.1, 0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 wt%.
  • the hydrophilicity of the contact lens may be insufficient and the comfort of wearing the lens may be reduced.
  • the contact lens can also have excellent hydrophilicity.
  • the above concentration range can already make the contact lens have sufficient hydrophilicity.
  • the soaking time is from 0.5 minutes to 60 minutes. For example: 0.5, 1, 5, 10, 20, 30, 40, 50 or 60 minutes.
  • polymerizing the initiator adsorbed on the lens with at least one hydrophilic vinylic monomer includes the following operations.
  • the lens absorbing the initiator is soaked in a monomer solution containing at least one hydrophilic vinylic monomer. Heating lens and monomer solution.
  • the lens is soaked in the starter solution first, and then soaked in another monomer solution, and the starter solution and the monomer solution are stored in different containers.
  • the manufacturing method of the present disclosure includes two steps of soaking the lens. Compared with the method of soaking the lens in the solution containing both the initiator and the hydrophilic vinylic monomer, the manufacturing method of the present disclosure can reuse the initiator solution, which can save manufacturing cost and avoid wasting the initiator.
  • the lens and monomer solution are heated to a temperature of 60°C to 130°C.
  • the temperature is 60, 70, 80, 90, 100, 110, 120 or 130°C.
  • the lens and monomer solution are heated for 0.5 minutes to 140 minutes.
  • the lens and monomer solution are heated for 30 minutes to 120 minutes.
  • the time is 0.5, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130 or 140 minutes.
  • the initiator adsorbed on the lens undergoes a polymerization reaction with the hydrophilic vinyl monomer, thereby stably and firmly combining with the lens to achieve a good lens modification effect and make the lens Has excellent hydrophilic properties.
  • adding 0.1wt% initiator to the initiator solution can make the surface of the lens have good hydrophilic properties
  • adding 1wt% initiator can further improve the hydrophilic property of the lens surface
  • adding 2wt% % initiator can make the surface of the lens have the best hydrophilic properties.
  • Examples 5-9 in Table 2 that the concentration of DMA in the monomer solution is 1 wt%-12 wt%, which can make the contact lenses have excellent hydrophilic properties. It can be seen from Examples 6-7 that, compared with the monomer solution containing a single monomer, the contact lens has better hydrophilic properties when the monomer solution containing two different monomers is used for the reaction. It can be known from Examples 7-8 that, compared with the monomer solution containing a single monomer, the contact lens has better hydrophilic properties when the monomer solution containing three different monomers is used for the reaction.
  • the average retardation angles of the contact lenses of Examples 6, 8, and 9 are similar to those of the contact lenses of Comparative Examples 1 and 2 in Table 3, which proves that the contact lenses of the present disclosure have excellent hydrophilic properties compared with commercially available contact lenses.
  • the initiator is 2,2'-azobisisobutylamidine disalt acid salt (AAPH).
  • AAPH 2,2'-azobisisobutylamidine disalt acid salt
  • a hydrophilic polymer layer is formed on it.
  • the lens was moved to 70° C. saline and soaked for 60 minutes, and packaged and sterilized with saline to obtain a contact lens covered with a hydrophilic polymer layer. Please refer to Table 5 below for the experimental results.
  • the manufacturing method of the present disclosure can be applied to lenses of different materials, and can produce contact lenses covered with a hydrophilic polymer layer with good hydrophilicity.
  • the disclosure provides a contact lens and a manufacturing method thereof.
  • the manufacturing method includes: making the lens absorb the initiator, and polymerizing the initiator adsorbed on the lens with at least one hydrophilic vinyl monomer to form a hydrophilic polymer layer and intertwined with the lens, thereby achieving
  • the lens is modified to make the contact lens have excellent hydrophilicity.
  • the manufacturing method of the present disclosure has a simple flow, can improve the manufacturing efficiency, and the cost of the equipment used is low, which can reduce the manufacturing cost.
  • the manufacturing method of this disclosure can be applied to modify the surface of hydrogel lenses or silicone hydrogel lenses, so lenses of various materials can be surface modified by the manufacturing method of this disclosure, so this manufacturing method has wide applicability .
  • the present disclosure can have excellent hydrophilic properties with retardation angles as low as 4.9 degrees.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Ophthalmology & Optometry (AREA)
  • General Health & Medical Sciences (AREA)
  • Eyeglasses (AREA)
  • Optical Couplings Of Light Guides (AREA)

Abstract

提供一种隐形眼镜及其制造方法。隐形眼镜包括镜片及亲水性聚合物层。亲水性聚合物层与镜片相互缠结。亲水性聚合物层与镜片形成互穿聚合物网络或半互穿聚合物网络。亲水性聚合物层是由使吸附于镜片上的起始剂与至少一个亲水性乙烯型单体进行聚合反应而形成。隐形眼镜具有优异的亲水性质。由于制造隐形眼镜的方法流程简易，故可提升制造效率，降低制造成本。并且，制造方法可应用于各种材质的镜片，对其进行表面改质，故应用性广泛。

Description

隐形眼镜及其制造方法 技术领域
本揭示内容是关于一种隐形眼镜及其制造方法。
背景技术
由于硅水胶隐形眼镜具有高透氧性，让氧气可通过镜片到达眼角膜，进而可减轻眼睛干涩与红眼等现象，使得硅水胶材质成为近几年来隐形眼镜的市场主流。然而，硅水胶隐形眼镜具有一些缺点，例如：有机硅主体材料的疏水性会造成镜片与眼睛磨损导致不适与干燥感，且镜片表面容易产生蛋白质吸附及沉积。
为保留硅水胶隐形眼镜的高透氧性的优点，可借由镜片表面改质技术，以提升配戴的舒适性。然而，传统的表面改质技术具有一些缺点。举例来说，可利用等离子体处理进行隐形眼镜表面改质，然而，隐形眼镜在进行等离子体处理前通常必须经过干燥处理，且等离子体处理设备昂贵，因此，等离子体处理会提升制造隐形眼镜的成本。此外，可利用将亲水性聚合物质接枝至隐形眼镜上进行表面改质，然而，此方法仅能适用于部分类型的水凝胶隐形眼镜材料，其必须具有特定的官能基。此外，可利用将润湿剂添加到制造硅水胶隐形眼镜的镜片配方中，制得隐形眼镜，然而，湿润剂可能与镜片配方中的聚硅氧组份不相容而导致镜片发生雾浊，对镜片性质造成不利影响。鉴于上述，需要提供一种新的隐形眼镜及隐形眼镜制造方法以克服上述问题。
发明内容
本揭示内容提供一种隐形眼镜，其包括镜片及亲水性聚合物层。亲水性聚合物层与镜片相互缠结。亲水性聚合物层与镜片形成互穿聚合物网络(Interpenetrating polymer network,IPN)或半互穿聚合物网络(Semi-interpenetrating polymer network,Semi-IPN)。亲水性聚合物层是由使吸附于镜片上的起始剂与至少一个亲水性乙烯型单体进行聚合反应而形成。
在一些实施方式中，起始剂包括过硫酸钾(Potassium persulfate,KPS)、偶氮二异丁腈(Azobisisobutyronitrile,AIBN)、2,2'-偶氮二异丁基脒二盐酸盐(2,2'-Azobis[2-methylpropionamidine]dihydrochloride,AAPH)、2,2'-偶氮-二-(2-甲基丁腈)(2,2'-Azobis-(2-methybutyronitrile),AMBN)、2,2'-偶氮-二-(2,4-二甲基戊腈)(2,2'-Azobis(2,4-dimethyl)valeronitrile,ADVN)、4,4'-偶氮-4-氰基戊酸(4,4'-Azobis(4-cyanovaleric acid),ACVA)、过氧化叔丁醇(2-Methylpropane-2-peroxol,TBHP)、偶氮二异丁咪唑啉盐酸盐、过氧化氢异丙苯、过氧化二第三丁基(Di-tert-butyl peroxide,DTBP)、过氧化苯甲酰或其组合。
在一些实施方式中，至少一个亲水性乙烯型单体包括丙烯酸、甲基丙烯酸、丙烯酰胺(Acrylamide)、甲基丙烯酰胺、N,N-二甲基丙烯酰胺(N,N-Dimethylacrylamide,DMA)、N,N-二甲基甲基丙烯酰胺(N,N-Dimethyl-2-propenamide,DMMA)、N,N-二甲基甲基丙烯酰胺、N-羟乙基丙烯酰胺(N-Hydroxyethylacrylamide,NHEMAA)、N-[三(羟甲基)甲基]-丙烯酰胺、2,3-二羟基丙基甲基丙烯酸酯(2,3-Dihydroxypropyl methacrylate；Glycerol monomethacrylate,GMMA)、甲基丙烯酸羟乙酯(HEMA)、2-丙烯酰氨基-2-甲基-1-丙磺酸、N-乙烯基吡咯烷酮、甲基丙烯 酸甲酯(Methyl methacrylate,MAA)、乙二醇二丙烯酸酯、丙烯酸羟丙基酯、甲基丙烯酸羟丙基酯、三甲基铵甲基丙烯酸2-羟丙基酯盐酸盐、甲基丙烯酸胺基丙基酯盐酸盐、甲基丙烯酸二甲基胺基乙酯、甘油甲基丙烯酸酯、N-乙烯基-2-吡咯烷酮(N-Vinylpyrrolidone,NVP)、烯丙醇、乙烯基吡啶、N-乙烯基甲酰胺、N-乙烯基乙酰胺、N-乙烯基异丙酰胺、N-乙烯基-N-甲基乙酰胺、烯丙醇、N-乙烯基己内酰胺或其组合。
在一些实施方式中，至少一个亲水性乙烯型单体包括不同的第一亲水性乙烯型单体及第二亲水性乙烯型单体，第一亲水性乙烯型单体与第二亲水性乙烯型单体的重量比为20:1至1:1。
在一些实施方式中，至少一个亲水性乙烯型单体包括不同的第一亲水性乙烯型单体、第二亲水性乙烯型单体及第三亲水性乙烯型单体。
在一些实施方式中，镜片包括水胶镜片或硅水胶镜片。
本揭示内容提供一种制造隐形眼镜的方法，包括以下操作。使镜片吸附起始剂。使吸附于镜片上的起始剂与至少一个亲水性乙烯型单体进行聚合反应，以形成亲水性聚合物层与镜片相互缠结，其中亲水性聚合物层与镜片形成互穿聚合物网络或半互穿聚合物网络。
在一些实施方式中，使镜片吸附起始剂包括：将镜片浸泡于含有起始剂的起始剂溶液中。
在一些实施方式中，在起始剂溶液中，起始剂的浓度为0.1wt％至10wt％。
在一些实施方式中，使吸附于镜片上的起始剂与至少一个亲水性乙烯型单体进行聚合反应包括以下操作。将吸附起始剂的镜片浸泡于含有至少一个亲水性乙烯型单体的单体溶液中。加热镜片及单体溶液。
在一些实施方式中，加热镜片及单体溶液的温度为60℃至130℃。
在一些实施方式中，加热镜片及单体溶液的时间为0.5分钟至140分 钟。
在一些实施方式中，加热镜片及单体溶液的时间为30分钟至120分钟。
在一些实施方式中，起始剂包括过硫酸钾(KPS)、偶氮二异丁腈(AIBN)、2,2'-偶氮二异丁基脒二盐酸盐(AAPH)、2,2'-偶氮-二-(2-甲基丁腈)(AMBN)、2,2'-偶氮-二-(2,4-二甲基戊腈)(ADVN)、4,4'-偶氮-4-氰基戊酸(ACVA)、过氧化叔丁醇(TBHP)、偶氮二异丁咪唑啉盐酸盐、过氧化氢异丙苯、过氧化二第三丁基(DTBP)、过氧化苯甲酰或其组合。
在一些实施方式中，至少一个亲水性乙烯型单体包括丙烯酸、甲基丙烯酸、丙烯酰胺、甲基丙烯酰胺、N,N-二甲基丙烯酰胺(DMA)、N,N-二甲基甲基丙烯酰胺(DMMA)、N,N-二甲基甲基丙烯酰胺、N-羟乙基丙烯酰胺(NHEMAA)、N-[三(羟甲基)甲基]-丙烯酰胺、2,3-二羟基丙基甲基丙烯酸酯(GMMA)、甲基丙烯酸羟乙酯(HEMA)、2-丙烯酰氨基-2-甲基-1-丙磺酸、N-乙烯基吡咯烷酮、甲基丙烯酸甲酯(MAA)、乙二醇二丙烯酸酯、丙烯酸羟丙基酯、甲基丙烯酸羟丙基酯、三甲基铵甲基丙烯酸2-羟丙基酯盐酸盐、甲基丙烯酸胺基丙基酯盐酸盐、甲基丙烯酸二甲基胺基乙酯、甘油甲基丙烯酸酯、N-乙烯基-2-吡咯烷酮(NVP)、烯丙醇、乙烯基吡啶、N-乙烯基甲酰胺、N-乙烯基乙酰胺、N-乙烯基异丙酰胺、N-乙烯基-N-甲基乙酰胺、烯丙醇、N-乙烯基己内酰胺或其组合。
参考以下描述和所附申请专利范围，可更理解本揭示内容的这些和其他特征、特点和优点。
应该理解的是，前述的一般性描述和下列具体说明仅仅是示例性和解释性的，并旨在提供所要求的本揭示内容的进一步说明。
实现发明的最佳方式
在本文中，由「一数值至另一数值」表示的范围，是一种避免在说明书中一一列举该范围中的所有数值的概要性表示方式。因此，某一特定数值范围的记载，涵盖该数值范围内的任意数值以及由该数值范围内的任意数值界定出的较小数值范围，如同在说明书中明文写出该任意数值和该较小数值范围一样。
本文使用的「约」、「近似」、「本质上」、或「实质上」包括所述值和在本领域普通技术人员确定的特定值的可接受的偏差范围内的平均值，考虑到所讨论的测量和与测量相关的误差的特定数量(即，测量系统的限制)。例如，「约」可以表示在所述值的一个或多个标准偏差内，或例如±30％、±20％、±15％、±10％、±5％内。再者，本文使用的「约」、「近似」、「本质上」、或「实质上」可依测量性质、涂布性质或其它性质，来选择较可接受的偏差范围或标准偏差，而可不用一个标准偏差适用全部性质。
虽然下文中利用一系列的操作或步骤来说明在此揭露的方法，但是这些操作或步骤所示的顺序不应被解释为本揭示内容的限制。例如，某些操作或步骤可以按不同顺序进行及/或与其它步骤同时进行。此外，并非必须执行所有绘示的操作、步骤及/或特征才能实现本揭示内容的实施方式。此外，在此所述的每一个操作或步骤可以包含数个子步骤或动作。
本揭示内容提供一种隐形眼镜，其包括镜片及亲水性聚合物层。亲水性聚合物层与镜片相互缠结。亲水性聚合物层与镜片形成互穿聚合物网络或半互穿聚合物网络。亲水性聚合物层是由使吸附于镜片上的起始剂与至少一个亲水性乙烯型单体进行聚合反应而形成。在一些实施方式中，亲水性聚合物层为亲水性聚合物网络。
更详细来说，由于隐形眼镜具有网状结构，因此，起始剂会吸附在隐 形眼镜的表面，亦会进入到网状结构的内部。因此，当起始剂产生自由基，与亲水性乙烯型单体进行聚合反应后，会形成亲水性聚合物层的网络与隐形眼镜的网状结构相互缠结的交错结构，借此改质镜片的表面。在本揭示内容的隐形眼镜中，亲水性聚合物层并非以与镜片形成共价键的方式固定在镜片上。在一些实施方式中，亲水性聚合物层与镜片间并未形成共价键。镜片的表面性质可被亲水性聚合物层改质，而具有良好的亲水性。在一些实施方式中，隐形眼镜的迟滞角为4度～63度。举例来说，迟滞角为4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、30、40、50、60或63度。
在一些实施方式中，起始剂包括过硫酸钾(KPS)、偶氮二异丁腈(AIBN)、2,2'-偶氮二异丁基脒二盐酸盐(AAPH)、2,2'-偶氮-二-(2-甲基丁腈)(AMBN)、2,2'-偶氮-二-(2,4-二甲基戊腈)(ADVN)、4,4'-偶氮-4-氰基戊酸(ACVA)、过氧化叔丁醇(TBHP)、偶氮二异丁咪唑啉盐酸盐、过氧化氢异丙苯、过氧化二第三丁基(DTBP)、过氧化苯甲酰或其组合。
在一些实施方式中，至少一个亲水性乙烯型单体包括丙烯酸、甲基丙烯酸、丙烯酰胺、甲基丙烯酰胺、N,N-二甲基丙烯酰胺(DMA)、N,N-二甲基甲基丙烯酰胺(DMMA)、N,N-二甲基甲基丙烯酰胺、N-羟乙基丙烯酰胺(NHEMAA)、N-[三(羟甲基)甲基]-丙烯酰胺、2,3-二羟基丙基甲基丙烯酸酯(GMMA)、甲基丙烯酸羟乙酯(HEMA)、2-丙烯酰氨基-2-甲基-1-丙磺酸、N-乙烯基吡咯烷酮、甲基丙烯酸甲酯(MAA)、乙二醇二丙烯酸酯、丙烯酸羟丙基酯、甲基丙烯酸羟丙基酯、三甲基铵甲基丙烯酸2-羟丙基酯盐酸盐、甲基丙烯酸胺基丙基酯盐酸盐、甲基丙烯酸二甲基胺基乙酯、甘油甲基丙烯酸酯、N-乙烯基-2-吡咯烷酮(NVP)、烯丙醇、乙烯基吡啶、N-乙烯基甲酰胺、N-乙烯基乙酰胺、N-乙烯基异丙酰胺、N-乙烯基-N-甲基乙酰胺、烯丙 醇、N-乙烯基己内酰胺或其组合。
在一些实施方式中，本揭示内容可同时使用二种不同的亲水性乙烯型单体与起始剂进行反应。相较于以单一种亲水性乙烯型单体与起始剂进行反应，使用二种亲水性乙烯型单体可使隐形眼镜具有更佳的亲水性及湿润性。可根据镜片设计需求，调整亲水性乙烯型单体的种类和重量比例。在一些实施方式中，至少一个亲水性乙烯型单体包括不同的第一亲水性乙烯型单体及第二亲水性乙烯型单体。在一些实施方式中，第一亲水性乙烯型单体具有胺基，第二亲水性乙烯型单体具有羟基。举例来说，第一亲水性乙烯型单体为N,N-二甲基丙烯酰胺(DMA)，第二亲水性乙烯型单体为2,3-二羟基丙基甲基丙烯酸酯(GMMA)。举例来说，第一亲水性乙烯型单体与第二亲水性乙烯型单体的重量比为20:1至1:1。举例来说：20:1、18:1、16:1、14:1、12:1、10:1、8:1、6:1、4:1、2:1或1:1。当重量比落于上述区间，可使隐形眼镜具有良好的亲水性及湿润性。
在一些实施方式中，本揭示内容可同时使用三种或三种以上不同的亲水性乙烯型单体与起始剂进行反应。相较于以单一种亲水性乙烯型单体与起始剂进行反应，使用三种亲水性乙烯型单体可使隐形眼镜具有更佳的亲水性及湿润性。可根据镜片设计需求，调整亲水性乙烯型单体的种类和重量比例。在一些实施方式中，至少一个亲水性乙烯型单体包括不同的第一亲水性乙烯型单体、第二亲水性乙烯型单体及第三亲水性乙烯型单体。在一些实施方式中，第一亲水性乙烯型单体具有胺基，第二亲水性乙烯型单体具有羟基，第三亲水性乙烯型单体具有基团
Figure PCTCN2021130237-appb-000001
举例来说，第一亲水性乙烯型单体为N,N-二甲基丙烯酰胺(DMA)，第二亲水性乙烯型单体为2,3-二羟基丙基甲基丙烯酸酯(GMMA)，第三亲水性乙烯型单体为(NVP)。
在一些实施方式中，镜片包括水胶镜片或硅水胶镜片。在一些实施方式中，水胶镜片是由非含硅水胶材料制得，非含硅水胶材料包括至少一个羟基乙烯基单体、亲水性单体、交联单体以及起始剂。在一些实施方式中，硅水胶镜片是由硅水胶材料制得，硅水胶材料包括至少一个聚硅氧单体、亲水性单体、交联单体以及起始剂。各种材质的镜片均可以本揭示内容的制造方法进行表面改质，因此此制造方法应用性广泛。
本揭示内容提供一种制造隐形眼镜的方法，包括以下操作。(a)使镜片吸附起始剂。(b)使吸附于镜片上的起始剂与至少一个亲水性乙烯型单体进行聚合反应，以形成亲水性聚合物层与镜片相互缠结，其中亲水性聚合物层与镜片形成互穿聚合物网络或半互穿聚合物网络。起始剂、亲水性乙烯型单体及镜片的实施方式可参考前述的实施方式，在此不再赘述。
在一些实施方式中，本揭示内容的制造方法可借由一次改质，在镜片上形成一层亲水性聚合物层，就能够有效提升配戴隐形眼镜的舒适性。制作流程简易，可提升制造效率，并且，相较于以等离子体处理镜片的制程来说，本揭示内容的制造方法所用的设备成本低，可降低制造成本。本揭示内容的制造方法可应用于改质水胶镜片或硅水胶镜片的表面，因此应用性广泛。
在一些实施方式中，使镜片吸附起始剂包括：将镜片浸泡于含有起始剂的起始剂溶液中。在一些实施方式中，在起始剂溶液中，起始剂的浓度为0.1wt％至10wt％。举例来说，浓度为0.1、0.2、0.3、0.4、0.5、1、2、3、4、5、6、7、8、9或10wt％。当起始剂低于0.1wt％，可能会使隐形眼镜亲水性不足，而降低配戴镜片的舒适感。当起始剂高于10wt％，亦可使隐形眼镜具有优异的亲水性。然上述浓度范围已能够使隐形眼镜具有足够的亲水性。在一些实施方式中，浸泡时间为0.5分钟至60分钟。例如：0.5、 1、5、10、20、30、40、50或60分钟。
在一些实施方式中，使吸附于镜片上的起始剂与至少一个亲水性乙烯型单体进行聚合反应包括以下操作。将吸附起始剂的镜片浸泡于含有至少一个亲水性乙烯型单体的单体溶液中。加热镜片及单体溶液。值得注意的是，本揭示内容是将镜片先浸泡于起始剂溶液中，再浸泡于另一单体溶液中，起始剂溶液和单体溶液盛放于不同的容器中。由此可知，本揭示内容的制造方法包括两个浸泡镜片的步骤。相较于将镜片浸泡于同时含有起始剂及亲水性乙烯型单体的溶液的方法，本揭示内容的制造方法可重复利用起始剂溶液，可节省制造成本，避免浪费起始剂。
在一些实施方式中，加热镜片及单体溶液的温度为60℃至130℃。举例来说，温度为60、70、80、90、100、110、120或130℃。在一些实施方式中，加热镜片及单体溶液的时间为0.5分钟至140分钟。在一些实施方式中，加热镜片及单体溶液的时间为30分钟至120分钟。举例来说，时间为0.5、1、5、10、20、30、40、50、60、70、80、90、100、110、120、130或140分钟。在上述温度范围和时间范围内，吸附于镜片上的起始剂与亲水性乙烯型单体发生聚合反应，从而稳定和牢固地与镜片结合在一起，达到良好的镜片改质效果，使镜片具有优异的亲水性质。
下文将参照实验例1至4，更具体地描述本揭示内容的特征。虽然描述了以下实施例，但是在不逾越本揭示内容范畴的情况下，可适当地改变所用材料、其量及比率、处理细节以及处理流程等等。因此，不应由下文所述的实施例对本揭示内容作出限制性地解释。
实验例1：制造隐形眼镜
将干燥的实施例1至4的硅水胶镜片分别置于含有不同起始剂浓度的起始剂溶液中浸泡30分钟，起始剂为2,2'-偶氮二异丁基脒二盐酸盐 (AAPH)。将镜片移至含有8wt％N,N-二甲基丙烯酰胺(DMA)及1wt％2,3-二羟基丙基甲基丙烯酸酯(GMMA)的单体溶液中并放进90℃的烘箱内加热，使吸附于硅水胶镜片上的AAPH与DMA及GMMA进行聚合反应40分钟，以在镜片上形成亲水性聚合物层。将镜片移至70℃的盐水中浸泡60分钟，以盐水进行封装灭菌，得到覆盖有亲水性聚合物层的隐形眼镜。测试隐形眼镜的动态接触角(Dynamic contact angle,DCA)。将镜片置于盐水液面下，以俘获气泡法(Captive bubble method)测量前进角(Advancing angle)及后退角(Receding angle)，以两者角度差值计算出迟滞角，其亦可称为接触角迟滞(Contact angle hysteresis)。迟滞角数值越小，代表隐形眼镜亲水性越佳。N代表用于计算平均迟滞角的隐形眼镜数量。实验结果请参以下表1。
表1
Figure PCTCN2021130237-appb-000002
由表1可知，在起始剂溶液中添加0.1wt％的起始剂就能够使镜片表面具有良好的亲水性质，添加1wt％的起始剂能够进一步提升镜片表面的亲水性质，添加2wt％的起始剂能够使镜片表面具有最佳的亲水性质。
实验例2：制造隐形眼镜
将干燥的实施例5至10的硅水胶镜片置于2wt％的起始剂溶液中浸泡30分钟，起始剂为2,2'-偶氮二异丁基脒二盐酸盐(AAPH)。将镜片移至含 有不同成分及浓度的单体溶液中并放进90℃的烘箱内加热，使吸附于硅水胶镜片上的AAPH与单体溶液内的单体进行聚合反应60分钟，以在镜片上形成亲水性聚合物层。将镜片移至70℃的盐水中浸泡60分钟，以盐水进行封装灭菌，得到覆盖有亲水性聚合物层的隐形眼镜。计算隐形眼镜的迟滞角。实验结果请参以下表2。以下表3列出比较例1及2的市售隐形眼镜，以与实施例5至10进行对照。
表2
Figure PCTCN2021130237-appb-000003
表3
  隐形眼镜 平均迟滞角(N＝5)
比较例1 DAILIES TOTAL1 4.9
比较例2 ACUVUE oasys 6.4
由表2实施例5～9可知，单体溶液的DMA的浓度为1wt％～12wt％，可使隐形眼镜均具有优异的亲水性质。由实施例6～7可知，相较于以含单一种 单体的单体溶液进行反应，以含有两种不同单体的单体溶液进行反应，可使隐形眼镜具有较佳的亲水性质。由实施例7～8可知，相较于以含单一种单体的单体溶液进行反应，以含有三种不同单体的单体溶液进行反应，可使隐形眼镜具有较佳的亲水性质。实施例6、8及9的隐形眼镜的平均迟滞角与表3的比较例1及2的隐形眼镜相近，可证明本揭示内容的隐形眼镜具有与市售隐形眼镜一般优异的亲水性质。
实验例3：制造隐形眼镜
将干燥的实施例11至15的硅水胶镜片置于2wt％的起始剂溶液中浸泡30分钟，起始剂为2,2'-偶氮二异丁基脒二盐酸盐(AAPH)。将镜片移至含有8wt％DMA及1wt％GMMA的单体溶液中并放进90℃的烘箱内加热，使吸附于硅水胶镜片上的AAPH与单体溶液内的单体在不同时间下进行聚合反应，以在镜片上形成亲水性聚合物层。将镜片移至70℃的盐水中浸泡60分钟，以盐水进行封装灭菌，得到覆盖有亲水性聚合物层的隐形眼镜。计算隐形眼镜的迟滞角。实验结果请参以下表4。
表4
Figure PCTCN2021130237-appb-000004
由表4可知，隐形眼镜的亲水性质会随着聚合反应时间增加而提升，故平均迟滞角会随着聚合反应时间增加而降低。当聚合反应时间为20分钟， 隐形眼镜已呈现亲水改质效果；当聚合反应时间为30分钟，隐形眼镜已具有良好的亲水性质；当聚合反应时间为60分钟，隐形眼镜具有最佳的亲水性质。
实验例4：制造隐形眼镜
将硅水胶镜片和甲基丙烯酸羟乙酯(HEMA)水胶镜片置于2wt％的起始剂溶液中浸泡30分钟，起始剂为2,2'-偶氮二异丁基脒二盐酸盐(AAPH)。将镜片移至含有8wt％DMA及1wt％GMMA的单体溶液中并放进90℃的烘箱内加热，使吸附于硅水胶镜片上的AAPH与DMA及GMMA进行聚合反应40分钟，以在镜片上形成亲水性聚合物层。将镜片移至70℃的盐水中浸泡60分钟，以盐水进行封装灭菌，得到覆盖有亲水性聚合物层的隐形眼镜。实验结果请参以下表5。
表5
Figure PCTCN2021130237-appb-000005
由表5可知，本揭示内容的制造方法，可应用于不同材质的镜片，皆可制得具有良好亲水性的覆盖有亲水性聚合物层的隐形眼镜。
综上所述，本揭示内容提供一种隐形眼镜及其制造方法。制造方法包括：使镜片吸附起始剂，使吸附于镜片上的起始剂与至少一个亲水性乙烯型单体进行聚合反应，以形成亲水性聚合物层与镜片相互缠结，从而达到镜片改质，使隐形眼镜具有优异的亲水性。本揭示内容的制造方法流程简易，可提升制造效率，且所用的设备成本低，可降低制造成本。并且，本 揭示内容的制造方法可应用于改质水胶镜片或硅水胶镜片的表面，因此各种材质的镜片均可以本揭示内容的制造方法进行表面改质，因此此制造方法应用性广泛。本揭示内容可具有优异的亲水性质，迟滞角最低可达4.9度。
尽管已经参考某些实施方式相当详细地描述了本揭示内容，但是亦可能有其他实施方式。因此，所附申请专利范围的精神和范围不应限于此处包括的实施方式的描述。
对于所属技术领域人员来说，显而易见的是，在不脱离本揭示内容的范围或精神的情况下，可以对本揭示内容的结构进行各种修改和变化。鉴于前述内容，本揭示内容意图涵盖落入所附权利要求范围内的本揭示内容的修改和变化。

Claims (15)

  1. 一种隐形眼镜，其特征在于，包括：
    镜片；以及
    亲水性聚合物层，与该镜片相互缠结，该亲水性聚合物层与该镜片形成互穿聚合物网络或半互穿聚合物网络，其中该亲水性聚合物层是由使吸附于该镜片上的起始剂与至少一个亲水性乙烯型单体进行聚合反应而形成。
  2. 根据权利要求1所述的隐形眼镜，其特征在于，该起始剂包括过硫酸钾、偶氮二异丁腈、2,2'-偶氮二异丁基脒二盐酸盐、2,2'-偶氮-二-(2-甲基丁腈)、2,2'-偶氮-二-(2,4-二甲基戊腈)、4,4'-偶氮-4-氰基戊酸、过氧化叔丁醇、偶氮二异丁咪唑啉盐酸盐、过氧化氢异丙苯、过氧化二第三丁基、过氧化苯甲酰或其组合。
  3. 根据权利要求1所述的隐形眼镜，其特征在于，该至少一个亲水性乙烯型单体包括丙烯酸、甲基丙烯酸、丙烯酰胺、甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N,N-二甲基甲基丙烯酰胺、N,N-二甲基甲基丙烯酰胺、N-羟乙基丙烯酰胺、N-[三(羟甲基)甲基]-丙烯酰胺、2,3-二羟基丙基甲基丙烯酸酯、甲基丙烯酸羟乙酯、2-丙烯酰氨基-2-甲基-1-丙磺酸、N-乙烯基吡咯烷酮、甲基丙烯酸甲酯、乙二醇二丙烯酸酯、丙烯酸羟丙基酯、甲基丙烯酸羟丙基酯、三甲基铵甲基丙烯酸2-羟丙基酯盐酸盐、甲基丙烯酸胺基丙基酯盐酸盐、甲基丙烯酸二甲基胺基乙酯、甘油甲基丙烯酸酯、N-乙烯基-2-吡咯烷酮、烯丙醇、乙烯基吡啶、N-乙烯基甲酰胺、N-乙烯基乙酰胺、N-乙烯基异丙酰胺、N-乙烯基-N-甲基乙酰胺、烯丙醇、N-乙烯基己内酰胺或其组合。
  4. 根据权利要求1所述的隐形眼镜，其特征在于，该至少一个亲水性乙烯型单体包括不同的第一亲水性乙烯型单体及第二亲水性乙烯型单体，该第一亲水性乙烯型单体与第二亲水性乙烯型单体的重量比为20:1至1:1。
  5. 根据权利要求1所述的隐形眼镜，其特征在于，该至少一个亲水性乙烯型单体包括不同的第一亲水性乙烯型单体、第二亲水性乙烯型单体及第三亲水性乙烯型单体。
  6. 根据权利要求1所述的隐形眼镜，其特征在于，该镜片包括水胶镜片或硅水胶镜片。
  7. 一种制造隐形眼镜的方法，其特征在于，包括：
    使镜片吸附起始剂；以及
    使吸附于该镜片上的该起始剂与至少一个亲水性乙烯型单体进行聚合反应，以形成亲水性聚合物层与该镜片相互缠结，其中该亲水性聚合物层与该镜片形成互穿聚合物网络或半互穿聚合物网络。
  8. 根据权利要求7所述的方法，其特征在于，使该镜片吸附该起始剂包括：将该镜片浸泡于含有该起始剂的起始剂溶液中。
  9. 根据权利要求8所述的方法，其特征在于，在该起始剂溶液中，该起始剂的浓度为0.1wt％至10wt％。
  10. 根据权利要求7所述的方法，其特征在于，使吸附于该镜片上的该起始剂与该至少一个亲水性乙烯型单体进行该聚合反应包括：
    将吸附该起始剂的该镜片浸泡于含有该至少一个亲水性乙烯型单体的单体溶液中；以及
    加热该镜片及该单体溶液。
  11. 根据权利要求10所述的方法，其特征在于，加热该镜片及该单体溶液的温度为60℃至130℃。
  12. 根据权利要求10所述的方法，其特征在于，加热该镜片及该单体溶液的时间为0.5分钟至140分钟。
  13. 根据权利要求12所述的方法，其特征在于，加热该镜片及该单体溶液的时间为30分钟至120分钟。
  14. 根据权利要求7所述的方法，其特征在于，该起始剂包括过硫酸钾、偶氮二异丁腈、2,2'-偶氮二异丁基脒二盐酸盐、2,2'-偶氮-二-(2-甲基丁腈)、2,2'-偶氮-二-(2,4-二甲基戊腈)、4,4'-偶氮-4-氰基戊酸、过氧化叔丁醇、偶氮二异丁咪唑啉盐酸盐、过氧化氢异丙苯、过氧化二第三丁基、过氧化苯甲酰或其组合。
  15. 根据权利要求7所述的方法，其特征在于，该至少一个亲水性乙烯型单体包括丙烯酸、甲基丙烯酸、丙烯酰胺、甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N,N-二甲基甲基丙烯酰胺、N,N-二甲基甲基丙烯酰胺、N-羟 乙基丙烯酰胺、N-[三(羟甲基)甲基]-丙烯酰胺、2,3-二羟基丙基甲基丙烯酸酯、甲基丙烯酸羟乙酯、2-丙烯酰氨基-2-甲基-1-丙磺酸、N-乙烯基吡咯烷酮、甲基丙烯酸甲酯、乙二醇二丙烯酸酯、丙烯酸羟丙基酯、甲基丙烯酸羟丙基酯、三甲基铵甲基丙烯酸2-羟丙基酯盐酸盐、甲基丙烯酸胺基丙基酯盐酸盐、甲基丙烯酸二甲基胺基乙酯、甘油甲基丙烯酸酯、N-乙烯基-2-吡咯烷酮、烯丙醇、乙烯基吡啶、N-乙烯基甲酰胺、N-乙烯基乙酰胺、N-乙烯基异丙酰胺、N-乙烯基-N-甲基乙酰胺、烯丙醇、N-乙烯基己内酰胺或其组合。
PCT/CN2021/130237 2021-11-12 2021-11-12 隐形眼镜及其制造方法 WO2023082166A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US17/772,147 US20240168200A1 (en) 2021-11-12 2021-11-12 Contact lens and manufacturing method thereof
CN202180005076.1A CN116438252A (zh) 2021-11-12 2021-11-12 隐形眼镜及其制造方法
PCT/CN2021/130237 WO2023082166A1 (zh) 2021-11-12 2021-11-12 隐形眼镜及其制造方法
TW111101158A TWI820572B (zh) 2021-11-12 2022-01-11 隱形眼鏡及其製造方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2021/130237 WO2023082166A1 (zh) 2021-11-12 2021-11-12 隐形眼镜及其制造方法

Publications (1)

Publication Number Publication Date
WO2023082166A1 true WO2023082166A1 (zh) 2023-05-19

Family

ID=86334823

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/130237 WO2023082166A1 (zh) 2021-11-12 2021-11-12 隐形眼镜及其制造方法

Country Status (4)

Country Link
US (1) US20240168200A1 (zh)
CN (1) CN116438252A (zh)
TW (1) TWI820572B (zh)
WO (1) WO2023082166A1 (zh)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003177360A (ja) * 2001-12-10 2003-06-27 Fuji Photo Film Co Ltd コンタクトレンズ
WO2013164989A1 (ja) * 2012-05-02 2013-11-07 株式会社メニコン 表面処理樹脂成形体の製造方法及び表面処理樹脂成形体
CN106716233A (zh) * 2014-05-09 2017-05-24 茵洛有限公司 具有润湿性表面的水凝胶隐形镜片及其制备方法
US20200284951A1 (en) * 2017-10-04 2020-09-10 University Of Florida Research Foundation Methods and compositions for improved comfort contact lens

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI582118B (zh) * 2012-05-25 2017-05-11 壯生和壯生視覺關懷公司 含水溶性ｎ－（２羥烷基）（甲基）丙烯醯胺聚合物或共聚物之隱形眼鏡

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003177360A (ja) * 2001-12-10 2003-06-27 Fuji Photo Film Co Ltd コンタクトレンズ
WO2013164989A1 (ja) * 2012-05-02 2013-11-07 株式会社メニコン 表面処理樹脂成形体の製造方法及び表面処理樹脂成形体
CN106716233A (zh) * 2014-05-09 2017-05-24 茵洛有限公司 具有润湿性表面的水凝胶隐形镜片及其制备方法
US20200284951A1 (en) * 2017-10-04 2020-09-10 University Of Florida Research Foundation Methods and compositions for improved comfort contact lens

Also Published As

Publication number Publication date
TWI820572B (zh) 2023-11-01
US20240168200A1 (en) 2024-05-23
CN116438252A (zh) 2023-07-14
TW202319529A (zh) 2023-05-16

Similar Documents

Publication Publication Date Title
JP6807011B2 (ja) 表面にホスホリルコリン基含有親水性ポリマーを有するコンタクトレンズ
TWI753090B (zh) 用於隱形眼鏡的單體組合物、用於隱形眼鏡的聚合物及其製備方法、以及隱形眼鏡及其製造方法
JP6836503B2 (ja) ゲル、ゲルの製造方法、レンズ、コンタクトレンズ表面改質剤、重合性組成物及び重合体
JP5631655B2 (ja) コンタクトレンズ及びその製造方法
KR20190017634A (ko) 표면 변형을 갖는 콘택트 렌즈 및 그 마련 방법
AU2015201371A1 (en) Silicone acrylamide copolymer
WO2023082166A1 (zh) 隐形眼镜及其制造方法
JP4123648B2 (ja) ポリマーおよびそれを用いた眼用レンズ
TW201922882A (zh) 眼用鏡片及其製造方法
JP6077455B2 (ja) 防曇性プラスチックレンズ
WO2013164989A1 (ja) 表面処理樹脂成形体の製造方法及び表面処理樹脂成形体
JP3901749B2 (ja) 含水性コンタクトレンズの表面処理方法及びそれによって得られた含水性コンタクトレンズ
TWI754546B (zh) 隱形眼鏡的製造方法
TWI813875B (zh) 隱形眼鏡用單體組合物、隱形眼鏡用聚合物及其製備方法、以及隱形眼鏡及其製造方法
TWI551616B (zh) 一種應用於眼科物件之矽水凝膠的製造方法
JP3069926B2 (ja) コンタクトレンズ用処理溶液
TWI421306B (zh) 具有高含水率之聚矽氧水膠
JPH11305172A (ja) 含水性ソフトコンタクトレンズ
JP7490177B2 (ja) 含水材料用重合体
TWI826534B (zh) 隱形眼鏡用單體組合物及隱形眼鏡用聚合物、以及隱形眼鏡及其製造方法
JPH08334732A (ja) ソフトコンタクトレンズ
JP7424372B2 (ja) ホスホリルコリン基含有ビニル系単量体
WO2022179477A1 (zh) 隐形眼镜材料及隐形眼镜镜片
WO2023106395A1 (ja) 硬化性組成物、成形体、シリコーンハイドロゲル及びその製造方法、マクロモノマー
JPH10177152A (ja) 含水性ソフトコンタクトレンズ

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 17772147

Country of ref document: US