CN111154028A - High-refractive-index corneal contact lens material and application thereof - Google Patents

High-refractive-index corneal contact lens material and application thereof Download PDF

Info

Publication number
CN111154028A
CN111154028A CN202010009396.1A CN202010009396A CN111154028A CN 111154028 A CN111154028 A CN 111154028A CN 202010009396 A CN202010009396 A CN 202010009396A CN 111154028 A CN111154028 A CN 111154028A
Authority
CN
China
Prior art keywords
contact lens
corneal contact
lens material
crosslinking agent
corneal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010009396.1A
Other languages
Chinese (zh)
Inventor
姜勇
刘后涛
晋亚紧
陈玲
王小雨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Southeast University
Original Assignee
Southeast University
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 Southeast University filed Critical Southeast University
Priority to CN202010009396.1A priority Critical patent/CN111154028A/en
Publication of CN111154028A publication Critical patent/CN111154028A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/26Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • GPHYSICS
    • G02OPTICS
    • G02CSPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00Optical parts
    • G02C7/02Lenses; Lens systems ; Methods of designing lenses
    • G02C7/04Contact lenses for the eyes
    • G02C7/049Contact lenses having special fitting or structural features achieved by special materials or material structures

Landscapes

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

Abstract

The invention discloses a high-refractive index corneal contact lens material and application thereof, wherein the material comprises the following raw materials in parts by weight: 18-52 parts of polymerizable vinyl monomer with a substituted aromatic ring structure, hydrophilic monomer: 21-80 parts of a cross-linking agent: 0.1-1 part of free radical initiator: 0.1 to 1 portion. The cornea contact lens made of the cornea contact lens material has good elongation and rebound resilience, better mechanical strength, high refractive index and optical transparency. Meanwhile, the corneal contact lens prepared from the material is simple in preparation method, does not need a solvent, and improves the safety of wearing by human eyes.

Description

High-refractive-index corneal contact lens material and application thereof
Technical Field
The invention belongs to the technical field of corneal contact lens materials, and particularly relates to a high-refractive-index corneal contact lens material and application thereof.
Background
The contact lenses are also called as contact lenses, and compared with the common lenses, the contact lenses have the advantages of beautiful wearing and stable wearing, are more and more popular among people, and the number of users is greatly increased. Statistics show that the number of people wearing the corneal contact lens accounts for about 1.5% of the world population; in developed countries such as the united states and japan, the number of corneal contact lenses used is about 10% of the total population of the country. In China, the incidence rate of myopia of teenagers is always high, so that the market of the corneal contact lens in China develops rapidly. In addition, with the improvement of living standard and the progress of medical field, development and application of protective corneal contact lenses, cosmetic corneal contact lenses and medical corneal contact lenses are also promoted. Statistically, in recent years, the market for chinese corneal contact lenses has grown at a rate of up to 20% per year.
Various materials for making contact lenses are known in the art. The earliest contact lenses were made of glass material. However, glass causes severe eye irritation, making the lenses impossible to wear for extended periods of time. To overcome this drawback, contact lenses were later developed that were made of Polymethylmethacrylate (PMMA). However, early PMMA lenses did not allow oxygen to enter the cornea, resulting in ocular discomfort and edema. Contact lens materials must not only have acceptable oxygen transmission levels, but must also have high refractive indices to provide visual near and far distance acuity, sufficient surface wettability, good dimensional stability, resistance to surface deposits, and must be durable to withstand handling.
Hydrogels are hydrated cross-linked polymeric systems that contain water in an equilibrium state and have good hydrophilicity. The hydrogel material not only can keep a stable shape, but also can allow small molecular substances to permeate and diffuse, and has important application in the field of biomedical engineering. The hydrogel is widely existed in nature, and a plurality of living body tissues are natural hydrogel, so that the hydrogel contact lens material is easily accepted by human bodies.
However, the current hydrogel contact lenses still have some defects, such as low refractive index, poor mechanical strength, and still are difficult to meet the requirements.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the technical problems, the invention provides a high-refractive-index corneal contact lens material and application thereof. The hydrogel cornea contact lens made of the material has good elongation and rebound resilience and super-strong mechanical strength. Meanwhile, the hydrogel cornea contact lens has high water content, high refractive index, optical transparency and biocompatibility, and the manufacturing method is simple, does not need to use a solvent, and improves the safety of wearing by human eyes.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:
a corneal contact lens material comprises the following raw materials in parts by weight:
18-52 parts of polymerizable vinyl monomer with a substituted aromatic ring structure, hydrophilic monomer: 21 to 80 parts by weight of a reaction product,
a crosslinking agent: 0.1-1 part of free radical initiator: 0.1 to 1 portion.
Preferably, the method comprises the following steps:
the polymerizable vinyl monomer with the substituted aromatic ring structure has the following structure:
Figure BDA0002356559440000021
wherein:
a is (CH)2)w,w=0-5;
B is (CH)2)mOr [ O (CH)2)2]n,m=2-5,n=6-9;
C is H, CH3、CH2CH3Or CH2OH;
X is absent, O or S.
More preferably, when X is O or S, B is (CH)2) m, wherein m is 2-5.
The hydrophilic monomer is a mixture of 2-hydroxyethyl methacrylate (HEMA), N-vinyl pyrrolidone (NVP) and N, N-Dimethylacetamide (DMA).
The cross-linking agent is a mixture consisting of a dimethylacrylic acid bond type cross-linking agent and a diacrylic acid bond type cross-linking agent, wherein the dimethylacrylic acid bond type cross-linking agent is any one of Ethylene Glycol Dimethacrylate (EGDMA), triethylene glycol dimethacrylate (TEGDMA), diethylene glycol dimethacrylate (DEGDMA) and trimethylolpropane trimethacrylate (TMPTMA); the diacrylic bond type cross-linking agent is any one of 1, 4-hexanediol diacrylate (HDDA), tetraethylene glycol diacrylate (TTEGDA) and neopentyl glycol diacrylate (NPGDA).
The free radical initiator is 2-hydroxy-2-methyl propiophenone or azodiisobutyronitrile. 2-hydroxy-2-methyl propiophenone is used as a photoinitiator. Azobisisobutyronitrile is a thermal initiator.
The invention also provides a method for preparing a corneal contact lens by using the corneal contact lens material, which comprises the following steps: the preparation method comprises the steps of mixing polymerizable vinyl monomers with substituted aromatic ring structures, hydrophilic monomers, cross-linking agents and free radical initiators, uniformly stirring, adding into a corneal contact lens mold, and curing a reaction mixture by a thermal initiation or ultraviolet initiation method to form the corneal contact lens.
The preparation method is simple and easy to operate. Most of the existing preparation methods add solvents. Unlike the existing preparation method, the preparation method of the invention does not add any solvent. The preparation method of the invention has simple post-treatment process and less irritation to human body. Post-processing simply involves both ease of release from the mold and the elimination of the need to remove the solvent. This can save production cost. The preparation method of the invention adopts the copolymerization of reactants to prepare the cornea contact lens.
Has the advantages that: compared with the prior art, the hydrogel corneal contact lens made of the corneal contact lens material has the advantages of high water content, high refractive index, optical transparency, biocompatibility, good elongation and rebound resilience, and super-strong mechanical strength. In addition, the use of the dimethylacrylic acid bond type cross-linking agent and the diacrylic acid bond type cross-linking agent can enable the prepared contact lens material to have better elongation and super-strong mechanical strength. And the addition of the polymerizable vinyl monomer with a substituted aromatic ring structure in the reaction mixture can enable the cornea contact lens to obtain higher refractive index. Finally, the preparation method adopts a bulk polymerization mode, the post-treatment is simple, and the residue is less.
Drawings
FIG. 1 is a transmission test chart of a high refractive index corneal contact lens made of the material of the present invention.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings.
Examples 1 to 8
(1) The composition and the amount of each raw material are shown in the numbers 1-8 in the table 1:
TABLE 1 (unit: wt%)
Figure BDA0002356559440000031
Figure BDA0002356559440000041
Wherein:
1) the polymerizable vinyl monomer having a substituted aromatic ring structure of examples 1, 3, 4 was o-phenylethoxyacrylate. The polymerizable vinyl monomer having a substituted aromatic ring structure of examples 2, 5, 6 was 4-phenylbutyl methacrylate. The polymerizable vinyl monomer having a substituted aromatic ring structure of examples 7, 8 was 5-phenylpentyl methacrylate.
2) The dimethacrylate bond-type crosslinking agents of examples 1, 4 and 5 were ethylene glycol dimethacrylate. The dimethacrylate-based crosslinking agent of examples 2, 7 and 8 was triethylene glycol dimethacrylate. The dimethacrylate bonding type crosslinking agent of example 3 was diethylene glycol dimethacrylate. The dimethacrylate bonding type crosslinking agent of example 6 was trimethylolpropane trimethyl lactone.
3) The dienoenoic acid bond type cross-linking agent of examples 1, 2, and 7 was 1.4-hexanediol dienoenoic acid ester. The diacrylic bond type crosslinking agent of examples 3 and 5 was tetraethyleneglycol diacrylate. The diacrylic bond type crosslinking agent of examples 4, 6, 8 was neopentyl glycol diacrylate.
4) The free radical initiator in examples 1-8 was the photoinitiator 2-hydroxy-2-methyl propiophenone.
(2) Corneal contact lenses prepared by reacting the components shown in Table 1
The reactants were mixed at room temperature (identified as 25 ℃) to produce a curable mixture. Placing the mixture in a corneal contact lens mold, opening an ultraviolet curing device, adjusting the intensity of ultraviolet light to 3uw/cm2, stabilizing for 15-30min, and then placing the filled corneal contact lens mold in the ultraviolet curing device, wherein the reaction time is 1 h.
Comparative example:
as shown in Table 1, reference numeral 9, the lens of this comparative example was a corneal contact lens of the prior art composed of 70% by weight of HEMA, 10% by weight of NVP, 19.7% by weight of SIGMA, 0.1% by weight of EGDMA, and 00.1% by weight of ethylene glycol dimethacrylate.
The method for preparing the corneal contact lens by using the same is the same as the examples 1 to 8.
Test examples
Corneal contact lenses are typically tested for a number of different performance parameters including curvature, diameter, center thickness, water cut, transmittance, and the like.
Dry center thickness was measured using a Mitutoyo Digimatic Indicator model 1D110-ME equipped on a DGS-E type bench.
Wet corneal contact lens diameter and sagittal height were measured on Optimec model B contact lens Analyzer model SAG and curvature was calculated.
All corneal contact lens samples were equilibrated at 21 ± 1 ℃ for a minimum of 2 hours in saline solution prior to measurement and gently blotted with non-delinted cotton to remove excess surface moisture just prior to measurement. The bulk water content can be measured analytically by means of gravimetric measurements.
The corneal contact lens sample was placed in phosphate buffer, placed in a sample chamber, and the mean visible light transmission was measured using an ultraviolet-visible spectrophotometer uv 2450.
The refractive index of the contact lens was measured by a WAY-2W Abbe refractometer.
The results of the measurements of the parameters are shown in table 2:
TABLE 2
Figure BDA0002356559440000051
As can be seen from the data in table 2, the contact lenses of the invention have good shape, water content, transmission and refractive index. From the value of the refractive index, the corneal contact lens of the present invention has a very high refractive index. While comparative example 9, having a refractive index of 1.476, is much lower than the contact lenses of the invention.
As can be seen from figure 1, the corneal contact lens of the invention has a transmittance of over 90%, which meets the standard of commercial corneal contact lenses.

Claims (7)

1. A corneal contact lens material is characterized by comprising the following raw materials in parts by weight:
18-52 parts of polymerizable vinyl monomer with a substituted aromatic ring structure, hydrophilic monomer: 21 to 80 parts by weight of a reaction product,
a crosslinking agent: 0.1-1 part of free radical initiator: 0.1 to 1 portion.
2. The corneal contact lens material of claim 1, wherein the polymerizable vinyl monomer having a substituted aromatic ring structure has the following structure:
Figure FDA0002356559430000011
wherein:
a is (CH)2)w,w=0-5;
B is (CH)2)mOr [ O (CH)2)2]n,m=2-5,n=6-9;
C is H, CH3、CH2CH3Or CH2OH;
X is absent, O or S.
3. The corneal contact lens material of claim 2, wherein X is O or S and B is (CH)2) m, wherein m is 2-5.
4. The corneal contact lens material of claim 1, wherein said hydrophilic monomer is a mixture of 2-hydroxyethyl methacrylate, N-vinyl pyrrolidone, and N, N-dimethylacetamide.
5. The corneal contact lens material according to claim 1, wherein said crosslinking agent is a mixture of a dimethacrylate bonding type crosslinking agent and a diacrylate bonding type crosslinking agent, and said dimethacrylate bonding crosslinking agent is any one of ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; the diacrylic bond type cross-linking agent is any one of 1, 4-hexanediol diacrylate, tetraethylene glycol diacrylate and neopentyl glycol diacrylate.
6. The corneal contact lens material of claim 1, wherein the free radical initiator is 2-hydroxy-2-methyl propiophenone or azobisisobutyronitrile.
7. A method for producing a contact lens using the contact lens material according to any one of claims 1 to 6, comprising the steps of: the preparation method comprises the steps of mixing polymerizable vinyl monomers with substituted aromatic ring structures, hydrophilic monomers, cross-linking agents and free radical initiators, uniformly stirring, adding into a corneal contact lens mold, and curing a reaction mixture by a thermal initiation or ultraviolet initiation method to form the corneal contact lens.
CN202010009396.1A 2020-01-06 2020-01-06 High-refractive-index corneal contact lens material and application thereof Pending CN111154028A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010009396.1A CN111154028A (en) 2020-01-06 2020-01-06 High-refractive-index corneal contact lens material and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010009396.1A CN111154028A (en) 2020-01-06 2020-01-06 High-refractive-index corneal contact lens material and application thereof

Publications (1)

Publication Number Publication Date
CN111154028A true CN111154028A (en) 2020-05-15

Family

ID=70561310

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010009396.1A Pending CN111154028A (en) 2020-01-06 2020-01-06 High-refractive-index corneal contact lens material and application thereof

Country Status (1)

Country Link
CN (1) CN111154028A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113321763A (en) * 2021-08-02 2021-08-31 微创视神医疗科技(上海)有限公司 Polymer, application thereof and ophthalmic medical equipment

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1155845A (en) * 1995-06-07 1997-07-30 阿尔康实验室公司 Improved high refractive index ophthalmic lens materials
CN1353726A (en) * 1999-09-07 2002-06-12 爱尔康通用有限公司 Foldable ophthalmic and otorhinolaryngological device materials
CN1371394A (en) * 1999-09-07 2002-09-25 爱尔康公司 Ophthalmic and otorhinolaryngological device materials
US20090227702A1 (en) * 2008-03-07 2009-09-10 Hermann Neidlinger High refractive index oxygen permeable contact lens system and method
CN103941419A (en) * 2014-04-18 2014-07-23 江苏海伦隐形眼镜有限公司 Hydrogel cornea contact lens and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1155845A (en) * 1995-06-07 1997-07-30 阿尔康实验室公司 Improved high refractive index ophthalmic lens materials
CN1353726A (en) * 1999-09-07 2002-06-12 爱尔康通用有限公司 Foldable ophthalmic and otorhinolaryngological device materials
CN1371394A (en) * 1999-09-07 2002-09-25 爱尔康公司 Ophthalmic and otorhinolaryngological device materials
US20090227702A1 (en) * 2008-03-07 2009-09-10 Hermann Neidlinger High refractive index oxygen permeable contact lens system and method
CN103941419A (en) * 2014-04-18 2014-07-23 江苏海伦隐形眼镜有限公司 Hydrogel cornea contact lens and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113321763A (en) * 2021-08-02 2021-08-31 微创视神医疗科技(上海)有限公司 Polymer, application thereof and ophthalmic medical equipment

Similar Documents

Publication Publication Date Title
EP2453292B1 (en) Soft hybrid contact lens, method for producing same, and hydration method
KR101918645B1 (en) Silicone hydrogel soft contact lens having wettable surface
EP0811393B1 (en) Soft intraocular lens
CN103467652B (en) A kind of hydrogel contact glass and preparation method thereof
US4139692A (en) Copolymer for contact lens, its preparation and contact lens made thereof
EP0231572B1 (en) Silicone-sulfone and silicone-fluorocarbon-sulfone gas permeable contact lenses and compositions thereof
KR102295439B1 (en) (meth)acrylamid polymers for contact lens and intraocular lens
CN103941419B (en) Hydrogel cornea contact lens and preparation method thereof
EP0186789B1 (en) Hydrophilic copolymers, their use as biomedical materials and contact lenses made of these copolymers
CZ23194A3 (en) Polymer for producing eye lenses with built-in acyclic monomer
KR20020040661A (en) Ocular lenz materials and process for producing the same
CN102617787B (en) Hydrogel contact lens material and preparation method thereof
TWI630931B (en) Ophthalmic lens and manufacturing method thereof
JPH10339857A (en) Manufacture of chemical slow controlled releasing contact lens and chemical slow controlled releasing contact lens obtained by the same
KR20100087152A (en) Hydrogel with high water content and stability
CN107260655A (en) Silicon substrate hydrogel contact lens medicine-carried system that a kind of vitamin E is modified and preparation method thereof
CN111154028A (en) High-refractive-index corneal contact lens material and application thereof
KR100286971B1 (en) Ocular lens material and process for producing the same
CN105037629A (en) Silicone hydrogel with good resilience and preparation method and application method therefor
CN110643055A (en) Hydrogel and preparation method thereof, and biological membrane fixing device and application
CN107641168B (en) Polymer, preparation method and application thereof
EP0332179B1 (en) Highly water-absorptive ocular lens material
KR101237489B1 (en) Contact lens comprising vinylphenylboronic acid and manufacturing method thereof
CN113164642B (en) Medical device
TW202344600A (en) Contact lens with anti-friction and high moisturizing property and manufacturing method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20200515

RJ01 Rejection of invention patent application after publication