CN106366241B - Ophthalmic materials and application thereof with fluorescent characteristic - Google Patents
Ophthalmic materials and application thereof with fluorescent characteristic Download PDFInfo
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- CN106366241B CN106366241B CN201510436323.XA CN201510436323A CN106366241B CN 106366241 B CN106366241 B CN 106366241B CN 201510436323 A CN201510436323 A CN 201510436323A CN 106366241 B CN106366241 B CN 106366241B
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- fluorescer
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Abstract
The present invention relates to the ophthalmic materials with fluorescent characteristic comprising basis material and fluorescer, the invention further relates to the method for preparing the ophthalmic materials and the Medical Devices prepared by the ophthalmic materials.
Description
Technical field
The present invention relates to the ophthalmic materials with fluorescent characteristic comprising basis material and fluorescer.The invention further relates to
The Medical Devices for preparing the method for the ophthalmic materials and being prepared by the ophthalmic materials.
Background technique
Hard corneal contact lens or Ortho-K are general to require testing for the first time with process or compartment time during wearing
Carry out the suitability inspection of eyeglass and cornea.At present mainly by way of cornea fluorescent staining, pass through the glimmering of observation cornea
Light distribution assesses suitability.The extrinsic fluorescence agent used is fluorescein sodium, the entitled 9-(neighbour's carboxyl benzene of chemistry of fluorescein sodium
Base) -6- hydroxyl -3H- xanthene -3- ketone disodium salt, it can be used for canthus membrane damage, Fundus angiography diagnosis and blood circulation time
Measurement.But it is found in clinic there are the allergic reactions such as nausea and vomiting, skin nettle rash, cough.(Liu steps on Liu Dengzhong etc.
A gram phenanthrene fluorescein sodium corneal dyeing is caused the world case with anaphylactic shock due [J] ophthalmology magazine by loyalty, Zheng Weiguo, and 2008,01:
It 185) is even more to have reported fluorescein sodium corneal dyeing to cause anaphylactic shock.
Fluorescein sodium is the relatively small fluorescer of stimulation, the irritations such as other fluorescers such as Hu Hong (Bengal rose red)
It is stronger, and inherently there is cytotoxicity, the application of fluorescer direct staining cornea is by very big the problem of due to safety
Limitation.And the pupil region for needing to develop the color in contact lense suitability inspection is only the region of contact lense covering, existing cornea
Decoration method dyes all corneas wholes, brings security risk, if fluorescer enters blood allergic reaction meeting more using excessive
What is added is strong.
201641967 U of patent CN, which is reported, is fixed on paper for fluorescein sodium and lissamine green (acid rhodamine B) absorption
Material carrier rinses perfusion liquid or physiological saline visual function improving with intraocular when inspection, and test paper is posted on ocular and carries out ocular dyeing, this
Kind of method solves the problems such as inconvenience that liquid coloring agent clinically uses, sterilizing in advance, coloring agent is needed to overflow eye folder.
203458370 U of patent CN has reported a kind of corneal dyeing device, there is a small ball at the top of hand-held stick, and surface is coated with fluorescein
Sodium.But the above both methods substantially or using coloring agent makes corneal dyeing, and is possible to penetrate into intraocularly, thus draws
The stimulation and allergic reaction risen can not solve.
Therefore, now need to develop a kind of material, fluorescer is dispersed in basis material such as high score in a manner of polymerizeing or adulterate etc.
Sub- material internal or with surface grafting, the modes such as surface modification or surface coating are fixed on substrate material surface.Fluorescer and base
Body material can be stable combination, material cornea do not make corneal dyeing, but under crack lamp source or Pentero microscope
Material can fluoresce, and oculist is capable of the suitability of clear, clear judgement material and cornea, thoroughly get rid of exogenous angle
Film fluorescent dye, this method is without adding any additional reagent (including fluorescer).
Summary of the invention
Summary of the invention
In view of the above-mentioned problems in the prior art, inventor has developed the eye with fluorescent characteristic by research extensively and profoundly
Section's material, the laminating degree of eye medical instrument and cornea can be diagnosed by corneal dyeing by enabling oculist not, or
Person can see eye structure, eye ground, blood vessel situation etc. clearly.The present invention provides the ophthalmic materials with fluorescent characteristic, lead to
It crosses the means such as turning, injection molding, pressing mold, centrifugal casting and required ophthalmological instruments is made.Ophthalmic materials of the present invention are in visible light or ultraviolet
Under light or X-ray or Infrared irradiation, autofluorescence.
The present invention relates to the ophthalmic materials with fluorescent characteristic for manufacturing ophthalmic medical instrument, and provide preparation tool
There are the method for the ophthalmic materials of fluorescent characteristic and the product containing this ophthalmic materials with fluorescent characteristic；Specifically, this hair
The bright product for being related to having the ophthalmic materials of fluorescent characteristic, detect resulting product can using fluorescent characteristic, in particular, eye
Section's equipment, e.g., eyeglass (especially ophthalmic lens), the intraocular lens with fluorescent characteristic, cornea with fluorescent characteristic connect
Touch mirror, Ortho-K, iris hooks, internal oculoscope, artificial cornea, cornea inner ring, capsular tension ring, intracorneal lens, green light
Eye drain valve, slow releasing carrier of medication, Ocular tamponades, eyeground filler, glasses, goggles, Medical Devices lens, telescope,
Surveillance mirror etc..
The present invention relates to the ophthalmic materials with fluorescent characteristic comprising:
Basis material；
At least one fluorescer；
Wherein, fluorescer is selected from the combination of basis material: fluorescer polymerize with polymerisable monomer, fluorescer disperses
In basis material, fluorescer substrate material surface is fixed on surface grafting, surface modification and/or surface coating method.
One embodiment of the invention, the launch wavelength range of the fluorescer are 300-850 nanometers, it is preferable that described
The maximum emission wavelength range of fluorescer is 500-850 nanometers.
Another embodiment of the invention, fluorescer are selected from: fluoresceins (sodium), cyanine fluorochrome, isothiocyanic acid
Fluorescein, the rhodamine substance with fluorescent characteristic, the lanthanide chelate with fluorescent characteristic, phycoerythrin (P-
Phycoerythrin, PE), generate for example more dinoflagellate phyllochlorins (PerCP) of substance of fluorescence after enzyme effect, propidium iodide with
And it is other modify with maximum emission wavelength based on the above fluorescer at 300-850 nanometers the derivatives of modification or will more than
The fluorescer that compound sensible load is formed into nano material.
Another embodiment of the invention, fluorescer are selected from fluoresceins (sodium), indocyanine green and O- methacrylic acid
Fluorescein ester.
Another embodiment of the invention, basis material be selected from hydrogel, silicone-hydrogel, fluorine Si acrylate, silicone,
Polystyrene and methyl methacrylate.
Another embodiment of the invention is related to the method for preparing ophthalmic materials of the present invention, includes the following steps:
1) polymerisable monomer and optional additives such as crosslinking agent, thermal initiator, ultraviolet absorber etc. are mixed；
2) fluorescer is added, and makes it dissolve, then polymerize.
Another embodiment of the invention is related to the method for preparing ophthalmic materials of the present invention, includes the following steps:
1) polymerisable monomer and optional additives such as crosslinking agent, thermal initiator, ultraviolet absorber etc. are mixed, is then polymerize
Obtain basis material；
2) fluorescer of optional used additives such as polymerisable monomer dissolution is added, is then polymerize such as graft polymerization or surface
Modification.
Another embodiment of the invention is related to Medical Devices comprising ophthalmic materials of the present invention.The medical treatment
Equipment is ophthalmic medical equipment, is preferably selected from: intraocular lens, contact lens, Ortho-K, rainbow with fluorescent characteristic
Film drag hook, internal oculoscope, artificial cornea, cornea inner ring, capsular tension ring, intracorneal lens, Glaucoma Drainage valve, medicament slow release carry
Body, Ocular tamponades, eyeground filler, glasses, goggles, Medical Devices lens, telescope, surveillance mirror.For example, institute of the present invention
Ophthalmic materials are stated coated on the surface of Medical Devices.
The invention further relates to ophthalmic materials of the present invention to prepare the purposes in ophthalmic medical equipment, wherein ophthalmic medical equipment
Be selected from: with the intraocular lens of fluorescent characteristic, contact lens, Ortho-K, iris hooks, internal oculoscope, artificial cornea,
Cornea inner ring, capsular tension ring, intracorneal lens, Glaucoma Drainage valve, slow releasing carrier of medication, Ocular tamponades, eyeground filling
Object, glasses, goggles, Medical Devices lens, telescope, surveillance mirror.
The invention further relates to the method that detection ophthalmic medical equipment is in contact with it the suitability of object such as cornea, wherein this method
Using Medical Devices of the present invention, prepared by ophthalmic materials of the present invention.The method of the detection suitability is only
Using only Medical Devices of the present invention, without adding any additional reagent.
Detailed description of the invention
The combination of fluorescer and basis material of the present invention is selected from:
(1) fluorescer participates in polymerization in basis material forming process；
(2) fluorescer is added in basis material in basis material forming process by physical dispersion；
(3) fluorescer is fixed on molded substrate material surface in a manner of surface grafting, surface modification；And/or
(4) fluorescer is fixed on molded substrate material surface with surface coating method.
When (1) fluorescer is that fluorescer participates in polymerizeing in basis material forming process with the combination of basis material
When, basis material is the material comprising polymerisable monomer.
When the combination of (2) fluorescer and basis material is that fluorescer is divided in basis material forming process by physics
It dissipates when being added in basis material, basis material can be any suitable material, optionally include polymerisable monomer.
When the combination of (3) fluorescer and basis material is that fluorescer is fixed in a manner of surface grafting, surface modification
When molded substrate material surface, basis material is molded material, but on the surface of the material includes polymerizable groups.
Polymerizable groups herein can be, such as: vinyl, allyl, butylene, acryloxy, methacryl
Oxygroup, acrylamido, methacryl amido, vinyl ether, alkynyl, hydroxyl, sulfydryl, amino, imino group, carboxyl, acid anhydrides,
Aldehyde radical, isocyanate group, siloxy group, epoxy group, ring nitrogen base, etc..
When the combination of (4) fluorescer and basis material is that fluorescer is fixed on molded base with surface coating method
When body material surface, basis material is molded material, can be any material that can be coated by fluorescer.
Basis material of the present invention preferably is selected from acrylic polymer or silicone quasi polymer or preferred good biocompatibility
Any suitable material, such as polymer material.
Fluorescer of the present invention is any fluorescer that launch wavelength range is 300-850 nanometers.
In one embodiment of the present invention, fluorescer and basis material obtain the present invention by copolymerization and have fluorescent characteristic
Ophthalmic materials when, basis material preferably is selected from by the resulting material of the polymerisable monomer containing groups such as vinyl, acrylics.
When containing polymerizable groups in fluorescent molecules structure, such as: vinyl, allyl, butylene, acryloxy, metering system
Acyloxy, acrylamido, methacryl amido, vinyl ether, alkynyl, hydroxyl, sulfydryl, amino, imino group, carboxyl, acid
Acid anhydride, aldehyde radical, isocyanate group, siloxy group, epoxy group, ring nitrogen base, etc. can be with one starting of polymerisable monomer of basis material
Raw copolyreaction, fluorescent molecules are present in matrix material molecules chain in the form of covalent bond, and fluorescer is fixed on matrix material
In material, therefore the toxicity of fluorescer itself can be ignored completely.
In another embodiment of the present invention, when fluorescer dispersion (as being blended or adulterating) obtains this in basis material
When inventing the ophthalmic materials with fluorescent characteristic, basis material preferably comprises the basis material of good biocompatibility.Work as fluorescer
It is dispersed in basis material in a manner of being blended or adulterating etc., fluorescent molecules and matrix material molecules chain are with hydrogen bond or Van der Waals force
Effect is combined together, and fluorescent molecules are bound in basis material, cannot be freely accessible in blood or other body fluid.
In another embodiment of the present invention, when fluorescer is fixed on matrix material in a manner of surface grafting, surface modification
When expecting surface, basis material is selected from polymerizable basis material, preferably on the surface includes the polymerizable groups of good biocompatibility.
In the case, contain polymerizable groups in basis material and/or fluorescent molecules structure, such as: vinyl, allyl, fourth
Alkene, acryloxy, methacryloxy, acrylamido, methacryl amido, vinyl ether, alkynyl, hydroxyl, mercapto
Base, amino, imino group, carboxyl, acid anhydrides, aldehyde radical, isocyanate group, siloxy group, epoxy group, ring nitrogen base, etc. wherein matrix material
Material is preferably the basis material of good biocompatibility, can be with the base on corresponding basis material and/or fluorescent molecules side chain
Graft reaction occurs for group, and basis material and fluorescent molecules are combined together in the form of covalent bond, and fluorescer is fixed on matrix
On material internal or its surface, cannot equally it be freely accessible in blood or other body fluid.
In another embodiment of the present invention, when fluorescer is fixed on substrate material surface with surface coating method,
Basis material be selected from good biocompatibility any suitable basis material, as hydrogel, silicone-hydrogel, fluorine Si acrylate,
Silicone, polystyrene, methyl methacrylate etc..
In another preferred scheme, fluorescer be dispersed in dissolve, in a manner of suspended, emulsification etc. other auxiliary agents (such as:
Cosolvent, lubricant, hydrophilic coating, carries medicine, color masterbatch, ultraviolet absorber, crosslinking agent, coupling agent, pH adjusting agent, resists emulsifier
Electrostatic agent, release agent, etc.) in, and be coated in the surface of basis material, fluorescent molecules and matrix material molecules chain with hydrogen bond or
Van der Waals interaction is combined together, and fluorescer is bound in the surface of basis material, cannot be freely accessible to blood or other bodies
In liquid.
It is glimmering in order to enhance the affinity between fluorescent molecules and matrix material molecules in another preferred scheme
Photo etching molecule can carry out chemical modification under the premise of not changing photoactive；Basis material can also be activated, packet
It includes but is not limited to, corona treatment, sided corona treatment, flame treatment, strong acid treatment, highly basic processing etc..
Being suitable for the invention typical polymerisable monomer is the monomer that those are amenable to such as Raolical polymerizable.With regard to this
For term used by specification, term " acrylic acid " is generally used to refer to wherein at least containing a kind of including acrylic acid and methyl
The acrylic or methacrylic acid type monomer of acrylic acid, acrylate or methacrylate and their substitutive derivative
Polymer." (methyl) acrylic acid " includes acrylic acid and methacrylic acid derivative.This kind of monomer is ripe for the art
Know.The example of this acrylic monomers include: (methyl) alkyl acrylate for example methyl methacrylate, ethyl acrylate,
Methyl acrylate, n-butyl acrylate, 2-EHA, lauryl acrylate, cyclohexyl acrylate, acrylic acid
Isopropyl esters, isobutyl acrylate, acrylic acid n-pentyl ester, acrylic acid n-propyl ester, ethyl methacrylate, toluene propylene
Sour n-propyl ester, n-butyl methacrylate, isopropyl methacrylate, methacrylic acid n-octyl ester, metering system
Sour dodecyl ester, acrylic acid neopentyl ester, n-myristyl base ester, methacrylic acid n-tetradecane base ester, methyl-prop
Olefin(e) acid isobutyl, methacrylic acid n-pentyl ester, methacrylic acid n-hexyl ester, methacrylic acid isoamyl base ester, methyl-prop
Olefin(e) acid cyclopentyl ester, methacrylic acid positive decyl ester etc.；Other acrylic acid and methacrylate such as methacrylic acid 2- bromine
Ethyl ester, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylic acid 2- benzene
Ethyl ester, acrylic acid 3- methoxy butyl acrylate, methacrylic acid 2- methoxy butyl acrylate and methacrylic acid 2- n-butoxy
Ethyl ester；Reactive hydrogen functional monomer comprising (methyl) acrylate that hydroxyl replaces, such as acrylic acid 2- hydroxyl ethyl ester and acrylic acid
3- hydroxypropyl ester；(methyl) acrylate such as methacrylic acid sulfoethyl ester and acrylic acid sulfopropyl ester comprising sulfonic acid；And
The acrylate of phosphoric acid such as, (methyl) acrylic acid 2- phosphine ethyl ester, or mixtures thereof.
Being suitable for the invention polymerisable monomer includes silane and siloxanes.This kind of monomer is for known to the art
, this kind of Exemplary monomers include: methyl trichlorosilane, dimethyldichlorosilane, methyltriethoxysilane, methyl trimethoxy oxygroup
Silane, phenyltrimethoxysila,e, (3,3,3- trifluoro propyl) methyl dimethoxysilane, vinyltriethoxysilane or second
Alkenyl trimethoxy silane, methacryloxypropyl three (trimethylsiloxane group) silane, 3-(methacryloxypropyl) propyl
The block copolymer of trimethoxy silane, dimethyl siloxane and diphenyl siloxane, divinyl blocks, vinyl silicone oil,
3-(isobutene acyl-oxygen) propyl trimethoxy silicane, allyltriethoxysilane, allyl three (three silyloxies) silane, 3-
Acryloyloxypropyltrimethoxysilane, hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, hybrid ring siloxane, three
Or mixtures thereof fluoropropyl methyl cyclotrisiloxane or tetrafluoro butyl methyl cyclotetrasiloxane,.
Can be used for other polymerisable monomers of the invention includes: butadiene, styrene, α-methylstyrene, styrene sulphur
Sour sodium, vinyltoluene, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, ethyl acrylonitrile, methyl vinyl ether, isopropyl
Vinyl ethers, n-butyl vinyl ether, isobutyl vinyl ether, tert-Butyl vinyl ether, 2- ethylhexyl vinyl ether, 4- hydroxyl
Butyl vinyl ether, 1,4-butanediol divinyl ether, diethylene glycol divinyl ether, vinyl esters such as, vinyl-acetic ester, alkane
Hydroxyl vinyl esters of carboxylic acids, vinyl propionate, vinyl butyrate, vinyl isobutyrate base ester, caproic acid vinyl esters, 2- ethyl saccharinic acid
Vinyl acetate and vinyl base ester；Allyl chloride, methallyl chloride, dichloroethylene, vinyl chloride, vinyl fluoride, difluoroethylene,
Sodium vinyl sulfonate, butyl vinyl sulfonate, phenyl vinyl sulfone, methyl ethylene sulfone, N- ethenyl pyrrolidone diketone, N-
Vinyl oxazolidinedione, methacrylaldehyde, acrylamide, Methacrylamide, N, N- dimethyl (methyl) acrylamide, methylol
Acrylamide, N- butoxy (methyl) acrylamide, isobutoxy (methyl) acrylamide etc., etc.；Other olefinics are unsaturated
Carboxylic acid and its ester such as, the dialkyl ester and trialkyl ester of binary and tricarboxylic acid (such as itaconic acid), including (the 2- second of maleic acid two
Base hexyl) ester, maleic acid dibutyl ester, dimethyl fumarate, dimethyl itaconate, citraconic acid diethyl ester, aconitic acid front three
Base ester, mesaconic acid diethyl ester, itaconic acid two (2- ethylhexyl) ester, itaconic acid two (2- chloroethyl) ester, maleic acid, maleic acid
Acid anhydride, fumaric acid, itaconic acid；Or mixtures thereof and alkene is such as, diisobutylene, 1- octene, 1- decene, 1- hexadecylene etc.,.
In one embodiment of the present invention, fluorescer polymerize with basis material obtains the eye that the present invention has fluorescent characteristic
When section's material, or when fluorescer is dispersed in basis material and obtains ophthalmic materials of the present invention with fluorescent characteristic, the present invention
Ophthalmic materials with fluorescent characteristic can be prepared by the method included the following steps:
1) polymerisable monomer and optional additives such as thermal cross-linking agent, initiator, ultraviolet absorber etc. are mixed；
2) fluorescer is added, and makes it dissolve, then polymerize.
More specifically, there are the present invention ophthalmic materials of fluorescent characteristic can be prepared by the method included the following steps:
1) polymerisable monomer is mixed with thermal initiator, crosslinking agent and/or ultraviolet absorber；
2) fluorescer is added, makes it dissolve；
3) 2) reaction system obtained is placed in mold；
4) it is polymerize, such as water-bath polymerization；
5) it polymerize again in drier.
In another embodiment of the present invention, when fluorescer is fixed on matrix material in a manner of surface grafting, surface modification
When expecting surface, there are the present invention ophthalmic materials of fluorescent characteristic can be prepared by the method included the following steps:
1) polymerisable monomer and optional additives such as crosslinking agent, thermal initiator, ultraviolet absorber etc. are mixed, is then gathered
It closes, obtains basis material；
2) fluorescer is added, and makes it dissolve, such as fluorescer is dissolved with suitable auxiliary agent (such as polymerisable monomer),
Then it is polymerize such as graft polymerization or surface modification or trans-printing.
More specifically, there are the present invention ophthalmic materials of fluorescent characteristic can be prepared by the method included the following steps:
1) polymerisable monomer is mixed with thermal initiator, crosslinking agent and/or ultraviolet absorber；
2) 1) reaction system obtained is transferred in mold；
4) it is polymerize, such as water-bath polymerization；
5) it polymerize again in drier；
6) fluorescer is dissolved, for example, the suitable polymerisable monomer of fluorescer is dissolved；
7) system of above-mentioned acquisition is polymerize again such as graft polymerization or surface modification or trans-printing.
In another embodiment of the present invention, when fluorescer is fixed on substrate material surface with surface coating method,
There are the present invention ophthalmic materials of fluorescent characteristic can be prepared by the method included the following steps:
1) suitable basis material is obtained；
2) by fluorescer, such as by a kind of suitable solvent dissolution of fluorescer, it is coated in substrate material surface.
In the methods of the invention, dosage of crosslinking agent is 0.1-20 weight %, the preferably 0.5-15% of polymerisable monomer, particularly
1-5%.Ultraviolet absorber dosage is 0-10 weight %, the preferably 0-5% of polymerisable monomer, particularly 0-1%.Initiator amount is can
0.01-10 weight %, the preferably 0.01-5% of polymerized monomer, particularly 0.05%-1.0%.
Conventional application techniques such as routine or airless spraying, roller coating, brushing, curtain painting, showering and dip-coating method can be used
By ophthalmic materials of the present invention coated on required ground.Usual printing techniques such as conventional letter press, recessed can be used simultaneously
The methods of version printing, offset printing, silk-screen printing, heat transfer printing, xerography, ink jet printing or 3D printing are by eye of the present invention
Section's material is coated on required ground.It, can be optionally in room temperature or height after ophthalmic materials of the present invention are applied on ground
The lower solidification of temperature.
The other optional components that can be used in the present invention include cosolvent, pigment, filler, dispersing agent, curing agent, wetting
Agent, defoaming agent, ultraviolet absorbing agent, antioxidant, bactericidal agent and stabilizer.
In the present invention, there is no specific restriction to the method for being used to prepare ophthalmological instruments, traditional known formula can be selected from
Method, such as turning method, compression molding method, injection moulding, centrifugal casting.
The invention further relates to the method that detection ophthalmic medical equipment is in contact with it the suitability of object such as cornea, wherein this method
Medical Devices prepared by the present invention, which are only used only, can be carried out.Specifically, for example, being tested for the first time with process or wearing process
The suitability inspection of middle eyeglass and cornea, can be only by the fluorescent material cornea (nothing of tool of the present invention
Fluorescer need to additionally be added and make corneal dyeing), material can fluoresce under crack lamp source or Pentero microscope, due to
Medical Devices prepared by the present invention have fluorescence, and oculist is capable of being adapted to for clear, clear judgement material and cornea
Property.It can be seen that Medical Devices prepared by material of the present invention and the present invention thoroughly get rid of exogenous cornea fluorescence dye
Toner, the method that the present invention detects the suitability that ophthalmic medical equipment is in contact with it object such as cornea are not necessarily to add any additional examination
Agent (including fluorescer).
Following example is used to further illustrate various forms of the invention, rather than in any way to the scope of the invention
Limitation.Following abbreviations are suitable for whole embodiments.
Specific embodiment
Hereinafter, the present invention will be described more fully by specific embodiment, provided embodiment is only to say
Bright property and be not intended to limit the present invention
Embodiment 1: the preparation of rhodamine B hydrogel ophthalmological instruments
In 250ml beaker, precise is put into 0.35g 2- [2- hydroxyl -5- [2- (methacryloxypropyl) ethyl] benzene
Base] -2H- benzotriazole, 0.12 g azodiisobutyronitrile, 3.5g ethylene glycol dimethacrylate, 96g hydroxyethyl methacrylate second
Ester, 0.002 g Sulforhodamine B.
After being stirred well to fluorescer whole dissolution, system is transferred in test tube made of a polyethylene, height is passed through
Then test tube sealing is put into 65 DEG C of water baths 24 hours, taking-up is put by the nitrogen of purity at least 30 minutes in mixed liquor
Further it polymerize 12 hours in the drying chamber in 90 DEG C of blast driers.After taking out cooled to room temperature after molding, it is cut into
Cylindrical body.Then vacuum drying obtains material requested at a certain temperature.By corresponding optical design through lathe process, polishing,
At soft contact lens after cleaning.
Embodiment 2: the preparation of Bengal rose red hydrogel ophthalmological instruments
In 250ml beaker, precise is put into 0.35g 2- [2- hydroxyl -5- [2- (methacryloxypropyl) ethyl] benzene
Base] -2H- benzotriazole, 0.12 g azodiisobutyronitrile, 3.5 ethylene glycol dimethacrylate, 76g hydroxyethyl methacrylate second
Ester, 20g n-vinyl pyrrolidone, 0.004 g Bengal rose red.
After being stirred well to fluorescer whole dissolution, system is transferred in test tube made of a polyethylene, height is passed through
Then test tube sealing is put into 65 DEG C of water baths 24 hours, taking-up is put by the nitrogen of purity at least 30 minutes in mixed liquor
Further it polymerize 12 hours in the drying chamber in 90 DEG C of blast driers.After taking out cooled to room temperature after molding, it is cut into
Institute is cylindrical.Then vacuum drying obtains material requested at a certain temperature.By corresponding optical design through lathe process, throwing
At soft contact lens after light, cleaning.
Embodiment 3: the preparation of indocyanine green hydrogel ophthalmological instruments
In 250ml beaker, precise is put into 0.35g 2- [2- hydroxyl -5- [2- (methacryloxypropyl) ethyl] benzene
Base] -2H- benzotriazole, 0.12 g azodiisobutyronitrile, 3.5 ethylene glycol dimethacrylate, 76g hydroxyethyl methacrylate second
Ester, 20g n-vinyl pyrrolidone, 0.004 g indocyanine green.
After being stirred well to fluorescer whole dissolution, system is transferred in test tube made of a polyethylene, height is passed through
Then test tube sealing is put into 65 DEG C of water baths 24 hours, taking-up is put by the nitrogen of purity at least 30 minutes in mixed liquor
Further it polymerize 12 hours in the drying chamber in 90 DEG C of blast driers.After taking out cooled to room temperature after molding, it is cut into
Institute is cylindrical, and then vacuum drying obtains material requested at a certain temperature.By corresponding optical design through lathe process, throwing
At soft contact lens after light, cleaning.
Embodiment 4: the preparation of fluorescein hard air-permeable material and instrument
0.1g fluorescein sodium is dissolved in the hydroxyethyl methacrylate of 10g first, is configured to the fluorescein of 1% concentration
Sodium hydroxyethyl methacrylate solution, then in 250ml beaker, precise is put into 60g methacrylic acid hexafluoro isopropyl ester,
25g methacryloxypropyl three (trimethylsiloxane group) silane, 5g ethylene glycol dimethacrylate, 5g M2D25, 4.9g
Methacrylic acid is eventually adding the fluorescein sodium hydroxyethyl methacrylate solution of 1% concentration of 0.1g.
After being sufficiently stirred, system is transferred in test tube made of a polyethylene, is passed through the nitrogen of high-purity in mixing
At least 30 minutes in liquid, then test tube sealing is put into 65 DEG C of water baths 24 hours, taking-up is put into 90 DEG C of blast driers
Further it polymerize 12 hours in the drying chamber.After taking out cooled to room temperature after molding, it is cut into cylindrical, then one
Determine to be dried in vacuo at temperature.At Ortho-K or hard air-permeable cornea contact mirror etc. after lathe process, cleaning.
The preparation of embodiment 5:O- methacrylic acid fluorescein ester hard air-permeable material and instrument
First in 250ml beaker, precise is put into 60g methacrylic acid hexafluoro isopropyl ester, 25g methacryloxypropyl
Propyl three (trimethylsiloxane group) silane, 5g ethylene glycol dimethacrylate, 5g M2D25, 5.0g methacrylic acid, finally
It is added 0.01g O- methacrylic acid fluorescein ester (AlfaAesar (China) Chemical Co., Ltd.).
After being stirred well to fluorescer dissolution, system is transferred in test tube made of a plastics, high-purity is passed through
Then test tube sealing is put into 65 DEG C of water baths 24 hours, taking-up is put into 90 DEG C of drums by nitrogen at least 30 minutes in mixed liquor
Further it polymerize 12 hours in the drying chamber in wind drier.After taking out cooled to room temperature after molding, it is cut into cylindrical body
Shape is then dried in vacuo at a certain temperature,.It is connect after lathe process, cleaning at Ortho-K or hard air-permeable cornea
Touch mirror etc..
Embodiment 6: the preparation of silicone-hydrogel material and instrument
In 250ml beaker, precise is put into 0.35g 2- [2- hydroxyl -5- [2- (methacryloxypropyl) ethyl] benzene
Base] -2H- benzotriazole, 0.12 g azodiisobutyronitrile, 3.5 ethylene glycol dimethacrylate, 10g methacryloxypropyl third
Base three (trimethylsiloxane group) silane, 60g N,N-DMAA, 26g n-vinyl pyrrolidone, 0.004g are glimmering
Light element sodium.
After being sufficiently stirred, system is transferred in test tube made of a polyethylene, is passed through the nitrogen of high-purity in mixing
At least 30 minutes in liquid, then test tube sealing is put into 65 DEG C of water baths 24 hours, taking-up is put into 90 DEG C of blast driers
Further it polymerize 12 hours in the drying chamber.After taking out cooled to room temperature after molding, it is cut into cylindrical, then one
Determine to be dried in vacuo at temperature.At internal oculoscope etc. after CNC lathe process, cleaning.
Embodiment 7: the preparation of compression molding fluorescent material instrument
In 250ml beaker, precise is put into 0.35g 2- [2- hydroxyl -5- [2- (methacryloxypropyl) ethyl] benzene
Base] -2H- benzotriazole, 0.12 g azodiisobutyronitrile, 3.5 ethylene glycol dimethacrylate, 96g hydroxyethyl methacrylate second
Ester, 0.004 g fluorescein sodium.
Mixed monomer is poured between negative camber and outcurve face mould, designed eyeglass form is squeezed into, is molded into
By polishing after type, at contact lens after cleaning.
Embodiment 8: plasma surface is grafted fluorescer hard air-permeable material
In 250ml beaker, precise is put into 60g methacrylic acid hexafluoro isopropyl ester, 25g methacryloxypropyl
Three (trimethylsiloxane group) silane, 5g ethylene glycol dimethacrylate, 5g M2D25, 5g methacrylic acid.
It after being sufficiently stirred, is transferred in the columnar mould that one is made of plastics, the nitrogen for being passed through high-purity is molten in mixing
At least 30 minutes in liquid, then plastic mould sealing is put into 65 DEG C of water baths 24 hours, taking-up, which is put into baking oven, is pressed
Mold forming.After taking out cooled to room temperature after molding, it is cut into required shape, is then dried in vacuo at a certain temperature, passed through
At Ortho-K or hard air-permeable cornea contact mirror etc. after lathe process, cleaning.
After being processed into contact lens, the contact lens that material makes are placed in plasma cleaner, oxygen gas
Under atmosphere, plasma power is set as 100w, and the processing time is 300s, carries out surface active to contact lens, will after activation
Eyeglass is placed into the preparatory prepared hydroxyethyl methacrylate solution for containing 1% O- methacrylic acid fluorescein ester, shaking table
After shaking 2 hours, takes out, be put into plasma washing machine after draining, under argon atmosphere, plasma power is set as
100w handles time 100s, carries out inert gas plasma auxiliary grafting.The advantage of the mode of such addition fluorescer is
It being individually grafted on one side in instrument inner surface or outer surface by the modes such as covering selectivity.
Embodiment 9: trans-printing method coats fluorescer
In 250ml beaker, precise is put into 0.35g 2- [2- hydroxyl -5- [2- (methacryloxypropyl) ethyl] benzene
Base] -2H- benzotriazole, 0.12 g azodiisobutyronitrile, 3.5g ethylene glycol dimethacrylate, 96g hydroxyethyl methacrylate second
Ester.
After being stirred well to dissolution, system is transferred in test tube made of a polyethylene, the nitrogen of high-purity is passed through
At least 30 minutes in mixed liquor, then test tube sealing is put into 65 DEG C of water baths 24 hours, it is dry that taking-up is put into 90 DEG C of air blast
Further it polymerize 12 hours in the drying chamber in dry device.After taking out cooled to room temperature after molding, it is cut into cylindrical body.Then
Vacuum drying obtains material requested at a certain temperature.By corresponding optical design at soft after lathe process, polishing, cleaning
Contact lenses.
By 0.002 g Sulforhodamine B, 0.35g 2- [2- hydroxyl -5- [2- (methacryloxypropyl) ethyl] benzene
Base] -2H- benzotriazole, 0.12 g azodiisobutyronitrile, 3.5g ethylene glycol dimethacrylate, 96g hydroxyethyl methacrylate second
Ester is put into 250ml beaker, and stirring to fluorescer is dissolved, and resulting mixture is placed in pre-polymerization 60 minutes at 80 DEG C, obtains viscosity 5000-
The polymer coating of 200000mPas.Contact lenses are placed in punch-pin, the side for passing through trans-printing with a kind of rubber mount
The shape transfer that dope layer is printed in etch plate is fixed to the surface of contact lenses, solidified in 90 DEG C of blast driers by method
Has fluoresent coating soft contact lens.
Technical solution of the present invention has the following characteristics that
1. contact ophthalmology tissue with the medical instrument of ophthalmic materials of the present invention production, fluorescer will not be from material
In drop in ophthalmology tissue and ocular tissue caused to dye, avoid any side effect；
2. the dosage of fluorescer is able to carry out reasonable control, to reach ideal display effect；
3. material prepared good biocompatibility, no cytotoxicity is non-stimulated to ocular tissue；
4. flexible in a manner of the sterilization of medical instrument of this material production, the levels of sterility of medical instrument is to be fully ensured.
It can not have to worry that fluorescence can be destroyed using a variety of sterilization methods such as high-temperature heat sterilization, irradiation sterilization, ethylene oxide sterilizings
The effect of agent.
The above description is only a preferred embodiment of the present invention, is not intended to restrict the invention, it is clear that those skilled in the art
Various changes and modifications can be made to the invention by member without departing from the spirit and scope of the present invention.If in this way, of the invention
Within the scope of the claims of the present invention and its equivalent technology, then the present invention is also intended to encompass these to these modifications and variations
Including modification and variation.
Claims (12)
1. the method that detection ophthalmic medical equipment is in contact with it the suitability of object, it includes following ophthalmic materials that wherein this method, which uses,
Medical Devices, wherein the ophthalmic materials include:
Basis material；
At least one fluorescer；
Wherein, the combination of fluorescer and basis material is selected from:
Fluorescer participates in polymerization in basis material forming process；
Fluorescer is added in basis material in basis material forming process by physical dispersion；And/or
Fluorescer is fixed on substrate material surface in a manner of surface grafting, surface modification,
Wherein the contactant is cornea.
2. according to the method for preceding claims 1, wherein the launch wavelength range of the fluorescer is 300-850 nanometers.
3. according to the method for preceding claims 1 or 2, wherein the launch wavelength range of the fluorescer is 500-850 nanometers.
4. wherein fluorescer is selected from according to the method for preceding claims 1 or 2: fluoresceins, cyanine fluorochrome, different sulphur cyanogen
Sour fluorescein, the rhodamine substance with fluorescent characteristic, the lanthanide chelate with fluorescent characteristic, phycoerythrin, enzyme effect
Afterwards generate fluorescence substance, propidium iodide and it is other 300-850 nanometer have launch wavelength based on the above fluorescer modification
Or mixtures thereof or modified derivative or the fluorescer for forming the above compound sensible load into nano material,.
Or mixtures thereof 5. according to the method for preceding claims 1 or 2, wherein fluorescer is selected from fluoresceins, indocyanine green,.
6. according to the method for preceding claims 1 or 2, wherein basis material be selected from hydrophobic type acrylate, silica gel, hydrogel,
Fluorine Si acrylate, silicone, polystyrene and polymethyl methacrylate, polycarbonate, polysiloxanes, methylsiloxane, benzene
Or mixtures thereof radical siloxane, vinylsiloxane, acrylate radical siloxane and methacrylate siloxanes,.
7. the substance for wherein generating fluorescence after enzyme effect includes more dinoflagellate phyllochlorins according to the method for preceding claims 4
PerCP。
8. wherein fluoresceins are fluorescein sodiums according to the method for preceding claims 4.
9. wherein fluoresceins are fluorescein sodiums according to the method for preceding claims 5.
10. wherein fluoresceins are O- methacrylic acid fluorescein esters according to the method for preceding claims 4.
11. wherein fluoresceins are O- methacrylic acid fluorescein esters according to the method for preceding claims 5.
12. wherein hydrogel includes acrylate hydrogel, silicone-hydrogel according to the method for preceding claims 6.
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| CN109796557A (en) * | 2019-01-11 | 2019-05-24 | 华诺森（武汉）生物医药技术有限公司 | A kind of ultraviolet absorber improves the preparation method of contact lenses uvioresistant performance |
| CN109796556B (en) * | 2019-01-11 | 2021-06-11 | 华诺森（武汉）生物医药技术有限公司 | Preparation method of mechanically demouldable silicone hydrogel contact lens |
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