CN101050294A - Color changeable transparent ophthalmic lens material, and application - Google Patents
Color changeable transparent ophthalmic lens material, and application Download PDFInfo
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- CN101050294A CN101050294A CN 200610039527 CN200610039527A CN101050294A CN 101050294 A CN101050294 A CN 101050294A CN 200610039527 CN200610039527 CN 200610039527 CN 200610039527 A CN200610039527 A CN 200610039527A CN 101050294 A CN101050294 A CN 101050294A
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Abstract
This invention discloses a color-changeable ophthalmic lens material, which comprises a transparent ophthalmic lens material and at least one color-changeable dye. The structural formula of the color-changeable dye is shown in this invention, wherein, R1 and R2 are selected from H, CH3, alkyl, aryl, hetero-substituted alkyl, hetero-substituted aryl with different chain lengths, and polymerizable unsaturated groups. The color-changeable ophthalmic lens material is yellow or dark yellow in sunlight or UV radiation via the conversion of discoloration dye to an isomer with longer absorption wavelength, and is pale or colorless in room via returning to the original isomer. Thus the color-changeable ophthalmic lens material can reduce the damage to human eyes by short wavelength blue light, and does not influence indoor application without sunlight.
Description
Technical field
The present invention relates to a kind of color changeable transparent ophthalmic lens material, with and making ophthalmic lens device, especially artificial lens Application for Field.
Background technology
Along with the increase of age, the mineral crystal of human body intraocular will become harder because of various factors causes the mineral crystal of intraocular, and color is darker and opaque.These factors comprise that factors such as gene, uviolizing are converted into the cystinic acid structure with natural crystalline intravital aminothiopropionic acid structure oxidation, thereby cause crystal to become harder and muddy.
10%～15% the people of having an appointment among the above old man of threescore has the cataract eye illness, and these people's mineral crystal will lose eyesight forever if can not be replaced by artificial lens.
Thereby the sixties in last century ophthalmology medical science and technology worker begins to attempt to replace muddy crystal of human eye with artificial lens and recovers cataract patient's eyesight.
Initial employed crystalline material is a polymethyl methacrylate materials, and the glass transition temperature of this material is higher, and hardness is also bigger, and the crystalline size is also bigger simultaneously.Therefore, the otch that needs during implantation is also bigger, and the intraocular cell runs off more, infects also comparatively seriously, has limited the possibility of the clinical use of crystal.
Until the eighties mid-term, after the back of the hand formula minicrystal design invention, the rigid crystal of methyl methacrylate has just finally been realized the marketization of product.But methyl methacrylate the back of the hand formula crystal still needs the above operative incision of 6.0mm when implanting, the intraocular cell runs off still more, and need sew on several pins, and is also longer relatively in the time that hospital stops.
In order to reduce the difficulty of operation, reduce in the surgical procedure damage to eyes.Usually, the ophthalmologic operation doctor always wishes that its operative incision is the smaller the better.The diameter of intraocular pupil is usually all greater than 4.25mm, and methyl methacrylate the back of the hand formula crystalline optical diameter is generally 5.5mm to 6.0mm.Therefore, when implanting such hard crystal, required mini-incision all must be greater than 6.0mm, and this not only needs to sew on several pins, and the injury to intraocular is also bigger simultaneously.
In order to realize its little otch implantation, the ophthalmology scientific workers take to the research and development of collapsible soft artificial lens, comprising the research and development of silica gel crystalline, the research and development of hydrophilic polyacrylic ester crystalline, the research and development of hydrophobic polypropylene acid esters crystalline.These folded iols have a common feature, and its vitreous state conversion temp all is lower than room temp, and artificial lens at room temperature can be folded the back and implant intraocular capsule bag, recovers its original crystal shape and implant the back.
In general, refractive index is high more, and the artificial lens of making is just thin more, and the required otch of performing the operation is just more little.But if want crystal in the suitable performance of human body intraocular capsule bag, its crystal also needs certain thickness.Now, the comparatively satisfied incision size of surgical doctor directly is 2.0～3.2mm.
The specific refractory power of silica gel crystalline material is low by 1.40～1.46, and its crystal is thicker, and otch is relatively large.Simultaneously, the vitreous state conversion temp of silica gel crystalline material is extremely low, is-120 ℃, the excellent elasticity of material.After the silica gel crystal was implanted intraocular capsule bag by little otch, crystal will resile immediately, and it is bigger to recover power, is easy to its intraocular capsule bag is destroyed.
The crystal that the hydrophilic polyacrylic ester multipolymer is made, its crystal contains a large amount of moisture content, and the aqueous solution of its crystals is easy to exchange with the liquid of intraocular.Simultaneously, nearly all hydrophilic polyacrylic ester material internal contains a large amount of hydroxyls, hydroxyl be easy to solution in the calcium ion complexing, then on the surface of artificial lens with innerly form calcification.Simultaneously, the surface of hydrophilic polyacrylic ester is easy to fibrosis.
The artificial lens that the hydrophobic polypropylene acid ester copolymer is made contains water molecules seldom, or moisture hardly.Simultaneously, hydrophobic polypropylene acid esters material does not contain any hydrophilic hydroxyl.Therefore, hydrophobic polypropylene acid esters material does not have calcification and Fibrotic situation to take place.The specific refractory power of such material is more than 1.47, and the thickness of the artificial lens of making is thin far beyond other crystal.Simultaneously, the glass transition temperature of hydrophobic polypropylene acid esters material is lower than room temperature but is higher than 0 ℃, the plasticity that makes this crystalloid material far beyond other materials for well.When artificial crystal material behind the little otch implantation intraocular capsule bag, slowly recovers its original-shape by one in several seconds or tens of second.Make its probability that destroys its capsule bag come lowly far beyond the silica gel crystal.
But after the artificial lens that hydrophobic acrylic acid's ester copolymer is made is implanted intraocular capsule bag, in the certain hour under the physiological saline temperature, a certain amount of water molecules can infiltrate the inside of artificial lens at leisure, then be gathered into diameter and be about 1 micron or bigger water molecules bubble, this water molecules that is formed by the gathering of crystals water molecules is steeped oneself-meeting and is formed reflective spot, and this shining point can be observed under slit lamp.Though these shining points do not influence its crystalline function, cataract patient and surgical doctor are all wished and its shining point can be eliminated.WO97/24382 discloses a kind of collapsible soft artificial crystal material, and such material contains the formation probability that a small amount of hydrophilic acrylate becomes to assign to reduce its shining point.But such material no longer is a hydrophobic material.
Mention in the previous Chinese patent application 200610037673.X of the applicant, at hydrophobic polypropylene acid esters material, infiltrate an amount of polymerizable alkylene hydrocarbon compound, this compounds does not contain any wetting ability atom, as oxygen, nitrogen, sulphur, chlorine etc.Make the hydrophobicity of acrylate copolymer better.Ooze under the bubble in the physiological saline temperature, enter intracrystalline water molecules much less comparatively speaking, the probability of assembling the water molecules bubble that forms 1 micron size is much smaller.When therefore under slit lamp, observing, observe water molecules shining point seldom, or almost do not observe the water molecules shining point.
All infiltrate UV light absorber in the previous described soft crystalline material and reduce the destruction of ultraviolet ray human body eye inner tissue.But we know, except ultraviolet ray has the injury effect human body ocular tissue.Short wavelength's the blue ray also eyes to the people is harmful.Therefore, people wish that artificial lens can absorb the blue ray that ultraviolet ray can absorb the short wavelength again.
U.S. Pat 5645767, US6153126, US6296785 disclose the patent of yellow hydrophobic material.But no matter the material of this patent disclosure is yellow having or do not have under the solar radiation, thereby has all become colored state when making the cataract patient watch thing under any condition.
Summary of the invention
The objective of the invention is: a kind of material of making color changeable transparent ophthalmic lens is provided.
Another object of the present invention is: with the application of material of the present invention as ophthalmic lens device manufactured materials.
Technical scheme of the present invention is: a kind of color changeable transparent ophthalmic lens material, and it comprises a kind of transparent ophthalmic lens material and at least a chromotropic dye composition, described chromotropic dye has following structural formula:
In the formula:
R
1Be H, CH
3, the alkyl that replaces of alkyl, aryl radical, heteroatoms of various different chain length, aryl radical, the polymerisable unsaturated group that heteroatoms replaces;
R
2Be H, CH
3, various different chain length the alkyl that replaces of alkyl, aryl radical, heteroatoms,, the heteroatoms aryl radical, the polymerisable unsaturated group that replace.
R in the described chromotropic dye structural formula
1Preferably from vinyl, 2-methyl ethylene, propenyl, 2-methylpropenyl, acryloxy, methacryloxy, acrylamido, methacryloyl amido, 4-vinyl phenyl, 3-vinyl phenyl, 2-vinyl phenyl.
R in the described chromotropic dye structural formula
2Preferably from vinyl, 2-methyl ethylene, propenyl, 2-methylpropenyl, acryloxy, methacryloxy, acrylamido, methacryloyl amido, 4-vinyl phenyl, 3-vinyl phenyl, 2-vinyl phenyl.
The present invention is with physics or chemical process, above-mentioned chromotropic dye is infiltrated or chemical bond links in transparent ophthalmic lens material.Allow crystalline material under solar radiation, convert the yellow that can absorb short wavelength's blue light or the crystal of deep yellow to.When under indoor light or rayless situation, convert the isomer that does not absorb short wavelength's blue light to, make crystal return to light color or colourless.
Above-mentioned chromotropic dye comprises, but be not limited to Luo oxazine (Spiro-naphthoxazines) family compounds, this compounds can be divided into polymerizable Luo oxazine (Spiro-naphthoxazines) and family's compounds that can not Ju Luo oxazine (Spiro-naphthoxazines).
The variable color mechanism of this chromotropic dye is, under sunlight and uviolizing, such chromotropic dye becomes can absorb longer wavelength or long wavelength's isomeric compound more, and wherein the light wave of longer wavelength is that blue wavelength makes ophthalmic lens material yellowing or deep yellow.And when not having sunlight or uviolizing, this chromotropic dye becomes original isomeric compound again, and it is light color or colourless that its ophthalmic lens material becomes again.
The preparation method of color changeable transparent ophthalmic lens material mainly is divided into the infiltration method of physics and the copolymerization method of chemistry.
So-called physical method is that its chromotropic dye is dissolved in the organic solvent, then transparent ophthalmic lens material (the crystal sheet wafer that makes in advance) is put into this mixing solutions, be allowed to condition under the certain high temperature, swelling and infiltration finally make the inside and outside swelling equilibrium that reaches of tabular crystal.Chromotropic dye is distributed in the inside of crystalline material uniformly.When solution after the coarse crystal material internal reaches capacity, slowly dry removing organic molecule, and the internal structure of coarse crystal material will be shunk gradually and the chromotropic dye molecule is fixed within the coarse crystal structure firmly.Because the molecular weight of chromotropic dye is bigger, only under organic solvent swelling ground situation, just can enter or run out of the coarse crystal material, in case after the contraction of exsiccant coarse crystal, the chromotropic dye molecule just is fixed in the inside of coarse crystal structure firmly.Simultaneously, the selected chromotropic dye of the present invention is the extremely strong organic molecule of hydrophobicity, may run out of crystal hardly in the aqueous solution or under the immersion of physiological saline.
So-called chemical process is to connect a polymerisable functional group in the method with chemistry on the molecular structure of chromotropic dye, these functional groups are selected from but are not limited only to: vinyl, 2-methyl ethylene, propylene, the 2-methylpropenyl, acryloxy, 2-methacryloxy, acrylamido, 2-methacryloyl amido, the 4-vinyl phenyl, 3-vinyl phenyl, groups such as 2-vinyl phenyl.One or more polymerizable chromotropic dye is sneaked in the monomer prescription of making transparent ophthalmic lens material, and copolymerization at high temperature forms the ophthalmic lens material of color changeable transparent.It is with chromotropic dye connection or crosslinked in the copolymerization structure of ophthalmic lens material by free radical reaction that this method is made the variable color ophthalmic lens material.
Making the transparent ophthalmic lens material that above-mentioned color changeable transparent ophthalmic lens material adopts can be the hydrophilic polyacrylic ester material, or silica gel material, or hydrophobic polypropylene acid esters material.
Make above-mentioned color changeable transparent ophthalmic lens material, its transparent ophthalmic lens material preferably adopts: hydrophobic polypropylene acid esters material, and its vitreous state conversion temp is lower than 25 degrees centigrade, and deformability is greater than 80%, and specific refractory power is higher than 1.46.
Make above-mentioned color changeable transparent ophthalmic lens material, its transparent ophthalmic lens material more preferably adopts: following hydrophobic polypropylene acid esters material:
(a) include the acrylate small molecule monomer of following structural (II):
In the formula: R is alkyl C
nH
2n+1, n is 2～16 integer, 2-phenylethyl, 3-phenyl propyl, 2-phenyl propyl, 4-phenyl butyl, 3-phenyl butyl, 2-phenyl butyl, 2-phenoxy group ethyl, 3-phenoxy propyl, 2-phenoxy propyl, 4-phenoxy group butyl, 3-phenoxy group butyl, 2-phenoxy group butyl.
The selection of its R, the vitreous state conversion temp that should satisfy this micromolecular homopolymer is lower than 25 ℃.
The monomer total amount that is contained in the structure (II) in this hydrophobic polypropylene acid esters material is about 35% to 70% usually.The preferred total weight range of monomer is 40% to 60%.
(b) include the methacrylic ester small molecule monomer of following structural (III):
In the formula: R is CH
3, C
2H
5, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, phenyl, benzyl, 2-phenylethyl, 3-phenyl propyl, 2-phenyl propyl, 4-phenyl butyl, 3-phenyl butyl, 2-phenyl butyl, 2-phenoxy group ethyl, 3-phenoxy propyl, 2-phenoxy propyl, 4-phenoxy group butyl, 3-phenoxy group butyl, 2-phenoxy group butyl.
The monomer total amount that is contained in the structure (III) in this hydrophobic polypropylene acid esters material is about 12% to 40% usually.The preferred total weight range of monomer is 20% to 30%.
(c) include the solid structure small molecule monomer of following structural (IV):
In the formula: R is H, CH
3, C
2H
5
n＝0、1；
R ' is H, CH
3, C
nH
2n+1, n is 1～12 integer, aryl radical, Cl, Br, alkoxyl group, phenoxy group;
The selection of its R, n, R ', the vitreous state conversion temp that should satisfy this solid structure small molecules homopolymer is higher than 40 ℃.
The monomer total amount that is contained in the structure (I) in this hydrophobic polypropylene acid esters material is about 1% to 16% usually.The preferred total weight range of monomer is 8% to 14%.
Among the present invention, but described hydrophobic polypropylene acid esters material further comprises the composition of crosslinking copolymerization agent, and the small molecule monomer of described linking agent is selected from: Ethylene glycol dimethacrylate, ethylene glycol diacrylate, the dimethyl allene acid propylene glycol ester, the diacrylate propylene glycol ester, dimethacrylate glycerine alcohol ester, diacrylate glycerine alcohol ester, trimethylammonium vinylformic acid glycerine alcohol ester, three vinylformic acid glycerine alcohol esters, tetramethylene dimethacrylate, the diacrylate butanediol ester, the dimethacrylate pentadiol ester, the diacrylate pentadiol ester, dimethacrylate hexylene glycol ester, hexanediol diacrylate, Vinylstyrene, trivinylbenzene, diallyl benzene, three propenylbenzenes, the methyl Vinylstyrene, methyl diallyl benzene.
Among the present invention, described hydrophobic polypropylene acid esters material further comprises the composition of ultraviolet absorption material, and described ultraviolet absorption material can be anyly can absorb the short wavelength and be lower than the following ultraviolet absorber compounds of 400 nanometers.Described ultraviolet absorption material preferably from: but but the benzophenone compounds of the benzotriazole compound copolymerization of copolymerization comprises the benzophenone of replacement and its derivative, the 2-C2-hydroxy-phenyl benzotriazole of replacement and its substituting group derivative.Polymerisable ultraviolet absorber compounds is sneaked in the mixing solutions of monomer and linking agent, copolymerization and making can absorb the variable color lens material that ultraviolet ray also can absorb short wavelength's blue ray simultaneously then.Preferred ultraviolet absorber compounds is disclosed 2-hydroxyl-5-acryloyl-oxy phenyl-2H-azimidobenzene in disclosed replacement 2-hydroxyl benzophenone and the United States Patent (USP) 4528311 in the United States Patent (USP) 4304895.
Among the present invention, described hydrophobic polypropylene acid esters material further comprises the composition of radical initiator, and described radical initiator is selected from, but is not limited to: oxidation of benzophenone, peroxy carbonates class, azonitrile compounds.Wherein, preferably peroxy carbonates class and azonitrile compounds.Azo dibutyronitrile more preferably wherein.
Copolymerization process of the present invention copolymerization process preparation routinely.Use chemical process to make hydrophobic polypropylene acid esters color changeable transparent material, can be at normal temperatures, be mixed in the three-necked bottle than with various small molecule monomers and linking agent by different molar weights, add then after an amount of UV light absorber and polymerisable chromotropic dye and the initiator, feed highly purified nitrogen or other rare gas elementes to remove the air in the mixing solutions, under nitrogen, mixing solutions is transferred in the previously prepd mould, carried out high temperature polymerization among after sealing mould being put into high temperature oven.After polymerization is finished, crystalline material is cut into the coarse crystal tabular crystal of certain shape.The polymerizable molecular of unpolymerized small molecules of part or small molecular weight.Remove by solvent-extracted mode under the high temperature.
The vitreous state conversion temp of hydrophobic polypropylene acid esters color changeable transparent material disclosed in this invention further is lower than 22 ℃, and more preferably its vitreous state conversion temp is lower than 13 ℃.
The specific refractory power of hydrophobic polypropylene acid esters color changeable transparent material disclosed in this invention further is higher than 1.47, and more preferably its specific refractory power is higher than 1.50.
The water content of hydrophobic polypropylene acid esters color changeable transparent material disclosed in this invention further is 0～1%, and more preferably its water content is 0～0.5%.
Color changeable transparent ophthalmic lens material disclosed in this invention, the especially coarse crystal of hydrophobic polypropylene acid esters color changeable transparent material, by cut mechanically, technologies such as polishing are made the artificial lens of various difform monomer-types or three-member type.
Color changeable transparent ophthalmic lens material disclosed in this invention, especially hydrophobic polypropylene acid esters color changeable transparent material is used for making, replace cataract crystalline artificial lens but be not limited to make, as implanting anterior chamber, the near-sighted artificial lens of back room, long sight artificial lens, presbyopic artificial lens.Can also be used to make other ophthalmology implantation or non-implantation device, these devices comprise ophthalmic lens, contact lens, cornea correction thing, intracorneal lens, cornea insert, corneal ring, glaucoma filtering apparatus.
Embodiment
Will be further understood that the present invention from following illustrative embodiment.
Embodiment 1
In 2000 milliliters three neck round-bottomed flasks, put into 4.0 gram 2-hydroxyl-5-acryloyl-oxy phenyl-2H-benzotriazoles, 73.0 gram substituted phenylethylene, 5.0 gram phenyl vinyl sulfone, 40.0 gram ethylene glycol dimethacrylate diester, 157.0 the gram Jia Jibingxisuanyizhi, 295.0 gram butyl acrylates, 0.7 gram azo dibutyronitrile.
Be accompanied by stirring, feed highly purified nitrogen in mixing solutions to remove air, under nitrogen, solution is transferred in the preprepared mould polymerization forming in high temperature oven.After the oven temperature cool to room temperature, from mould, shift out polymeric material, cut into the coarse crystal of definite shape.At high temperature extract at least 24 hours to remove the small molecules residue in the coarse crystal with alcoholic solvent.Dry at a certain temperature to remove alcoholic solvent.
Dry good coarse crystal has following physicals: at 25 ℃ of following refractive index is 1.4938, is 1.4920 at 35 ℃ of following refractive index, and physical strength is 820psi, and deformability is 90%, and the ultraviolet ray below 390nm is all absorbed.
In one 250 milliliters wide-necked bottle, put into 20.0 milligrams of Luo oxazines (Spiro-naphthoxazines) changeable colour dyestuff and 100 gram alcoholic solvents.Heating makes it dissolving, is cooled to room temperature, is 15.9mm with 100 diameters, and thickness is that the coarse crystal of 3.0mm is put into this solution, builds wide-necked bottle, and this bottle put into baking oven at least 48 hours under the certain temperature, filters dryly then to desolvate to remove.
Dry good coarse crystal has following physicals: under 25 ℃, refractive index is 1.4937, is 1.4921 under 35 ℃, and physical strength is 820psi, and deformability is 90%.Coarse crystal is placed 5 to 10 seconds under the sunlight, and coarse crystal becomes deep yellow, and the deep yellow crystal was put back under indoor visible light 5 to 10 minutes, and the deep yellow coarse crystal returns to original light color or colourless fully.Under room temperature, the following ultraviolet ray of 390nm is all absorbed.
Embodiment 2
In 2000 milliliters three neck round-bottomed flasks, put into 3.5 gram 2-hydroxyl-5-acryloyl-oxy phenyl-2H-benzotriazoles, 154.0 gram n-butyl acrylates, 215 gram n-BMAs, 34.5 gram vinylbenzene, 36.0 gram ethylene glycol dimethacrylate diester and 0.6 gram azo dibutyronitrile.
Be accompanied by stirring, feed highly purified nitrogen in mixing solutions to remove the air in the solution, under nitrogen pressure, mixing solutions is transferred in the preprepared mould, seal mould after, mould is inserted polymerization forming in the high temperature oven.After being cooled to room temperature, remove polymeric material, cut into certain coarse crystal wafer.At high temperature extract at least 24 hours to remove the small molecules residue in the coarse crystal with alcoholic solvent.Then, dry at a certain temperature to remove alcoholic solvent.
Have following physicals in dry good coarse crystal material: under 25 ℃, refractive index is 1.4865, is 1.4845 under 35 ℃, and physical strength is 560psi, and deformability is 75%, and the following ultraviolet ray of 385nm is all absorbed.
In one 250 milliliters wide-necked bottle, put into 20.0 milligrams of Luo oxazines (Spiro-naphthoxazines) changeable colour dyestuff and 100.0 gram alcoholic solvents.Heating makes it dissolving, be cooled to room temperature after, 100 15.9mm diameters and the thick coarse crystal of 3.0mm are put into this solvent, build wide-necked bottle, wide-necked bottle was inserted in the baking oven of certain temperature at least 48 hours.Filter, dry then to remove its alcoholic solvent.
Dry good coarse crystal has following physicals: under 25 ℃, specific refractory power is 1.4865, is 1.4845 under 35 ℃, and physical strength is 560psi, and deformability is 75%, and the following ultraviolet ray of 385nm is all absorbed.Coarse crystal is placed 5 to 10 seconds under the sunlight, and coarse crystal becomes deep yellow, and the deep yellow crystal was put back under indoor visible light 5 to 10 minutes, and the deep yellow coarse crystal returns to original light color or colourless fully.
Embodiment 3
In 1000 milliliters round bottom three-necked bottle, put into 35 gram hydroxyls and replace De Luo oxazine (Spiro-naphthoxazines) chromotropic dye and 250 milliliters of methylene dichloride, 15.0 milliliter pyridine, under the ice bath cooling, slowly drip 50 milliliters of dichloromethane solutions of 12 milliliters of methacrylic chlorides, add the back and under room temperature, continue to stir at least two hours.With 0.1N aqueous hydrochloric acid flushing three times (twice of 3 * 100ml) water flushing then (and 2 * 100ml), dry methylene chloride solution at least two hours (35 gram anhydrous magnesium sulfate).Filter, under reduced pressure remove and desolvate.After separating by silicagel column, thick product obtains the higher methacryloyl Luo of purity oxazine (Spiro-naphthoxazines) 25.0 grams, and yield 68.0%1H-NMR 8.01ppm (dd, 2H); 7.32ppm (m, 11H); 6.83ppm (m, 3H); 6.12ppm (t, 1H); 6.08ppm (s, 1H); 5.65ppm (s, 1H); 3.95ppm (s, 4H); 3.77ppm (d, 3H); 3.09ppm (s, 4H); 1.55ppm (t, 3H).
In 2000 milliliters three neck round-bottomed flasks, put into 2.6 gram 2-hydroxyl-5-acryloyl-oxy phenyl-2H-benzotriazoles, 0.30 gram azo dibutyronitrile, 35 gram vinylbenzene, 78 gram butyl methacrylate, 150 gram butyl acrylates, 15.5 gram ethylene glycol dimethacrylate diester, 25.0 milligrams of methacryloyl Luo oxazines (Spiro-naphthoxazines) chromotropic dye.
Be accompanied by stirring, feed highly purified nitrogen in mixing solutions to remove the air in the solution, under nitrogen pressure, mixing solutions is transferred in the preprepared mould, seal mould, mould is inserted polymerization forming in the high temperature oven.After the cool to room temperature, cut into the coarse crystal of desired shape, at high temperature extract at least 24 hours to remove the small molecules residue in the coarse crystal with alcoholic solvent.Carry out drying then at a certain temperature to remove alcoholic solvent.
Have following physicals in dry good coarse crystal material: under 25 ℃, refractive index is 1.4875, and under 35 ℃, refractive index is 1.4855, and physical strength is 620psi, and deformability is 85%, and the ultraviolet ray below 386nm is all absorbed.Become deep yellow 5 to 10 seconds under sunlight, the deep yellow crystal retracted returned to light color or colourless within the indoor visible light 5 to 10 minutes.
Should be pointed out that for the present invention also to have the embodiment of multiple conversion and remodeling, be not limited to the specific embodiment of above-mentioned embodiment through proving absolutely.The foregoing description is as just explanation of the present invention, rather than limitation of the present invention.In a word, protection scope of the present invention should comprise those conspicuous to those skilled in the art conversion or substitute and remodeling.
Claims (23)
1. color changeable transparent ophthalmic lens material, it comprises a kind of transparent ophthalmic lens material and at least a chromotropic dye composition, described chromotropic dye has following structural formula (I):
In the formula:
R
1Be H, CH
3, the alkyl that replaces of alkyl, aryl radical, heteroatoms of various different chain length, aryl radical, the polymerisable unsaturated group that heteroatoms replaces;
R
2Be H, CH
3, the alkyl that replaces of alkyl, aryl radical, heteroatoms of various different chain length, aryl radical, the polymerisable unsaturated group that heteroatoms replaces.
2. color changeable transparent ophthalmic lens material according to claim 1, R in the described chromotropic dye structural formula
1Be selected from vinyl, 2-methyl ethylene, propenyl, 2-methylpropenyl, acryloxy, methacryloxy, acrylamido, methacryloyl amido, 4-vinyl phenyl, 3-vinyl phenyl, 2-vinyl phenyl.
3. color changeable transparent ophthalmic lens material according to claim 1, R in the described chromotropic dye structural formula
2Be selected from vinyl, 2-methyl ethylene, propenyl, 2-methylpropenyl, acryloxy, methacryloxy, acrylamido, methacryloyl amido, 4-vinyl phenyl, 3-vinyl phenyl, 2-vinyl phenyl.
4. color changeable transparent ophthalmic lens material according to claim 1, described transparent ophthalmic lens material are transparent hydrophilic polyacrylic ester material.
5. color changeable transparent ophthalmic lens material according to claim 1, described transparent ophthalmic lens material are transparent silica gel material.
6. color changeable transparent ophthalmic lens material according to claim 1, described transparent ophthalmic lens material are transparent hydrophobic polypropylene acid esters material.
7. color changeable transparent ophthalmic lens material according to claim 6, described hydrophobic polypropylene acid esters material includes the acrylate small molecule monomer of following structural (II):
In the formula: R is alkyl C
nH
2n+1, n is 2～16 integer, 2-phenylethyl, 3-phenyl propyl, 2-phenyl propyl, 4-phenyl butyl, 3-phenyl butyl, 2-phenyl butyl, 2-phenoxy group ethyl, 3-phenoxy propyl, 2-phenoxy propyl, 4-phenoxy group butyl, 3-phenoxy group butyl, 2-phenoxy group butyl;
The selection of its R, the vitreous state conversion temp that should satisfy this micromolecular homopolymer is lower than 25 ℃.
8. color changeable transparent ophthalmic lens material according to claim 6, described hydrophobic polypropylene acid esters material includes the methacrylic ester small molecule monomer of following structural (III):
In the formula: R is CH
3, C
2H
5, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, phenyl, benzyl, 2-phenylethyl, 3-phenyl propyl, 2-phenyl propyl, 4-phenyl butyl, 3-phenyl butyl, 2-phenyl butyl, 2-phenoxy group ethyl, 3-phenoxy propyl, 2-phenoxy propyl, 4-phenoxy group butyl, 3-phenoxy group butyl, 2-phenoxy group butyl.
9. color changeable transparent ophthalmic lens material according to claim 6, described hydrophobic polypropylene acid esters material includes the solid structure small molecule monomer of following structural (IV):
In the formula: R is H, CH
3, C
2H
5
n＝0、1；
R ' is H, CH
3, C
nH
2n+1, n is 1～12 integer, aryl radical, Cl, Br, alkoxyl group, phenoxy group;
The selection of its R, n, R ', the vitreous state conversion temp that should satisfy this solid structure small molecules homopolymer is higher than 40 ℃.
10. color changeable transparent ophthalmic lens material according to claim 6, the vitreous state conversion temp of described hydrophobic polypropylene acid esters material is lower than 25 degrees centigrade, and deformability is greater than 80%, and specific refractory power is higher than 1.46; Described hydrophobic polypropylene acid esters material mainly is the solid structure small molecule monomer that is had structural formula (III) by one or more, have the solid structure small molecule monomer of structural formula (IV) with one or more, and one or more soft structure small molecule monomers with structural formula (II) are formed:
Soft structure small molecule monomer (II)
In the formula: R is alkyl C
nH
2n+1, n is 2～16 integer, 2-phenylethyl, 3-phenyl propyl, 2-phenyl propyl, 4-phenyl butyl, 3-phenyl butyl, 2-phenyl butyl, 2-phenoxy group ethyl, 3-phenoxy propyl, 2-phenoxy propyl, 4-phenoxy group butyl, 3-phenoxy group butyl, 2-phenoxy group butyl;
The selection of its R, the vitreous state conversion temp that should satisfy this micromolecular homopolymer is lower than 25 ℃;
Solid structure small molecule monomer (III)
In the formula: R is CH
3, C
2H
5, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, phenyl, benzyl, 2-phenylethyl, 3-phenyl propyl, 2-phenyl propyl, 4-phenyl butyl, 3-phenyl butyl, 2-phenyl butyl, 2-phenoxy group ethyl, 3-phenoxy propyl, 2-phenoxy propyl, 4-phenoxy group butyl, 3-phenoxy group butyl, 2-phenoxy group butyl;
The selection of its R, the vitreous state conversion temp that should satisfy this solid structure small molecules homopolymer is higher than 37 ℃;
Solid structure small molecule monomer (IV)
In the formula: R is H, CH
3, C
2H
5
n＝0、1；
R ' is H, CH
3, C
nH
2n+1, n is 1～12 integer, aryl radical, Cl, Br, alkoxyl group, phenoxy group;
The selection of its R, n, R ', the vitreous state conversion temp that should satisfy this solid structure small molecules homopolymer is higher than 40 ℃;
Containing (IV) small molecule monomer in the multipolymer is 1～16 weight %.
11. color changeable transparent ophthalmic lens material according to claim 10, but described hydrophobic polypropylene acid esters material further comprises the composition of crosslinking copolymerization agent, the small molecule monomer of described linking agent is selected from, Ethylene glycol dimethacrylate, ethylene glycol diacrylate, the dimethyl allene acid propylene glycol ester, the diacrylate propylene glycol ester, dimethacrylate glycerine alcohol ester, diacrylate glycerine alcohol ester, trimethylammonium vinylformic acid glycerine alcohol ester, three vinylformic acid glycerine alcohol esters, tetramethylene dimethacrylate, the diacrylate butanediol ester, the dimethacrylate pentadiol ester, the diacrylate pentadiol ester, dimethacrylate hexylene glycol ester, hexanediol diacrylate, Vinylstyrene, trivinylbenzene, diallyl benzene, three propenylbenzenes, the methyl Vinylstyrene, methyl diallyl benzene.
12. color changeable transparent ophthalmic lens material according to claim 10, described hydrophobic polypropylene acid esters material further comprises the composition of ultraviolet absorption material, described ultraviolet absorption material is selected from, but but the benzophenone compounds of the benzotriazole compound copolymerization of copolymerization.
13. color changeable transparent ophthalmic lens material according to claim 10, described hydrophobic polypropylene acid esters material further comprises the composition of radical initiator, described radical initiator is selected from, oxidation of benzophenone, peroxy carbonates class, azonitrile compounds.
14. color changeable transparent ophthalmic lens material according to claim 10, the vitreous state conversion temp of described color changeable transparent hydrophobic polypropylene acid esters ophthalmic lens material further is lower than 22 ℃.
15. color changeable transparent ophthalmic lens material according to claim 10, the vitreous state conversion temp of described color changeable transparent hydrophobic polypropylene acid esters ophthalmic lens material is more preferably less than 13 ℃.
16. color changeable transparent ophthalmic lens material according to claim 10, the specific refractory power of described color changeable transparent hydrophobic polypropylene acid esters ophthalmic lens material further is higher than 1.47.
17. color changeable transparent ophthalmic lens material according to claim 10, the specific refractory power of described color changeable transparent hydrophobic polypropylene acid esters ophthalmic lens material more preferably is higher than 1.50.
18. color changeable transparent ophthalmic lens material according to claim 10, the water content of described color changeable transparent hydrophobic polypropylene acid esters ophthalmic lens material further is 0～1%.
19. color changeable transparent ophthalmic lens material according to claim 10, the water content of described color changeable transparent hydrophobic polypropylene acid esters ophthalmic lens material more preferably 0～0.5%.
20. according to each described color changeable transparent ophthalmic lens material in the claim 1～19 as the application of ophthalmic lens device manufactured materials.
21. ophthalmic lens material according to claim 20 is used, described ophthalmic lens device is selected from artificial lens, ophthalmic lens, contact lens, cornea correction thing, intracorneal lens, cornea insert, corneal ring, glaucoma filtering apparatus.
22. ophthalmic lens material according to claim 20 is used, described ophthalmic lens device is to replace cataract crystalline artificial lens.
23. ophthalmic lens material according to claim 20 is used, described ophthalmic lens device is to implant anterior chamber, the near-sighted artificial lens of back room, long sight artificial lens, presbyopic artificial lens.
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| CN 200610039527 CN101050294A (en) | 2006-04-03 | 2006-04-03 | Color changeable transparent ophthalmic lens material, and application |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200610039527 CN101050294A (en) | 2006-04-03 | 2006-04-03 | Color changeable transparent ophthalmic lens material, and application |
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| CN101050294A true CN101050294A (en) | 2007-10-10 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102599992A (en) * | 2012-03-16 | 2012-07-25 | 无锡蕾明视康科技有限公司 | Artificial lens with iris diaphragm |
| CN102600502A (en) * | 2012-03-16 | 2012-07-25 | 无锡蕾明视康科技有限公司 | Dynamic zooming artificial lens and preparation method of dynamic zooming artificial lens |
| CN103340703A (en) * | 2013-06-17 | 2013-10-09 | 无锡蕾明视康科技有限公司 | Implantable myopia lens and preparation method thereof |
| CN112679651A (en) * | 2020-12-29 | 2021-04-20 | 沈阳百奥医疗器械有限公司 | Light-sensitive blue-light-proof optical material and application thereof |
| CN113896736A (en) * | 2021-11-18 | 2022-01-07 | 南开大学 | Aryl-substituted spirooxazine photochromic compound and preparation method and application thereof |
| CN113912775A (en) * | 2021-11-03 | 2022-01-11 | 江苏海伦隐形眼镜有限公司 | Indicator material and preparation method and application thereof |
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- 2006-04-03 CN CN 200610039527 patent/CN101050294A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102599992A (en) * | 2012-03-16 | 2012-07-25 | 无锡蕾明视康科技有限公司 | Artificial lens with iris diaphragm |
| CN102600502A (en) * | 2012-03-16 | 2012-07-25 | 无锡蕾明视康科技有限公司 | Dynamic zooming artificial lens and preparation method of dynamic zooming artificial lens |
| CN102600502B (en) * | 2012-03-16 | 2015-11-25 | 廖秀高 | Intraocular lens of dynamically changeable Jiao and preparation method thereof |
| CN103340703A (en) * | 2013-06-17 | 2013-10-09 | 无锡蕾明视康科技有限公司 | Implantable myopia lens and preparation method thereof |
| WO2014201956A1 (en) * | 2013-06-17 | 2014-12-24 | 无锡蕾明视康科技有限公司 | Implantable myopia lens and preparation method therefor |
| EP3005981A4 (en) * | 2013-06-17 | 2016-06-08 | Wuxi Vision Pro Ltd | Implantable myopia lens and preparation method therefor |
| CN112679651A (en) * | 2020-12-29 | 2021-04-20 | 沈阳百奥医疗器械有限公司 | Light-sensitive blue-light-proof optical material and application thereof |
| CN113912775A (en) * | 2021-11-03 | 2022-01-11 | 江苏海伦隐形眼镜有限公司 | Indicator material and preparation method and application thereof |
| CN113912775B (en) * | 2021-11-03 | 2023-01-10 | 江苏海伦隐形眼镜有限公司 | Indicator material and preparation method and application thereof |
| CN113896736A (en) * | 2021-11-18 | 2022-01-07 | 南开大学 | Aryl-substituted spirooxazine photochromic compound and preparation method and application thereof |
| CN113896736B (en) * | 2021-11-18 | 2023-03-03 | 南开大学 | Aryl-substituted spirooxazine photochromic compound and preparation method and application thereof |
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