CN100474036C - Ocular lens material and method for producing the same - Google Patents
Ocular lens material and method for producing the same Download PDFInfo
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- CN100474036C CN100474036C CNB200580016610XA CN200580016610A CN100474036C CN 100474036 C CN100474036 C CN 100474036C CN B200580016610X A CNB200580016610X A CN B200580016610XA CN 200580016610 A CN200580016610 A CN 200580016610A CN 100474036 C CN100474036 C CN 100474036C
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- lens material
- ocular lens
- compound
- contact lenses
- phosphorylcholine
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Abstract
Disclosed is a method for producing an ocular lens material which comprises a step for reacting and covalently bonding a compound having a phosphorylcholine group represented by the formula (1) below with the surface of an ocular lens material. This method for producing an ocular lens material is characterized in that a phosphorylcholine group-containing compound represented by the formula (2) below is reacted with an ocular lens material, in an organic solvent, thereby being covalently bonded thereto by an acetal bond. With such a method, there can be provided an ocular lens material which prevents protein adsorption. In the formula (2), n is a natural number of 1-18.
Description
Technical field
The present invention relates to ocular lens material, its manufacture methods such as contact lenses, prevent the method for protein adsorption.More particularly, the present invention relates to aftertreatment, ocular lens material surface (particularly contact lenses) are handled, prevent the method for protein contamination by the compound of novel phosphorus-containing acid choline base.
Background technology
The monomer polymerization that will contain phosphorylcholine is used as contact lens material, and this is known (patent documentation 1-3).A kind of property of water-bearing soft contact lens is for example disclosed in the patent documentation 1, these contact lenses contain (methyl) acrylate of phosphoric acid choline base as structural unit, and put down in writing its water percentage, oxygen permeability, pulling strengrth excellence, the protein adsorption amount is few, but the adhering to of contaminant restraining.
As the post-processing approach of contact lenses, put down in writing in the patent documentation 4 and made monomer and the contact lens surface polymerization that contains phosphorylcholine, manufacturing possess hydrophilic property surface, the contact lenses that protein adsorption is few.
Disclose in the patent documentation 5 and made low molecule phosphocholine carboxyl compound and contact lens surface chemical bond, to reduce protein adsorption.
That is, put down in writing the chemical structural formula that the phosphocholine carboxyl compound changes active ester in the reaction equation 6 on the 5th of patent documentation 5 the page of bottom right bar (V), the 6th page of hurdle, bottom right.But, all not on the books about its synthetic method, embodiment, therefore can't carry out demonstration test, not talkative invention disclosed.According to general organic chemistry general knowledge, with this compound is synthetic when having the phosphocholine carboxyl compound of the structure of put down in writing, its method is extremely complicated, and yield is low, so can easily infer its shortage practicality.In addition, put down in writing among the embodiment 5 on the 9th page of upper left hurdle choline glycerophosphatide is carried out 1,1 '-carbonyl dimidazoles is handled, and imports the method for phosphorylcholine to the contact lens surface that contains methacrylic acid 4-hydroxyl ethyl ester multipolymer.But when the foregoing description was carried out demonstration test, the result also failed to obtain the desirable contact lenses of handling through phosphocholine.
On the other hand, the pollution of contact lenses is contained protein or lipid absorption in the tear, becomes pollution, and this pollution has the danger (non-patent literature 1) of eye diseases such as causing allergic reaction or infection.Be the moisture soft contact lens of principal ingredient or the high moisture soft glasses that obtain of the ionic monomer methacrylic acid of minor amounts of copolymerized or wherein particularly with N-vinyl pyrrolidone or N with the polymkeric substance of 2-hydroxyethyl methacrylate, in the soft contact lens of the polymkeric substance of N-DMAA as the hydrophilic monomer principal ingredient, the pollution of protein is fatal problem.
Patent documentation 1: Japanese kokai publication hei 10-177152 communique
Patent documentation 2: TOHKEMY 2000-111847 communique
Patent documentation 3: TOHKEMY 2000-169526 communique
Patent documentation 4: TOHKEMY 2001-337298 communique
Patent documentation 5: the flat 5-505121 communique of Japanese Unexamined Patent Application Publication
Non-patent literature 1: " ソ Off ト コ Application Network ト レ Application ズ
れ と そ analyzes ", マ テ リ ア Le ス テ-ジ, Vol.4, No.1,2004
Summary of the invention
The invention provides a kind of contact lenses,, make the direct and contact lens surface covalent bond of phosphorylcholine, suppress the protein adsorption of contact lenses, thereby prevent protein contamination wherein by contact lenses are carried out aftertreatment.
Promptly, purpose of the present invention is not the method for putting down in writing in above-mentioned patent documentation 1-3, make the monomer polymerization manufacturing of containing phosphorylcholine prevent the contact lenses of protein adsorption, but, make it have the excellent function that prevents protein adsorption by contact lenses are carried out aftertreatment.
Purpose of the present invention neither make the monomer polymerization of phosphoric acid choline base as the method for patent documentation 4 records on the surface of contact lenses, use the other polymkeric substance different with contact lenses to cover, and imports phosphorylcholine thus.Contact lenses of the present invention do not need polymkeric substance to cover and direct and phosphorylcholine covalent bond, obtain excellent in te pins of durability thus, can not change the intrinsic character of contact lenses because of polymkeric substance covers, and can bring into play the excellent effect that prevents protein adsorption.
Purpose of the present invention neither be as the method for citing document 5 record, when carrying out demonstration test, actually can't fully import phosphorylcholine at contact lens surface.The present invention can import the phosphorylcholine of q.s, the effect that prevents protein adsorption that performance is excellent.
Promptly, the invention provides the manufacture method of ocular lens material, this method comprises reacts and covalently bound step compound that contains the phosphorylcholine shown in the following formula (1) and the ocular lens material surface with hydroxyl, it is characterized in that: in organic solvent, the compound and the ocular lens material of following formula (2) are reacted, and by the ester bond covalent bond.
[compound 5]
(1)
[compound 6]
N is 1～18 natural number
(2)
The present invention also provides the manufacture method of ocular lens material, this method comprises makes compound and the ocular lens material surface of containing the phosphorylcholine shown in the following formula (1) react also covalently bound step, it is characterized in that: above-mentioned ocular lens material is carried out Cement Composite Treated by Plasma import hydroxyl, then in organic solvent, the compound and the ocular lens material of following formula (2) are reacted, and by the ester bond covalent bond.
[compound 7]
(1)
[compound 8]
N is 1～18 natural number
(2)
The present invention further provides ocular lens material, it is characterized in that: this material obtains via acid halide thing and the hydroxyl reaction that is present in the ocular lens material surface by the compound that makes above-mentioned phosphoric acid choline base.
The invention provides the method that prevents the ocular lens material adsorbed proteins, it is characterized in that: the aftertreatment of compound by making above-mentioned phosphoric acid choline base and ocular lens material reaction, make phosphorylcholine and ocular lens material surface covalent bond, thereby prevent that protein adsorption from arriving ocular lens material.
Manufacturing method according to the invention by easy post-processing approach, can make the direct covalent bond of phosphorylcholine and ocular lens material surface of any amount.
Ocular lens material of the present invention---contact lenses are to make phosphorylcholine and the direct covalent bond of contact lens surface, therefore can effectively suppress the protein adsorption of contact lenses, the anti-fouling effect that performance is excellent.Also can improve water-retaining property in addition, improve and wear sense.
In addition, its function can be made, therefore existing contact lenses can be easily the present invention be used for the protein adsorption of preventing by aftertreatment.
Because the present invention covers by polymkeric substance to import phosphorylcholine, so excellent in te pins of durability, can not make the intrinsic character variation of contact lenses basically.
The contact lenses that obtained by the present invention have the excellent sense of wearing.Therefore, it is former thereby be easy to generate the contact lenses of foreign body sensation to be preferred for flexibility difference etc. because of material.
Do not put down in writing the synthetic method of the compound of phosphoric acid choline base in the disposal route of patent documentation 5 records, when synthesizing based on general organic chemistry general knowledge, this method is extremely complicated and difficult, and step is many, and therefore the low shortcoming of yield is arranged.
In addition, the importing reaction that imports phosphorylcholine to contact lens surface also can't fully be carried out under the condition of being put down in writing, and its import volume is low, therefore can not show the excellent effect that prevents protein adsorption.
In contrast, post-processing approach of the present invention can import the phosphorylcholine of q.s, thereby can bring into play the excellent effect that prevents protein adsorption, is extremely practical method.
Description of drawings
Fig. 1 is the protein adsorption spirogram of contact lenses.
Embodiment
Below describe the present invention in detail.
(preparation method of the phosphoric acid choline based compound of formula (2))
Phosphorylcholine can prepare by synthesizing fully.But the synthesis condition complexity must be strict anhydrous condition, the preparation cost height.
On the other hand, phosphocholine can be with the constituent of cell membrane---and the form of lecithin is extracted, and in this case, removes fatty acid part by hydrolysis, can more low-cost and easily obtain 1-α-choline glycerophosphatide.The inventor finds: by making the glycol moiety oxidisability cracking of this 1-α-choline glycerophosphatide, can easily obtain to have the phosphoric acid choline based compound of carboxyl.
The most representative synthetic method is: with 1-α-choline glycerophosphatide in water and acetonitrile equal solvent by sodium metaperiodate and ruthenium trichloride oxidation, obtain the target carboxyl compound.(ocular lens material)
Among the present invention, ocular lens material is the moulding product that are worn on the material in the eyes, mainly is contact lenses.
Can be the contact lenses of any material.For example can make contact lenses of the present invention: by methacrylic acid (MAA) by following contact lenses, acrylic acid (AA), 2-hydroxyethyl methacrylate (HEMA), N-vinyl pyrrolidone (NVP), N,N-DMAA (DMAA), vinyl alcohol (VA), methyl methacrylate (MMA), trifluoroethyl methacrylate (TFEMA), cellulose acetate-butyrate (CAB), fluorosilicone, methacrylic acid hexafluoro isopropyl ester, perfluoroalkyl methacrylate, methacrylic acid siloxy group ester (SiMA), siloxy group styrene (SiSt), Ethylene glycol dimethacrylate (EGDMA), allyl methacrylate (AMA), the contact lenses that the polymkeric substance of silicone macromolecule monomer etc. or the multipolymer of two or more monomer constitute.The kind of the present invention and monomer is irrelevant, can be used for any of hard contact lens, soft contact lens.
With 2-hydroxyethyl methacrylate as the soft contact lens of the principal ingredient of the monomer that constitutes contact lenses and make methacrylic acid and ionic soft contact lens that its copolymerization obtains is representational soft contact lens, therefore adsorbed proteins is preferably handled by method of the present invention easily.
Also preferably handle as the principal ingredient of the monomer that constitutes contact lenses or the contact lenses of copolymer composition with vinyl alcohol with method of the present invention.
The contact lenses that contain 2-hydroxyethyl methacrylate or polyvinyl alcohol polymer have hydroxyl can covalently bound functional group as the phosphorylcholine of above-mentioned formula (1), therefore preferred.
But,, also can import hydroxyl by Cement Composite Treated by Plasma even do not have these functional groups.For example, the contact lenses that contain the N-vinyl pyrrolidone polymer import hydroxyl by Cement Composite Treated by Plasma, can make contact lenses of the present invention.That is, in the oxygen atmosphere or in the oxygen, atmosphere of hydrogen, import hydroxyl to contact lens surface by low temperature plasma.Specifically, contact lenses are put into reaction vessel for plasma, will vacuumize in the reaction vessel, import oxygen or oxygen, hydrogen then with vacuum pump.Then glow discharge can import hydroxyl to contact lens surface thus.
The phosphoric acid choline based compound of formula (2) and the hydroxyl of contact lens surface are by the ester bond covalent bond.As a result, by contact lenses are implemented aftertreatment, can obtain by directly imported the contact lenses of the phosphorylcholine of formula (1) with the contact lens surface chemical bond.
The contact lenses that obtained by the present invention are different with the lens of the material that the monomer polymerization that contains phosphorylcholine is obtained.Contained in the lens that the polymkeric substance of phosphorylcholine covers, the polymkeric substance of covering can peel off, or produces the influence that overlie polymer causes.
(manufacture method)
Manufacture method of the present invention is in organic solvent, makes the hydroxyl of contact lenses formation monomer or forms ester bond by the hydroxyl of new importings such as Cement Composite Treated by Plasma and the compound of formula (2) afterwards.
Specifically, phosphocholine compound (2) is dissolved or be suspended in the organic solvents such as dimethyl sulfoxide (DMSO), dimethyl formamide, tetrahydrofuran, use condensation agents such as carbonyl dimidazoles, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, thionyl chloride, phosphorus pentachloride, phosphoryl chloride phosphorus oxychloride, phosphorus tribromide, oxalyl chloride, with the hydroxyl formation ester bond of contact lens surface.
Wherein, use thionyl chloride, phosphorus pentachloride, phosphoryl chloride phosphorus oxychloride, phosphorus tribromide, oxalyl chloride etc., via the acid halide thing, make in the method for hydroxyl reaction on itself and ocular lens material surface, because favorable solubility can be handled with the form of homogeneous solution, therefore by controlling the equivalent of reagent, can control the importing rate of phosphorylcholine, thus preferred.In addition, this is with different by polymer coating importing phosphorylcholine, and is few to the variation that contact lenses bring, the key property of the glasses that therefore can remain undetected.
On the other hand, as described in patent documentation 5, use in the methods as condensation agent such as carbonyl dimidazoles, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, the dissolubility of the active ester of phosphocholine based compound is low in organic solvent, therefore from the importing rate of control phosphorylcholine, be method than the inventive method difference.
(method for preparing the ethyloic phosphocholine by the oxidation cracking of 1-α-choline glycerophosphatide)
The compound of formula (2) preferably uses the ethyloic phosphocholine (during n=1) that ftractures and obtain by the oxidation of 1-α-choline glycerophosphatide.
1-α-choline glycerophosphatide by periodate and ruthenium trichloride oxidation cracking, can be made into the ethyloic phosphocholine in water, acetonitrile mixed solvent.
This reaction can at room temperature easily be carried out, as long as have 3 equivalents or the above periodic acid and the ruthenium compound (ruthenium trichloride, tribromide ruthenium, tri acetylacetonato ruthenium etc. and hydrate thereof) of catalytic amount with respect to 1-α-choline glycerophosphatide.
(making the covalently bound method of hydroxyl of the phosphorylcholine and the contact lenses of formula (1))
There is hydroxyl in the contact lenses that contain methacrylic acid 2-hydroxyl polymerizable methacrylate thing or polyvinyl alcohol (PVA).Make carboxyl compound and this hydroxyl reaction of formula (2), then can import phosphorylcholine to contact lens surface by ester bond.
This reaction can be in organic solvents such as dimethyl formamide, dimethyl sulfoxide (DMSO), tetrahydrofuran, acetonitrile, at carbodiimides such as carbonyl dimidazoles or 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochlorides is coupling agent, and perhaps existence such as thionyl chloride, phosphorus pentachloride, phosphoryl chloride phosphorus oxychloride, phosphorus tribromide, oxalyl chloride are easily carried out down.
By the phosphorylcholine of the formula (1) of importings such as said method can be following quantitatively: use perchloric acid to carry out pre-treatment, by molybdenum blue method phosphorus carried out quantitative test (list of references: the 4th edition analysis of experimental chemistry lecture (14), 3.8.2 phosphorus ball is kind) then.
The phosphocholine base unit weight that imports toward contact lenses be preferably 0.0001 μ mol/mg or more than.Lack than 0.0001 μ mol/mg, then possibly can't obtain the effect of sufficient Profilin matter absorption, but only not subject to the limits to the situation of contact lens surface importing phosphorylcholine.On the other hand, import volume is many, and then the effect of Profilin matter absorption increases, so this import volume is not particularly limited.
Embodiment
Below, further describe the present invention according to embodiment.But the present invention is not subjected to the qualification of these embodiment.
(synthesizing of the compound of formula (2))
In the 1-α-water-soluble 70ml-acetonitrile of choline glycerophosphatide 5g 30ml.At ice-cooled 17g sodium metaperiodate and the 80mg ruthenium trichloride of adding down, stirring is spent the night.Filtering precipitate, concentrating under reduced pressure obtains target carboxyl methyl acid phosphate choline 3.86g (yield 82%) by methanol extraction.
The compound of the formula (2) when carboxyl methyl acid phosphate choline is n=1.
(manufacture method of being undertaken by aftertreatment)
Commercially available contact lenses are carried out aftertreatment with the compound of formula (2), form ester bond, make contact lenses of the present invention with this compound.
(embodiment 1: via the acid halide thing, make the compound of formula (2) and the contact lenses that Polymacon (the soft contact lens Medalist that BaushLomb company makes) forms ester bond)
The compound of 10mg formula (2) is added in the 2ml dimethyl formamide, add the 5mg thionyl chloride, stirred then 30 minutes.Soak 1 and fully replace the Polymacon that has removed water, add the 0.2ml triethylamine, reacted then 4 hours with dimethyl formamide.Reactant liquor is fully washed with pure water, obtain contact lenses.
" embodiment 2: the compound and NelfilconA (the チ バ PVC ジ that make formula (2)
ヨOff オ-カ ス デ イ リ イ that Application is made-ズ) forms the contact lenses of ester bond "
NelfilconA and dimethyl formamide are fully replaced except that anhydrating, be immersed in then in the 2ml dimethyl sulfoxide (DMSO), the compound 10mg of adding type (2), 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 7mg reacted 6 hours then.Reactant liquor is fully washed with pure water, obtain contact lenses.
(embodiment 3: make the compound of formula (2) and the contact lenses that Polymacon (the soft contact lens Medalist that Baush Lomb company makes) forms ester bond)
Water and dimethyl sulfoxide (DMSO) that Polymacon contained are fully replaced, be immersed in then in the 3ml dimethyl sulfoxide (DMSO).Add 10mg ethyloic phosphocholine, 6mg carbonyl dimidazoles, 10mg triethylamine, 25 ℃ of reactions 12 hours.With contact lenses earlier with dimethyl sulfoxide (DMSO), follow water and fully wash, obtain the target contact lenses.It is quantitative that the phosphorylcholine that imports is carried out phosphorus, and the result is 0.817 μ mol/mg.
By
(embodiment 4: the compound and NelfilconA (the チ バ PVC ジ that make formula (2)
ヨOff オ-カ ス デ イ リ イ that Application company makes-ズ) forms the contact lenses of ester bond)
Water and dimethyl formamide that NelfilconA contained are fully replaced, be immersed in then in the 3ml dimethyl formamide.Add 10mg ethyloic phosphocholine, 6mg dicyclohexylcarbodiimide, 10mg hydroxybenzotriazole, 10mg triethylamine, 25 ℃ of reactions 12 hours.With contact lenses earlier with dimethyl sulfoxide (DMSO), follow water and fully wash, obtain the target contact lenses.It is quantitative that the phosphorylcholine that imports is carried out phosphorus, and the result is 0.165 μ mol/mg.
The quantitative following of phosphorylcholine of the formula (1) that imports by covalent bond carries out.
＜quantivative approach 〉
The gained contact lenses are immersed in the perchloric acid, are heated to 180 ℃ of decomposition.With the dilution of gained solution with water, to wherein adding seven molybdic acids, six ammonium tetrahydrates and L ascorbic acid,, measure the absorbance of 710nm then 95 ℃ of colour developings 5 minutes, obtain import volume.Calibration curve adopts the biphosphate sodium water solution.
(comparative example 1)
According to the method for patent documentation 5, with 1-α-choline glycerophosphatide 10mg, 1,1-carbonyl dimidazoles 20mg, triethylamine 20mg add among the dimethyl sulfoxide (DMSO) 3ml, stir 2 hours at 50 ℃.The Polymacon that uses among the embodiment 1 is immersed in this solution, at room temperature reacted 12 hours.Earlier with dimethyl sulfoxide (DMSO), then water fully washs, it is quantitative to carry out phosphorus with contact lenses, and the phosphorylcholine of importing is below the detectability 0.0001 μ mol/mg, reacts and does not carry out.
(comparative example 2)
According to the method for patent documentation 5, with 1-α-choline glycerophosphatide 10mg, 1,1-carbonyl dimidazoles 20mg, triethylamine 20mg add among the dimethyl sulfoxide (DMSO) 3ml, stir 2 hours at 50 ℃.The NelfilconA that uses among the embodiment 2 is immersed in this solution, at room temperature reacted 12 hours.Earlier with dimethyl sulfoxide (DMSO), then water fully washs, it is quantitative to carry out phosphorus with contact lenses, and the phosphorylcholine of importing is below the detectability 0.0001 μ mol/mg, reacts and does not carry out.
(protein adsorption experiment)
For embodiment 1-2, comparative example 1-2, commercially available contact lenses (comparative example 3-7), by following evaluation method protein adsorption is suppressed effect and compare.
Comparative example 3.EtafilconA (trade name: ワ Application デ-ア キ
ユPVC
ユ-, J﹠amp; J company)
Comparative example 4.EtafilconA (trade name: ワ Application デ-ア Network エ ア-, オ キ
ユラ-サ イ エ Application ス company makes)
Comparative example 5.NelfilconA (trade name: Off オ-カ ス デ イ リ イ-ズ, チ バ PVC ジ
ヨApplication company makes)
Comparative example 6.Polymacon (trade name: メ ダ リ ス ト, ボ シ
ユThe ロ system is made)
Comparative example 7.VifilconA (trade name: Off オ-カ ス, チ バ PVC ジ
ヨApplication is made)
(evaluation method)
Contact lenses are immersed among the 3ml artificial tears, left standstill 24 hours at 37 ℃.By the BCA method albumen quality of solution part is carried out quantitatively (calibration curve: bovine serum albumin(BSA)), calculate as the protein adsorption amount with the reduction of solution partially protein.
The artificial tears is dissolved in following composition in the ultrapure water and obtains.
Lysozyme 1.20mg/ml, albumin 3.88mg/ml, gamma globulin 1.61mg/m l, sodium chloride 9.00mg/ml, potassium dihydrogen phosphate 0.14mg/ml, sodium phosphate dibasic heptahydrate 0.80mg/ml.
(list of references) FDA Guideline Draft:Testing guidelines for classIIIsoft (hydrophilic) contact lens solution, lens group compatibility test.July 15,1985.
The protein adsorption result of embodiment 1-2, comparative example 1-7 as shown in Figure 1.By this result as can be known: the absorption of the remarkable Profilin matter of contact lenses of the present invention.
Industrial applicability
According to the present invention, can highly suppress the contact lenses adsorbed proteins, significantly prevent albumen The pollution of matter.
Method of the present invention is preferred for the soft stealthy eye that protein contamination can cause fatal problem In the mirror. Especially preferably be used in the ionic soft contact lens that promotes protein adsorption.
Also preferred utilization is at the oxygen permeability of easy adsorbed proteins or the rigid stealthy eye of wearing continuously On the mirror.
Claims (4)
1. the manufacture method of ocular lens material, this method comprises that compound that makes the phosphorylcholine shown in (1) that has following formula and the ocular lens material surface with hydroxyl react and covalently bound step, it is characterized in that: in organic solvent, the compound and the ocular lens material of following formula (2) are reacted, and pass through the ester bond covalent bond:
[compound 1]
[compound 2]
N is 1～18 natural number
(2)。
2. the manufacture method of ocular lens material, this method comprises the compound that makes the phosphorylcholine shown in (1) that has following formula and react on the ocular lens material surface and covalently bound step, it is characterized in that: above-mentioned ocular lens material is carried out Cement Composite Treated by Plasma import hydroxyl, then in organic solvent, the compound and the ocular lens material of following formula (2) are reacted, and pass through the ester bond covalent bond:
[compound 3]
[compound 4]
N is the natural number of 1-18
(2)。
3. ocular lens material is characterized in that: this material is to obtain via acid halide thing and the hydroxyl reaction that is present in the ocular lens material surface by the compound that makes the phosphoric acid choline base shown in the following formula (1),
4. prevent the method for ocular lens material adsorbed proteins, it is characterized in that: the aftertreatment of compound by making the phosphoric acid choline base shown in the following formula (1) and ocular lens material reaction, make phosphorylcholine and ocular lens material surface covalent bond, thereby prevent the ocular lens material adsorbed proteins
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004153256 | 2004-05-24 | ||
| JP153256/2004 | 2004-05-24 | ||
| JP136845/2005 | 2005-05-10 |
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| Publication Number | Publication Date |
|---|---|
| CN1961242A CN1961242A (en) | 2007-05-09 |
| CN100474036C true CN100474036C (en) | 2009-04-01 |
Family
ID=38063734
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800164782A Expired - Fee Related CN100570435C (en) | 2004-05-24 | 2005-05-18 | Ocular lens material and manufacture method thereof |
| CN2005800168463A Expired - Fee Related CN1957288B (en) | 2004-05-24 | 2005-05-18 | Method for producing protein adsorption-preventing ocular lens material |
| CNB2005800167884A Expired - Fee Related CN100465700C (en) | 2004-05-24 | 2005-05-18 | Protein adsorption-preventing ocular lens material and method for producing same |
| CNB200580016610XA Expired - Fee Related CN100474036C (en) | 2004-05-24 | 2005-05-18 | Ocular lens material and method for producing the same |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2005800164782A Expired - Fee Related CN100570435C (en) | 2004-05-24 | 2005-05-18 | Ocular lens material and manufacture method thereof |
| CN2005800168463A Expired - Fee Related CN1957288B (en) | 2004-05-24 | 2005-05-18 | Method for producing protein adsorption-preventing ocular lens material |
| CNB2005800167884A Expired - Fee Related CN100465700C (en) | 2004-05-24 | 2005-05-18 | Protein adsorption-preventing ocular lens material and method for producing same |
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| CN (4) | CN100570435C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090295004A1 (en) * | 2008-06-02 | 2009-12-03 | Pinsly Jeremy B | Silicone hydrogel contact lenses displaying reduced protein uptake |
| JP4750211B1 (en) * | 2010-05-11 | 2011-08-17 | 株式会社 資生堂 | Surface modification method and surface modification material |
| CN103739621A (en) * | 2010-09-08 | 2014-04-23 | 上海生物医学工程研究中心 | Application of surface treating agent with phosphorylcholine-like structure in material surface modification |
| CN103948965B (en) * | 2014-04-30 | 2015-12-09 | 华南理工大学 | A kind of intraocular lens of surface modification and surface modifying method |
| TWI609703B (en) | 2017-04-10 | 2018-01-01 | 明基材料股份有限公司 | Ophthalmic lens and manufacturing method thereof |
| WO2019150260A1 (en) * | 2018-01-30 | 2019-08-08 | Novartis Ag | Contact lenses with a lubricious coating thereon |
| CN110804104B (en) * | 2019-10-30 | 2021-12-07 | 暨南大学 | Cell membrane bionic surface modified bacterial cellulose and preparation method and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8401534D0 (en) * | 1984-01-20 | 1984-02-22 | Royal Free Hosp School Med | Biocompatible surfaces |
| US4990582A (en) * | 1986-07-18 | 1991-02-05 | Salamone Joseph C | Fluorine containing soft contact lens hydrogels |
| JP3825502B2 (en) * | 1996-06-11 | 2006-09-27 | 日本油脂株式会社 | Modified protein production method and contact lens dirt remover |
| DE69920484T2 (en) * | 1998-07-17 | 2005-10-06 | Biocompatibles Uk Ltd., Farnham | METHOD FOR PRODUCING COATED MOLDED POLYMERIC ARTICLES |
| JP4772939B2 (en) * | 1998-09-29 | 2011-09-14 | 日油株式会社 | Polymerizable monomer composition and contact lens |
| WO2001005855A1 (en) * | 1999-07-14 | 2001-01-25 | Nof Corporation | Random copolymer, process for the production thereof and medical material |
| JP3959676B2 (en) * | 2001-11-07 | 2007-08-15 | 東洋紡績株式会社 | Highly safe polymer composition containing phosphorus-containing polymer |
-
2005
- 2005-05-18 CN CNB2005800164782A patent/CN100570435C/en not_active Expired - Fee Related
- 2005-05-18 CN CN2005800168463A patent/CN1957288B/en not_active Expired - Fee Related
- 2005-05-18 CN CNB2005800167884A patent/CN100465700C/en not_active Expired - Fee Related
- 2005-05-18 CN CNB200580016610XA patent/CN100474036C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1957288B (en) | 2012-01-11 |
| CN1961242A (en) | 2007-05-09 |
| CN100570435C (en) | 2009-12-16 |
| CN1957288A (en) | 2007-05-02 |
| CN1957286A (en) | 2007-05-02 |
| CN1957287A (en) | 2007-05-02 |
| CN100465700C (en) | 2009-03-04 |
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