CN100465700C - Protein adsorption-preventing ocular lens material and method for producing same - Google Patents
Protein adsorption-preventing ocular lens material and method for producing same Download PDFInfo
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- CN100465700C CN100465700C CNB2005800167884A CN200580016788A CN100465700C CN 100465700 C CN100465700 C CN 100465700C CN B2005800167884 A CNB2005800167884 A CN B2005800167884A CN 200580016788 A CN200580016788 A CN 200580016788A CN 100465700 C CN100465700 C CN 100465700C
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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 having an OH group in any one of water, an organic solvent and a water-organic solvent mixture, thereby being covalently bonded thereto by an acetal bond. The object of the present invention is to provide an eye lens material that prevents protein adsorption and a method of manufacturing thereof. 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 and prevent the method for protein adsorption.In particular, the present invention relates to aftertreatment, the surface (particularly contact lenses) of ocular lens material is handled, prevent the method for protein dirt by the compound of phosphoric acid choline base.
Background technology
The monomer polymerization that will contain phosphorylcholine, as contact lens material, this be 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 phosphoric acid choline base (methyl) acrylate as constituting the unit, and put down in writing water percentage, oxygen permeability, pulling strengrth excellence, the protein adsorption amount is few, can suppress adhering to of dirt.
As the post-processing approach of contact lenses, record in the patent documentation 4: make the monomer and the contact lens surface polymerization that contain phosphorylcholine, manufacturing possess hydrophilic property surface, the contact lenses that protein adsorption is few.
Disclose in the patent documentation 5 and made low molecule phosphoric acid compound choline and contact lens surface chemical bonding, reduced the method for protein adsorption.
Promptly, record among the embodiment 5 of patent documentation 5: methacrylic acid 4-hydroxyl ethyl ester is total to methacrylic acid copolymer contact lenses 2-[{2-(1-imidazoles ketonic oxygen base oxethyl) hydroxyl phosphino-} the oxygen base]-N, N, N-trimethyl hydroxyethyl (エ Na ミ ニ ウ system ニ De ロ キ シ De) inner salt is handled, and it is had suppress albumin and the lysozyme effect to the absorption of contact lenses.
But, in the method for putting down in writing in the patent documentation 5, a lot of operations of synthetic needs of the compound of phosphoric acid choline base and complicated method, the utmost point is difficult to high yield and high-purity obtains target product.And, being reflected to the importing that contact lens surface imports phosphorylcholine under the condition of above-mentioned patent documentation record and can't fully carrying out, its import volume is low, therefore shows the excellent protein adsorption effect that prevents.
On the other hand, the dirt of contact lenses is contained protein or lipid absorption in the tear, becomes dirt, and this dirt 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 methacrylic acid of the ionic monomer of minor amounts of copolymerized or wherein particularly as hydrophilic monomer with the polymkeric substance of 2-hydroxyethyl methacrylate, with N-vinyl pyrrolidone or N, the polymkeric substance of N-DMAA is in the soft contact lens of principal ingredient, and the dirt 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: " dirt of soft contact lens and analysis thereof ", マ テ リ ア Le ス テ one ジ, Vol.4, No.1,2004
Summary of the invention
The invention provides a kind of contact lenses,, can make the reaction of phosphorylcholine and contact lens surface and covalent bonding, suppress the protein adsorption of contact lenses, prevent the protein dirt via compound with terminal amino group 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, makes the monomer polymerization that contains phosphorylcholine, makes the contact lenses that prevent 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 be as the method for patent documentation 4 records, make the monomer polymerization of phosphoric acid choline base on the surface of contact lenses, cover with the other polymkeric substance different with contact lenses, import phosphorylcholine thus, cover but need not polymkeric substance, direct and phosphorylcholine covalent bonding obtains excellent in te pins of durability thus, do not change the original character of contact lenses, can bring into play the excellent effect that prevents protein adsorption because of polymkeric substance covers.
Purpose of the present invention neither be as the method for citing document 5 records, when carrying out demonstration test, actually can't fully import phosphorylcholine, but can import the phosphorylcholine of q.s, the effect that prevents protein adsorption that performance is excellent to contact lens surface.
Particularly the present invention and the essential distinction of method shown in the patent documentation 5 are that the importing efficient of phosphocholine basal orientation contact lens surface is different, thus, can produce the more effectively effect of the excellence of Profilin matter absorption.
The invention has the advantages that to have the contact lens material of hydroxyl,, in any solvent, can stably import phosphorylcholine by acetal bonds no matter in water or in the organic solvent for the surface.
Promptly, the invention provides the manufacture method of ocular lens material, the manufacture method of this ocular lens material has the surface reaction that makes the compound that has phosphorylcholine shown in the following formula (1) and ocular lens material and the operation of covalent bonding, it is characterized in that: in water or in the organic solvent or in water-organic solvent mixed liquor, the compound of the phosphoric acid choline base of following formula (2) is reacted, by the acetal bonds covalent bonding with the ocular lens material with OH base.
[changing 10]
[changing 11]
N is the natural number of 1-18
(2)
The present invention also provides the manufacture method of above-mentioned ocular lens material, it is characterized in that: constitute in the monomer of above-mentioned ocular lens material and contain the monomer with hydroxyl.
The present invention provides the manufacture method of above-mentioned ocular lens material again, it is characterized in that: constitute in the monomer of above-mentioned ocular lens material and contain 2-hydroxyethyl methacrylate.
The present invention also provides the manufacture method of above-mentioned ocular lens material, it is characterized in that: above-mentioned ocular lens material contains polyvinyl alcohol (PVA) as constituent.
The present invention provides the manufacture method of ocular lens material again, the manufacture method of this ocular lens material has the surface reaction of the compound that makes the phosphorylcholine shown in (1) that has following formula and ocular lens material and the operation of covalent bonding, it is characterized in that: pass through Cement Composite Treated by Plasma, surface to ocular lens material imports the OH base, then, in water or in the organic solvent or in water-organic solvent mixed liquor, make compound and its reaction of the phosphoric acid choline base of following formula (2), by the acetal bonds covalent bonding.
[changing 12]
[changing 13]
N is the natural number of 1-18
(2)
The present invention also provides ocular lens material, in surface reaction and in the manufacture method of the ocular lens material of the operation of covalent bonding with the compound that makes the phosphorylcholine shown in (1) that has following formula and ocular lens material, it is characterized in that: in water or in the organic solvent or in water-organic solvent mixed liquor, make the compound and ocular lens material reaction of the phosphoric acid choline base of following formula (2), obtain by the acetal bonds covalent bonding with OH base.
[changing 14]
[changing 15]
N is the natural number of 1-18
(2)
The present invention provides ocular lens material again, in surface reaction and in the manufacture method of the ocular lens material of the operation of covalent bonding with the compound that makes the phosphorylcholine shown in (1) that has following formula and ocular lens material, it is characterized in that: pass through Cement Composite Treated by Plasma, surface to ocular lens material imports the OH base, then, in water or in the organic solvent or in water-organic solvent mixed liquor, the compound of the phosphoric acid choline base of following formula (2) is obtained by the acetal bonds covalent bonding.
[changing 16]
[changing 17]
N is the natural number of 1-18
(2)
The invention provides the method that prevents protein adsorption, it is characterized in that: in water or in the organic solvent or in water-organic solvent mixed liquor, make the compound and ocular lens material reaction of the phosphoric acid choline base of following formula (2) with OH base, the aftertreatment of covalent bonding prevents the absorption of protein to ocular lens material by utilizing acetal bonds.
[changing 18]
N is the natural number of 1-18
(2)
Manufacturing method according to the invention by easy post-processing approach, can make the surface reaction of the phosphorylcholine of any amount and ocular lens material and covalent bonding by acetal bonds.
Can make water, organic solvent one of them, by the compound of acetal bonds introducing-type (2), this is important advantage.That is, different with the ester bond that esterification forms, can react by in water, the ocular lens material with hydroxyl being carried out aftertreatment, this is one of advantage.
Owing in water, do not carry out the condition of esterification, therefore,, preferably adopt acetalation as can be in water or contain the method that imports phosphorylcholine in the organic solvent of water system.
That is, manufacturing method according to the invention need not to carry out aftertreatment under the anhydrous condition of strictness.In addition, when carrying out following advantage is arranged in water: by aftertreatment, ocular lens material can not go bad because of organic solvent.
Ocular lens material of the present invention---contact lenses are by acetal bonds phosphorylcholine and contact lens surface to be reacted and covalent bonding, 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.
Can make it have the protein adsorption of preventing function by aftertreatment, therefore can easily the present invention be used in existing contact lenses.
Be not to cover by polymkeric substance to import phosphorylcholine, so excellent in te pins of durability, can not make the original character variation of contact lenses basically.
The contact lenses that obtained by the present invention are to wear the excellent contact lenses of sense.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.
Particularly the reaction yield of the compound of the OH of contact lens surface base and formula (2) is very excellent, controls import volume easily.Therefore, have can be effectively to the effect of the excellence of the phosphorylcholine of contact lens surface introducing-type (1).
The accompanying drawing summary
Fig. 1 is the protein adsorption spirogram table of the contact lenses of embodiment and comparative example.
Embodiment
Below describe the present invention in detail.
" preparation method of the compound of the phosphoric acid choline base of formula (2) "
This compound can be synthetic fully.But the synthesis condition complexity must be strict anhydrous condition, the manufacturing 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 the glycol moiety oxidisability cracking with this 1-α-choline glycerophosphatide, can obtain to have the compound of the phosphoric acid choline base of aldehyde radical.The most representative synthetic method is: 1-α-choline glycerophosphatide is passed through sodium periodate oxidation in water, obtain target aldehyde body.Oxygenant and solvent are not limited to above-claimed cpd.
" method of the compound of the oxidation cracking preparation formula (2) by 1-α-choline glycerophosphatide "
1-α-choline glycerophosphatide by the periodate oxidation cracking, can be made the compound of formula (2) in water.
" ocular lens material "
Among the present invention, ocular lens material is the moulding product that are worn on the material in the eyes.Mainly be 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), the N-vinyl pyrrolidone, N, the N-DMAA, vinyl acetate, methyl methacrylate, trifluoroethyl methacrylate, cellulose acetate butyrate, fluorosilicone, methacrylic acid hexafluoro isopropyl ester, perfluoroalkyl methacrylate, methacrylic acid siloxy group (シ ロ キ サ ニ Le) ester, siloxy group styrene, Ethylene glycol dimethacrylate, allyl methacrylate, the contact lenses that the multipolymer of the polymkeric substance of silicone macromolecule monomer etc. or two kinds or above monomer constitutes contain polyvinyl alcohol (PVA) in addition, polysiloxane is as the contact lenses of constituent.
The kind of the present invention and monomer is irrelevant, can be used for any of hard contact lens, soft contact lens.
As the monomer that constitutes contact lenses, be the soft contact lens of principal ingredient with the 2-hydroxyethyl methacrylate and make methacrylic acid and ionic soft contact lens that its copolymerization obtains is representational soft contact lens that protein adsorbs easily.Therefore preferably handle by method of the present invention.
Containing polyvinyl alcohol (PVA) or poly N-ethylene pyrrolidone also preferably handles with method of the present invention as the contact lenses of the constituent of contact lenses.
And, as the monomer that constitutes contact lenses, with (methyl) methyl acrylate be the hard contact lens of principal ingredient, particularly easily the oxygen permeability of adsorbed proteins or the hard contact lens worn continuously also preferably by method processing of the present invention.
As can with the functional group of the compound covalent bonding of the phosphoric acid choline base of following formula (2) have hydroxyl owing to contain the contact lenses of 2-hydroxyethyl methacrylate or polyvinyl alcohol polymer, 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, under oxygen atmosphere or under the oxygen, hydrogen atmosphere,, import hydroxyl to contact lens surface by low temperature plasma.Specifically, contact lenses are packed in the 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.
The compound of the phosphoric acid choline base of formula (2) and the hydroxyl of contact lens surface are by the firm covalent bonding of acetal bonds.
Implication of the present invention is: by aftertreatment, phosphorylcholine directly reacts and covalent bonding by acetal bonds and contact lens surface, and imports thus.Therefore, the compound of formula (2) is not comprised in the present invention with using polymkeric substance covering contact lens surface bonding gained contact lenses or said method with OH base.
" prevent the manufacture method of the contact lenses of protein adsorption "
The compound of phosphoric acid choline base and contact lens surface close via the acetal bonds direct covalent bonds shown in the formula (2), and this is an essence of the present invention, so the not qualification of its manufacture method, can carry out the acetal combination by any method.As mentioned above, do not comprise the polymkeric substance covering of contact lens surface with OH base, the scheme that combines with the compound acetal of formula (2).This is because the polymkeric substance that covers can be peeled off, or produces the influence that overlie polymer causes.
Specifically, in organic solvent, according to conventional method, contact lenses constitute the hydroxyl of monomer or afterwards by the compound covalent bonding of the new hydroxyl that imports such as Cement Composite Treated by Plasma with the phosphoric acid choline base of (2).
" in the hydroxyl of contact lenses, import the method for phosphorylcholine "
There is hydroxyl in the contact lenses that contain methacrylic acid 2-hydroxyl polymerizable methacrylate thing or polyvinyl alcohol (PVA).Make compound and this hydroxyl reaction of formula (2), then can import phosphorylcholine to contact lens surface by acetal bonds.This is reflected in the water, or in the organic solvent such as methyl alcohol, ethanol, dimethyl formamide, dimethyl sulfoxide (DMSO), tetrahydrofuran, perhaps in the mixed liquor of water and above-mentioned organic solvent, carries out easily under acid condition.
" disposal route 1 "
Contact lenses for HEMA (methacrylic acid 2-hydroxyl polymerizable methacrylate thing) material, can followingly carry out, with organic solvents such as water or dimethyl sulfoxide (DMSO), dimethyl formamide, tetrahydrofurans is medium, in the presence of acid catalysts such as hydrochloric acid, acetate, sulfuric acid, trifluoroacetic acid, p-toluenesulfonic acid,, the compound of formula (2) undertaken by being heated in the scope of room temperature～100 ℃.The control of importing rate can be passed through compound amount, the amount of acid catalyst, the temperature of reaction of the formula (2) of being added and carry out.
" disposal route 2 "
Contact lenses for PVA (polyvinyl alcohol (PVA)) material, can followingly carry out, with organic solvents such as water or dimethyl sulfoxide (DMSO), dimethyl formamide, tetrahydrofurans is medium, in the presence of acid catalysts such as hydrochloric acid, acetate, sulfuric acid, trifluoroacetic acid, p-toluenesulfonic acid,, the compound of formula (2) undertaken by being heated in the scope of room temperature～100 ℃.The control of importing rate can be carried out according to compound amount, the amount of acid catalyst, the temperature of reaction of the formula of being added (2).
The phosphorylcholine that imports to the formula (1) of contact lens surface by said method can be following quantitative: use perchloric acid to carry out pre-treatment, by molybdenum blue method phosphorus is carried out quantitative test (list of references: the 4th edition analysis of experimental chemistry lecture (14), 3.8.2 リ Application ball is kind) then.
The import volume of the phosphocholine basal orientation contact lenses of formula (1) be preferably 0.005 μ mol/mg or more than.Lack than 0.005 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.Import volume is many, and then the effect of Profilin matter absorption increases, so its 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.
" protein adsorption experiment "
Use commercially available contact lenses, make contact lenses of the present invention.Compare by the effect of following evaluation method the absorption of Profilin matter.
" 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 solution partially protein reduction.
The artificial tears is dissolved in following composition in the pure water and obtains.
1.20mg/ml lysozyme, 3.88mg/ml albumin, 1.61mg/ml gamma globulin, 9.00mg/ml sodium chloride, 0.14mg/ml potassium dihydrogen phosphate, 0.80mg/ml sodium phosphate dibasic heptahydrate.
(list of references) FDA Guideline Draft:Testing guidelines for classIII soft (hydrophilic) contact lens solution, lens group compatibility test.July 15,1985.
[changing 19]
n＝1
(2)
The compound of above-mentioned phosphoric acid choline base is the known compound that obtains by following synthesis example 1.
" aldehyde compound of synthesis example 1 phosphoric acid choline base "
450mg1-α-choline glycerophosphatide is dissolved in the 15ml distilled water, in ice-water bath, cools off.Add the 750mg sodium metaperiodate, stirred 5 hours.With reactant liquor concentrating under reduced pressure, drying under reduced pressure, by the methanol extraction target substance.
" aftertreatments of contact lenses "
Use Polymacon (the soft contact lens Medalist that Baush Lomb company makes), NelfilconA (manufacturing of チ バ PVC ジ ョ Application, Off オ one カ ス デ イ リ イ one ズ), by acetal bonds, make the compound and the contact lenses covalent bonding of formula (2).
" embodiment 1 "
1 Polymacon is immersed in the 2ml water phosphoric acid compound choline of dissolving 10mg formula (2).Then add 2ml2N hydrochloric acid, be adjusted to the concentration of hydrochloric acid that mixed liquor is 1M, then 70 ℃ of reactions 5 hours.Reactant liquor is cooled to room temperature, fully washs, obtain the target contact lenses with pure water.The import volume of the phosphorylcholine of formula (1) is 0.0734mol/mg.
" embodiment 2 "
1 NelfilconA is immersed in the 2ml water phosphoric acid compound choline of dissolving 10mg formula (2).Then add 2ml 2N hydrochloric acid, be adjusted to the concentration of hydrochloric acid that mixed liquor is 1M, then 40 ℃ of reactions 5 hours.Reactant liquor is cooled to room temperature, fully washs, obtain the target contact lenses with pure water.The import volume of the phosphorylcholine of formula (1) is 0.1688 μ mol/mg.
" quantivative approach of the phosphorylcholine of formula (1) "
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,, use the absorbance measurement of 710nm then 95 ℃ of colour developings 5 minutes, obtain import volume.Calibration curve adopts the biphosphate sodium water solution.
" comparative example 1～5 "
The contact lenses that use following commercial goods are product as a comparison.
Comparative example 1.EtafilconA (trade name: ワ Application デ one ア キ ュ PVC ユ one, J﹠amp; J makes)
Comparative example 2.EtafilconA (trade name: ワ Application デ one ア Network エ ア one, オ キ ユ ラ one サ イ エ Application ス make)
Comparative example 3.NelfilconA (trade name: Off オ one カ ス デ イ リ イ one ズ, チ バ PVC ジ ョ Application are made)
Comparative example 4.Polymacon (trade name: メ ダ リ ス ト, ボ シ ユ ロ system are made)
Comparative example 5.VifilconA (trade name: Off オ one カ ス, チ バ PVC ジ ョ Application are made)
" comparative example 6 "
According to the method for patent documentation 5, with 10mg1-α-choline glycerophosphatide, 20mg1,1-carbonyl dimidazoles, 20mg triethylamine add in the 3ml dimethyl sulfoxide (DMSO), 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 to detect below the lower limit 0.0001 μ mol/mg, reacts and does not carry out.
" comparative example 7 "
According to the method for patent documentation 5, with 10mg1-α-choline glycerophosphatide, 20mg1,1-carbonyl dimidazoles, 20mg triethylamine add in the 3ml dimethyl sulfoxide (DMSO), stir 2 hours at 50 ℃.The NelfilconA that uses among the embodiment 2 is immersed in this solution, at room temperature reacted 12 hours.With dimethyl sulfoxide (DMSO), then water fully washs, it is quantitative to carry out phosphorus with contact lenses, and the phosphorylcholine of importing is for detecting below the lower limit 0.0001 μ mol/mg, and reaction is not carried out.
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 that obtains by manufacture method of the present invention.
Below, in embodiment 2, change the reaction treatment condition when handling NelfilconA, the relation of the import volume of research phosphorylcholine.
The relation of the addition of the compound of the import volume of phosphorylcholine and temperature of reaction, acid catalysis dosage, formula (2) is shown in table 1～3.
The effect of＜temperature of reaction 〉
The compound of formula (2): 1 equivalent (with respect to the hydroxyl of contact lenses)
Acid catalyst: 1M hydrochloric acid
[table 1]
| Temperature of reaction | The phosphorylcholine import volume |
| 70℃ | 0.5842μmol/mg |
| 40℃ | 0.1688μmol/mg |
| 25℃ | 0.0328μmol/mg |
The effect of＜acid catalysis dosage 〉
The compound of formula (2): 1 equivalent (with respect to the hydroxyl of contact lenses)
40 ℃ of temperature of reaction
[table 2]
| HCl concentration | The phosphorylcholine import volume |
| 1M | 0.1688μmol/mg |
| 0.1M | 0.0149μmol/mg |
| 0.01M | 0.0032μmol/mg |
The effect of the addition of the compound of＜formula (2) 〉
Acid catalyst: 1M hydrochloric acid
40 ℃ of temperature of reaction
[table 3]
| The addition of the compound of formula (2) | The phosphorylcholine import volume |
| 5 equivalents | 0.1688μmol/mg |
| 3 equivalents | 0.1317μmol/ |
| 1 equivalent | 0.0477μmol/mg |
By the result of table 1～3 as can be known:, can easily carry out the control of phosphorylcholine import volume by changing the reaction treatment condition.Preferred reaction treatment condition is as follows.
Temperature of reaction: room temperature～80 ℃, more preferably 40 ℃～70 ℃
Concentration of hydrochloric acid: 0.01M～5M, more preferably 0.1～1M
Phosphocholine compound (2) addition: 0.1～10 equivalent, more preferably 1～5 equivalent
Industrial applicability
According to the present invention, can height CKIs matter adsorb contact lenses, significantly prevent the dirt of protein.
Method of the present invention preferably is used in the soft contact lens that the protein dirt can cause fatal problem. Particularly preferably be used in the ionic soft contact lens that promotes protein adsorption.
Also preferably be used in the oxygen permeability of easy adsorbed proteins or the hard contact lens of wearing continuously.
Claims (8)
1. the surface treatment method of ocular lens material, it has the surface reaction of the compound that makes the phosphorylcholine shown in (1) that has following formula and ocular lens material and the operation of covalent bonding, wherein in water or in the organic solvent or in water-organic solvent mixed liquor, the compound of the phosphoric acid choline base of following formula (2) is reacted with the ocular lens material with OH base, by the acetal bonds covalent bonding
N is the natural number of 1-18
(2)。
2. the surface treatment method of the ocular lens material of claim 1 is characterized in that: constitute in the monomer of above-mentioned ocular lens material and contain the monomer with hydroxyl.
3. the surface treatment method of the ocular lens material of claim 1 is characterized in that: constitute in the monomer of above-mentioned ocular lens material and contain 2-hydroxyethyl methacrylate.
4. the surface treatment method of the ocular lens material of claim 1, it is characterized in that: above-mentioned ocular lens material contains polyvinyl alcohol (PVA) as constituent.
5. the surface treatment method of ocular lens material, it has the surface reaction of the compound that makes the phosphorylcholine shown in (1) that has following formula and ocular lens material and the operation of covalent bonding, wherein pass through Cement Composite Treated by Plasma, surface to ocular lens material imports the OH base, then, in water or in the organic solvent or in water-organic solvent mixed liquor, make compound and its reaction of the phosphoric acid choline base of following formula (2), by the acetal bonds covalent bonding
N is the natural number of 1-18
(2)。
6. ocular lens material, it is by in the surface reaction with the compound that makes the phosphorylcholine shown in (1) that has following formula and ocular lens material and in the surface treatment method of the ocular lens material of the operation of covalent bonding, in water or in the organic solvent or in water-organic solvent mixed liquor, make the compound and ocular lens material reaction of the phosphoric acid choline base of following formula (2) with OH base, obtain by the acetal bonds covalent bonding
N is the natural number of 1-18
(2)。
7. ocular lens material, it is by in the surface reaction with the compound that makes the phosphorylcholine shown in (1) that has following formula and ocular lens material and in the surface treatment method of the ocular lens material of the operation of covalent bonding, pass through Cement Composite Treated by Plasma, surface to ocular lens material imports the OH base, then, in water or in the organic solvent or in water-organic solvent mixed liquor, the compound of the phosphoric acid choline base of following formula (2) is obtained by the acetal bonds covalent bonding
N is the natural number of 1-18
(2)。
8. prevent the method for protein adsorption, it is characterized in that: by in water or in the organic solvent or make the compound and ocular lens material reaction of the phosphoric acid choline base of following formula (2) in water-organic solvent mixed liquor with OH base, through acetal bonds and the aftertreatment of covalent bonding, thereby prevent the absorption of protein to ocular lens material
N is the natural number of 1-18
(2)。
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| CN2005800168463A Expired - Fee Related CN1957288B (en) | 2004-05-24 | 2005-05-18 | Method for producing protein adsorption-preventing ocular lens material |
| CNB2005800164782A Expired - Fee Related CN100570435C (en) | 2004-05-24 | 2005-05-18 | Ocular lens material and manufacture method thereof |
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| CN2005800168463A Expired - Fee Related CN1957288B (en) | 2004-05-24 | 2005-05-18 | Method for producing protein adsorption-preventing ocular lens material |
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|---|---|---|---|---|
| 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 |
| CN117270235A (en) * | 2018-01-30 | 2023-12-22 | 爱尔康公司 | Contact lens having 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 |
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| JPH09327288A (en) * | 1996-06-11 | 1997-12-22 | Nof Corp | Production of modified protein and fouling removing agent for contact lens |
| JP2000169526A (en) * | 1998-09-29 | 2000-06-20 | Nof Corp | Polymerizable monomer composition, copolymer, and contact lens |
| WO2001005855A1 (en) * | 1999-07-14 | 2001-01-25 | Nof Corporation | Random copolymer, process for the production thereof and medical material |
| JP2002520463A (en) * | 1998-07-17 | 2002-07-09 | バイオコンパテイブルズ・リミテツド | Method of providing a coated molded polymeric article |
| JP2003138144A (en) * | 2001-11-07 | 2003-05-14 | Toyobo Co Ltd | Polymer composition containing safe phosphorus- containing polymer |
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| 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 |
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- 2005-05-18 CN CNB200580016610XA patent/CN100474036C/en not_active Expired - Fee Related
- 2005-05-18 CN CN2005800168463A patent/CN1957288B/en not_active Expired - Fee Related
- 2005-05-18 CN CNB2005800164782A patent/CN100570435C/en not_active Expired - Fee Related
- 2005-05-18 CN CNB2005800167884A patent/CN100465700C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09327288A (en) * | 1996-06-11 | 1997-12-22 | Nof Corp | Production of modified protein and fouling removing agent for contact lens |
| JP2002520463A (en) * | 1998-07-17 | 2002-07-09 | バイオコンパテイブルズ・リミテツド | Method of providing a coated molded polymeric article |
| JP2000169526A (en) * | 1998-09-29 | 2000-06-20 | Nof Corp | Polymerizable monomer composition, copolymer, and contact lens |
| WO2001005855A1 (en) * | 1999-07-14 | 2001-01-25 | Nof Corporation | Random copolymer, process for the production thereof and medical material |
| JP2003138144A (en) * | 2001-11-07 | 2003-05-14 | Toyobo Co Ltd | Polymer composition containing safe phosphorus- containing polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1957287A (en) | 2007-05-02 |
| CN1957288A (en) | 2007-05-02 |
| CN100474036C (en) | 2009-04-01 |
| CN1961242A (en) | 2007-05-09 |
| CN1957288B (en) | 2012-01-11 |
| CN100570435C (en) | 2009-12-16 |
| CN1957286A (en) | 2007-05-02 |
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