CN1957288B - Method for producing protein adsorption-preventing ocular lens material - Google Patents
Method for producing protein adsorption-preventing ocular lens material Download PDFInfo
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- CN1957288B CN1957288B CN2005800168463A CN200580016846A CN1957288B CN 1957288 B CN1957288 B CN 1957288B CN 2005800168463 A CN2005800168463 A CN 2005800168463A CN 200580016846 A CN200580016846 A CN 200580016846A CN 1957288 B CN1957288 B CN 1957288B
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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 compound having a terminal amino group is introduced into the surface of the ocular lens material and then a compound represented by the formula (2) or (3) below is introduced thereinto through the compound having the terminal amino group. The object of the present invention is to provide a method of manufacturing a contact lens that prevents protein adsorption. In the formula (2), n is a natural number of 1-18.
Description
Technical field
The present invention relates to the manufacturing approach and the method that prevents protein adsorption of ocular lens materials such as contact lenses.In particular, relate to aftertreatment, the surface (particularly contact lenses) of ocular lens material is handled, prevent the method for protein dirt through the compound of phosphoric acid choline base.
Background technology
With the monomer polymerization of phosphoric acid choline base, as contact lens material, this is known method (patent documentation 1-3).For example; (methyl) acrylic ester of containing phosphoric acid choline base is disclosed in the patent documentation 1 as the property of water-bearing soft contact lens that constitutes the unit; And record: its water percentage, oxygen permeability, pulling strengrth excellence, the protein adsorption amount is few, can suppress adhering to of dirt.
About the post-processing approach of contact lenses, record in the patent documentation 4: the monomer that makes phosphoric acid choline base is made the contact lenses that possess hydrophilic property is surperficial, protein adsorption is few in the contact lens surface polymerization.
Disclose in the patent documentation 5: with low molecular phosphocholine compound and contact lens surface chemical bonding, to reduce the method for protein adsorption.
That is, put down in writing among the embodiment 5 of patent documentation 5 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 hydroxyl ethyl ester multipolymer.But when demonstration test was carried out in above-mentioned reaction, the result also failed to obtain the desirable contact lenses of handling through phosphocholine.
Put down in writing the chemical structural formula that the phosphocholine carboxyl compound changes active ester in the reaction equation 6 of patent documentation 5.All not on the books about its synthetic method, embodiment, therefore can't carry out demonstration test, but according to common organic chemistry general knowledge; Synthetic when having the phosphocholine carboxyl compound of the structure of being put down in writing; Its method is extremely complicated, and yield is low, therefore can easily analogize it and lack practicality.
As stated, the disposal route of being put down in writing in the patent documentation 5 is not put down in writing the synthetic method of the compound that contains carboxyl phosphoric acid choline base that contact lenses are handled, and can't implement the method for being put down in writing immediately.And the reaction that imports phosphorylcholine to contact lens surface also can't fully be carried out under the condition that these patent documentations are put down in writing, and its import volume is low, therefore can not show the excellent effect that prevents protein adsorption.
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.Particularly with the polymkeric substance of 2-hydroxyethyl methacrylate be the moisture soft contact lens of principal ingredient or wherein the high moisture soft glasses that obtain of the methacrylic acid of the ionic monomer of minor amounts of copolymerized, or as hydrophilic monomer; 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 the special table of Japan
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 present invention provides a kind of contact lenses, through contact lenses are carried out aftertreatment, via the compound with terminal amino group, makes phosphorylcholine and contact lens surface covalent bonding, and CKIs matter absorption contact lenses prevent the protein dirt.
Promptly; The object of the invention is not the method for in above-mentioned patent documentation 1-3, putting down in writing, and makes the monomer polymerization that contains phosphorylcholine, makes the contact lenses of anti-protein adsorption; But, make it have the excellent function that prevents protein adsorption through contact lenses are carried out aftertreatment.
The object of the 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; 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.
The object of the 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 essential distinction of method shown in the present invention and the patent documentation 5 is: among the present invention; The compound that it is characterized in that having terminal amino group imports the surface of ocular lens material, via this compound, makes the compound and the contact lens surface chemical bonding of the phosphoric acid choline base of low-molecular-weight, formula (2) or (3); Can suppress the distortion of lens thus, the absorption of CKIs effectively simultaneously.Promptly; When directly in the functional group that is present in contact lens surface, importing phosphorylcholine; Because its high-hydrophilic, lens have the tendency of expansion slightly, still; Have amino alkyl or alkoxy etc. through between lens surface and phosphorylcholine, importing two ends, can easily control this expansion.Water wettability with amino compound is low more, then has more to suppress the effect that lens expand.When alkyl chain length is 0-6, most preferably, can control expansion.During for oxyalkylene group, the influence of chain length is little.
Promptly; The present invention provides the manufacturing approach of ocular lens material; This method has surface reaction and the operation of covalent bonding of the compound that makes the phosphorylcholine shown in (1) that has following formula and ocular lens material; It is characterized in that: the compound that will have terminal amino group imports the surface of ocular lens material, then, imports the compound of following formula (2) via above-mentioned compound with terminal amino group.
[changing 5]
[changing 6]
N is the natural number of 1-18
(2)
The present invention also provides the manufacturing approach of ocular lens material; The manufacturing approach of this ocular lens material has surface reaction and the operation of covalent bonding of the compound that makes the phosphorylcholine shown in (1) that has following formula and ocular lens material; It is characterized in that: the compound that will have terminal amino group imports the surface of ocular lens material, imports the compound of the phosphoric acid choline base of following formula (3) then via above-mentioned compound with terminal amino group.
[changing 7]
[changing 8]
The present invention's fork provides the manufacturing approach of above-mentioned ocular lens material; It is characterized in that: above-mentioned compound with terminal amino group is that alkyl, the degree of polymerization with C0 (hydrazine)～C12 is that 1～10 Oxyranyle, the degree of polymerization are that 1～10 epoxypropane base, the degree of polymerization are that 1～20 ethylene imine, the degree of polymerization are the compound of 1～20 2-methyl ethylene imine, has the compound of piperazine or aniline.
The present invention also provides the method that prevents the ocular lens material adsorbed proteins; It is characterized in that: the surface to ocular lens material imports the compound with terminal amino group; The then compound through making above-mentioned phosphoric acid choline base and the ocular lens material aftertreatment of reacting; Make the surperficial covalent bonding of phosphorylcholine and ocular lens material, prevent the absorption of protein ocular lens material.
The present invention provides the method that prevents the ocular lens material adsorbed proteins again; It is characterized in that: import amino in the compound of the phosphoric acid choline base of upper quadrant (2) or (3); The then processing of the surface reaction through making itself and ocular lens material; Make the surperficial covalent bonding of phosphorylcholine and ocular lens material, prevent the absorption of protein ocular lens material.
The present invention also provides ocular lens material, and this ocular lens material is through amido link or alkanamine key, between the compound with phosphorylcholine of the surface of ocular lens material and the following formula of importing (2) or (3), imports spacer groups.
Manufacturing method according to the invention can be passed through easy post-processing approach, via the compound with terminal amino group, makes the phosphorylcholine of any amount and the surperficial covalent bonding of ocular lens material.
Ocular lens material of the present invention---contact lenses are via the compound with terminal amino group, make phosphorylcholine and contact lens surface covalent bonding, and therefore effectively CKIs matter is adsorbed contact lenses, the anti-dirt effect that performance is excellent.Also can improve water-retaining property, also can improve and wear sense.
In addition, be to have anti-protein adsorption function through aftertreatment, therefore can in existing contact lenses, easily utilize the present invention.
Be not to cover through 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, be preferred for feeling easily in the contact lenses of foreign body sensation because of reason such as the flexibility difference of material.
The yield of reaction of compound of compound and formula (2) and formula (3) that particularly has terminal amino group is fabulous, controls import volume easily.Therefore, having can be with the effect of extreme efficiency to the excellence of the phosphorylcholine of contact lens surface introducing-type (1).
According to this method, can also suppress the distortion of lens, simultaneously the effectively absorption of CKIs.Promptly; Directly when the functional group that is present in contact lens surface imported the high functional group of water wettability, lens had the tendency of expansion slightly, but through between lens surface and phosphorylcholine, selecting two ends to have amino functional group; Control its polarity, can easily control its expansion.
The accompanying drawing summary
Fig. 1 is the chart of protein adsorption amount of the contact lenses of embodiment and comparative example.
Embodiment
Below specify the present invention.
" compound " with terminal amino group
Compound with amino used in the present invention has: hydrazine, ethylenediamine, propane diamine, 1; 4-diaminobutane, 1; 6-diamino hexane, piperazine, ethylene glycol bisthioglycolate (2-amino-ethyl) ether, ethylene glycol bisthioglycolate (3-aminopropyl) ether etc., more than the various reagent that all can be used as buy.Its polarity also is in can preventing the scope that expands.In addition, three (2-amino-ethyl) amine or amino terminal dendrimer etc. have the compound of three or above terminal amino group also can be effectively as the amino compound that has that uses among the present invention.
" preparation method of the compound of the phosphoric acid choline base of formula (2) "
Phosphorylcholine can be synthetic fully.But synthesis condition is complicated, must be strict anhydrous condition, and manufacturing cost is high.
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 through hydrolysis, can be more low-cost and easily obtain 1-α-choline glycerophosphatide.The inventor finds to ftracture through the glycol moiety oxidisability with this 1-α-choline glycerophosphatide, has easily obtained to have the compound of the phosphoric acid choline base of carboxyl.
The most representative synthetic method is: 1-α-choline glycerophosphatide in water and acetonitrile equal solvent, is carried out oxidation through sodium metaperiodate and ruthenium trichloride, obtain the target carboxyl compound.
The compound of formula (2) preferably uses the carboxyl methyl acid phosphate choline (during n=1) by 1-α-choline glycerophosphatide oxidation cracking obtains.
" method for preparing carboxyl methyl acid phosphate choline through the oxidation cracking of 1-α-choline glycerophosphatide "
1-α-choline glycerophosphatide can carry out the oxidation cracking through periodate and ruthenium trichloride in water, acetonitrile mixed solvent, process carboxyl methyl acid phosphate choline.
That is, shown in embodiment, 5g 1-α-choline glycerophosphatide is dissolved in 70ml water-30ml acetonitrile.Ice-cooled 17g sodium metaperiodate and the 80mg ruthenium trichloride of adding down, stirred overnight, filtering precipitate, concentrating under reduced pressure obtains 3.86g (yield 82%) target carboxyl methyl acid phosphate choline through methanol extraction.
" preparation method of the compound of the phosphoric acid choline base of formula (3) "
Through known method, known choline glycerophosphatide is carried out the oxidation cracking.For example, use oxygenants such as periodic acid, periodate or bismuth trioxide, to 1, the 2-glycol carries out oxidation, makes the key cracking, can obtain the aldehyde body.Reaction is carried out in water or in the moisture organic solvent usually, and temperature of reaction is 0 a ℃～room temperature.Through balanced reaction, the aldehyde body also forms hydrate in water, and this is to not influence of reaction ensuing and amine.Below provide the example that preparation contains the monofunctional aldehyde body flow process of phosphorylcholine.
[changing 13]
" ocular lens material "
Among the present invention, ocular lens material is the moulding article that are worn on the material in the eyes.Mainly be contact lenses.Can be the contact lenses of any material.For example all can make contact lenses of the present invention: promptly by following contact lenses; By methacrylic acid (MAA), acrylic acid (AA), 2-hydroxyethyl methacrylate (HEMA), N-vinyl pyrrolidone (NVP), N, the multipolymer of the polymkeric substance of 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 (シ ロ キ サ ニ Le) ester (SiMA), siloxy group styrene (SiSt), GDMA (EGDMA), allyl methacrylate (AMA), silicone macromolecule monomer etc. or two kinds or above monomer constitutes.
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 through method of the present invention.
Monomer preferred for this invention is acrylic or methacrylic acid.If contain acrylic or methacrylic acid in the monomer of formation contact lenses,, therefore can easily above-mentioned compound with two terminal amino groups be imported through amido link because contact lens surface has carboxyl.
Even there are not the contact lenses of carboxyl, also can import carboxyl through surface modifier or plasma treatment.Concrete introduction method through plasma treatment is as follows.
< surface reaction through plasma treatment imports carboxyl >
Under carbon dioxide atmosphere, import carboxyl to contact lens surface through low temperature plasma.Specifically, contact lenses are packed in the reaction vessel for plasma, with vacuumizing in the reaction vessel, import carbon dioxide then with vacuum pump.Then carry out glow discharge, can import carboxyl to contact lens surface.
" preparation method "
At first, make compound with terminal amino group and contact lenses constitute the carboxyl of monomer or the carboxyl covalent bonding (amido link) that newly behind contact lens surface, imports through plasma treatment etc. through conventional method.
Specifically; The contact lenses that poly-HEMA is made are contained in the reaction vessel for plasma (サ system コ イ Application タ one Na シ ヨ Na Le research institute makes BP-1); Air in the container is replaced into carbon dioxide fully, at room temperature carries out 10 minutes anodizing (RFPower100), import carboxyl.Then; To be coupling agent at carbodiimides such as carbonyl dimidazoles or 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochlorides; Perhaps the contact lenses handled down of existence such as thionyl chloride, phosphorus pentachloride, phosphoryl chloride phosphorus oxychloride, phosphorus tribromide, oxalyl chloride are immersed in the excessive water or organic solvent that contains the compound with two terminal amino groups; Carry out amidation process, terminad imports amino, then washing.
Then, make the compound of formula (2) or (3) and unreacted amino carry out amide linkage.
Specifically; During for the compound of formula (2), with (2) compound dissolution or be scattered in water or N, in the organic solvents such as dinethylformamide, acetonitrile, dimethyl sulfoxide (DMSO); Adding carbodiimides such as carbonyl dimidazoles or 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride is coupling agent; Perhaps thionyl chloride etc. is processed active ester or chloride thing, carries out amidation process with the amino surface of contact lenses.
During for the compound of formula (3), in protonic solvent such as water or methyl alcohol or contain in the solvent of these materials, the dipping contact lenses reacts 4 hours, added the cyanic acid sodium borate again with (3) compound dissolution, and stirred overnight is washed then.
As a result, via compound with terminal amino group, can be to the phosphorylcholine of the surperficial introducing-type (1) of contact lenses.
About the importing of compound, so long as in the scope of record, all can react under the same conditions with two terminal amino groups.
Also can in contact lenses, directly import amino through plasma treatment.Known method is as shown in following.
< surface reaction through plasma treatment imports amino >
Under nitrogen atmosphere, import amino to contact lens surface through low temperature plasma.Specifically, contact lenses are packed in the reaction vessel for plasma, make in the reaction vessel with vacuum pump to vacuumize, import nitrogen then.Then, can import amino to lens surface through glow discharge.Relevant document about plasma treatment is as follows.
1.M.Muller，C.oehr
Plasma?aminofunctionalisation?of?PVDF?microfiltration?membranes：comparison?ofthe?in?plasma?modifications?with?a?grafting?method?using?ESCA?and?anamino-selective?fluorescent?probeSurface?and?Coatings?Technology?116-119(1999)802-807
2.Lidija?Tusek，Mirko?Nitschke，Carsten?Werner，Karin?Stana-Kleinschek，VolkerRibitsch
Surface?characterization?of?NH3?plasma?treated?polyamide?6?foilsColloids?and?Surfaces?A：Physicochem.Eng.Aspects?195(2001)81-95
3.Fabienne?Poncin-Epaillard，Jean-Claude?Brosse，Thierry?FalherReactivity?of?surface?groups?formed?onto?a?plasma?treated?poly(propylene)filmMacromol.Chem.Phys.200.989-996(1999)
Embodiment
Below, according to embodiment further explain the present invention.The present invention does not receive the qualification of these embodiment.
" synthesizing of the compound of formula (2) "
5g 1-α-choline glycerophosphatide is dissolved in 70ml water-30ml acetonitrile.Ice-cooled 17g sodium metaperiodate and 80mg ruthenium trichloride, the stirred overnight of adding down.Filtering precipitate, concentrating under reduced pressure obtains 3.86g (yield 82%) target carboxyl methyl acid phosphate choline through methanol extraction.
The compound of the formula (2) when carboxyl methyl acid phosphate choline is n=1.
" synthesizing of the compound of formula (3) "
450mg 1-α-choline glycerophosphatide is dissolved in 15ml distilled water, in ice-water bath, cools off.Add the 750mg sodium metaperiodate, stirred 5 hours.With the reactant liquor concentrating under reduced pressure, drying under reduced pressure is through the methanol extraction target substance.
" embodiment 1 " have the compound of formula (2) contact lenses (spacer groups: ethylenediamine) >
(trade name ワ Application デ one ア キ ユ PVC ユ one, J&J make, constitute monomer: HEMA-MAA) be immersed in the 3ml water with 1 commercially available soft contact lens EtafilconA; Add 30mg ethylenediamine, 10mg 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, 6mg N-hydroxy-succinamide, at room temperature stirred 3 hours.Contact lenses are fully washed with pure water; Be immersed in the 3ml water; Add compound, 10mg 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, the 6mg N-hydroxy-succinamide of 10mg chemical formula (2) then; At room temperature stirred 3 hours, water fully washs then, obtains the contact lenses of target phosphorylcholine and surface chemistry bonding.
" embodiment 2 " have the compound of formula (3) contact lenses (spacer groups: ethylenediamine) >
(trade name ワ Application デ one ア キ ユ PVC ユ one, J&J make, constitute monomer: HEMA-MAA) be immersed in the 3ml water with 1 commercially available soft contact lens EtafilconA; Add 30mg ethylenediamine, 10mg 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, 6mgN-HOSu NHS, at room temperature stirred 3 hours.Contact lenses are fully washed with pure water, be immersed in the 3ml water, add the compound of 10mg chemical formula (3) then; At room temperature stirred 4 hours, and added 3mg cyanic acid sodium borate then, stirred overnight; Water fully washs, and obtains the contact lenses of target phosphorylcholine and surface chemistry bonding.
" embodiment 3 " < contact lenses (spacer groups: 1,6-diamino hexane)>with compound of formula (2)
(trade name ワ Application デ one ア キ ユ PVC ユ one, J&J make, constitute monomer: HEMA-MAA) be immersed in 3ml N with 1 commercially available soft contact lens EtafilconA; In the dinethylformamide; Add 50mg 1; 6-diamino hexane, 10mg 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, 6mg N-hydroxy-succinamide at room temperature stirred 3 hours.Contact lenses are used N, and dinethylformamide fully washs, and is immersed in 3ml N; In the dinethylformamide; Then with the compound of 10mg chemical formula (2) and 1ml with the 6mg thionyl chloride at N, the solution that stirs 30 minutes gained in the dinethylformamide mixes, and reacts 4 hours; Water fully washs, and obtains the contact lenses of target phosphorylcholine and surface chemistry bonding.
" embodiment 4 " have the compound of formula (2) contact lenses (isolate group: ethylene glycol bisthioglycolate (2-amino-ethyl) ether) >
(trade name ワ Application デ one ア キ ユ PVC ユ one, J&J make, constitute monomer: HEMA-MAA) be immersed in 3ml N with 1 commercially available soft contact lens EtafilconA; In the dinethylformamide; Add 62mg ethylene glycol bisthioglycolate (2-amino-ethyl) ether, 10mg 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, 6mg N-hydroxy-succinamide, at room temperature stirred 3 hours.Contact lenses are used N, and dinethylformamide fully washs, and is immersed in 3ml N; In the dinethylformamide; Then with the compound of 10mg chemical formula (2) and 1ml with the 6mg thionyl chloride at N, the solution that stirs 30 minutes gained in the dinethylformamide mixes, and reacts 4 hours; Water fully washs, and obtains the contact lenses of target phosphorylcholine and surface chemistry bonding.
" comparative example 1～5 "
The contact lenses that use following commercial goods are as article relatively.
Comparative example 1.EtafilconA (trade name: ワ Application デ one ア キ ユ PVC ユ one, J&J make)
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 ヨ 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 ヨ Application are made)
Comparative example 6. comparing embodiments 1
Comparative example 7. comparing embodiments 2
" comparative example 6 "
According to the method for patent documentation 5, with 10mg 1-α-choline glycerophosphatide, 20mg 1,1-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 10mg 1-α-choline glycerophosphatide, 20mg 1,1-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 1～4, comparative example 1～7 is as shown in Figure 1.Can know by this result: the absorption of the remarkable CKIs matter of contact lenses of the present invention.
Industrial applicability
According to the present invention, can height CKIs matter adsorb contact lenses, significantly prevent the protein dirt.
Method of the present invention preferably is used in the protein dirt and can causes in the soft contact lens of fatal problem.Especially preferably be used in the ionic soft contact lens that promotes protein adsorption.
Claims (6)
1. the disposal route of contact lenses; The disposal route of these contact lenses has surface reaction and the operation of covalent bonding of the compound that makes the phosphorylcholine shown in (1) that has following formula and contact lenses; It is characterized in that: the compound that will have terminal amino group imports the surface of contact lenses; Then, import the compound of the phosphoric acid choline base of following formula (2) via above-mentioned compound with terminal amino group
2. the disposal route of contact lenses; The disposal route of these contact lenses has surface reaction and the operation of covalent bonding of the compound that makes the phosphorylcholine shown in (1) that has following formula and contact lenses; It is characterized in that: the compound that will have terminal amino group imports the surface of contact lenses; Then import the compound of the phosphoric acid choline base of following formula (3) via above-mentioned compound with terminal amino group
3. the disposal route of claim 1 or 2 contact lenses is characterized in that: above-mentioned compound with terminal amino group is that alkyl, the degree of polymerization with C0～C12 is that 1～10 Oxyranyle, the degree of polymerization are that 1～10 epoxypropane base, the degree of polymerization are that 1～20 the ethylene imine or the degree of polymerization are the compound of 1～20 2-methyl ethylene imine.
4. prevent the method for contact lenses adsorbed proteins; It is characterized in that: the surface to contact lenses imports the compound with terminal amino group; The then compound of the phosphoric acid choline base through making following formula (2) or (3) and the contact lenses aftertreatment of reacting; Make the surperficial covalent bonding of phosphorylcholine and contact lenses, prevent the absorption of protein contact lenses
5. prevent the method for contact lenses adsorbed proteins; It is characterized in that: in the compound of the phosphoric acid choline base of following formula (2) or (3), import amino; Then through with the processing of the surface reaction of contact lenses; Make the surperficial covalent bonding of phosphorylcholine and contact lenses, prevent the absorption of protein contact lenses
6. contact lenses; It is as the monomer that constitutes contact lenses; With the 2-hydroxyethyl methacrylate is the soft contact lens of principal ingredient, the ionic soft contact lens that perhaps methacrylic acid and 2-hydroxyethyl methacrylate copolymerization is obtained; Wherein imported the compound shown in following formula (2) or (3) through compound in its surface with phosphorylcholine with terminal amino group
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| Application Number | Priority Date | Filing Date | Title |
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| JP2004153256 | 2004-05-24 | ||
| JP153256/2004 | 2004-05-24 | ||
| JP136846/2005 | 2005-05-10 | ||
| JP2005136846A JP3738027B2 (en) | 2004-05-24 | 2005-05-10 | Method for producing ophthalmic material for preventing protein adsorption |
| PCT/JP2005/009083 WO2005114305A1 (en) | 2004-05-24 | 2005-05-18 | Method for producing protein adsorption-preventing ocular lens material |
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| CN1957288A CN1957288A (en) | 2007-05-02 |
| CN1957288B true CN1957288B (en) | 2012-01-11 |
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| CNB2005800164782A Expired - Fee Related CN100570435C (en) | 2004-05-24 | 2005-05-18 | Ocular lens material and manufacture method thereof |
| 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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| 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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| 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 |
| EP3746820B1 (en) * | 2018-01-30 | 2022-02-16 | Alcon Inc. | 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4721800A (en) * | 1984-01-20 | 1988-01-26 | Biocompatibles Ltd. | Biocompatible surfaces |
| CN87105002A (en) * | 1986-07-18 | 1988-02-03 | 奥蒂默斯公司 | fluorine-containing soft contact lens hydrogels |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| AU750236B2 (en) * | 1998-07-17 | 2002-07-11 | Biocompatibles Uk Limited | Method for providing coated moulded polymeric articles |
| JP4772939B2 (en) * | 1998-09-29 | 2011-09-14 | 日油株式会社 | Polymerizable monomer composition and contact lens |
| JP4691868B2 (en) * | 1999-07-14 | 2011-06-01 | 日油株式会社 | Random copolymer, method for producing the same, 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 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
- 2005-05-18 CN CNB200580016610XA patent/CN100474036C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4721800A (en) * | 1984-01-20 | 1988-01-26 | Biocompatibles Ltd. | Biocompatible surfaces |
| CN87105002A (en) * | 1986-07-18 | 1988-02-03 | 奥蒂默斯公司 | fluorine-containing soft contact lens hydrogels |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2003-138144A 2003.05.14 |
| JP特开2004-175830A 2004.06.24 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100465700C (en) | 2009-03-04 |
| CN1957288A (en) | 2007-05-02 |
| CN1957286A (en) | 2007-05-02 |
| CN100474036C (en) | 2009-04-01 |
| CN1957287A (en) | 2007-05-02 |
| CN1961242A (en) | 2007-05-09 |
| CN100570435C (en) | 2009-12-16 |
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