CN1957288A - Method for producing protein adsorption-preventing ocular lens material - Google Patents

Method for producing protein adsorption-preventing ocular lens material Download PDF

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CN1957288A
CN1957288A CNA2005800168463A CN200580016846A CN1957288A CN 1957288 A CN1957288 A CN 1957288A CN A2005800168463 A CNA2005800168463 A CN A2005800168463A CN 200580016846 A CN200580016846 A CN 200580016846A CN 1957288 A CN1957288 A CN 1957288A
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lens material
ocular lens
compound
phosphorylcholine
terminal amino
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CN1957288B (en
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石原一彦
隅田如光
宫泽和之
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Shiseido Co Ltd
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Shiseido Co Ltd
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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

Prevent the manufacture method of the ocular lens material of protein adsorption
Technical field
The present invention relates to the manufacture method 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 by 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) acrylate 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 in the contact lens surface polymerization, makes possess hydrophilic property surface, contact lenses that protein adsorption is few.
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 mentioned above, 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.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, by contact lenses are carried out aftertreatment, via the compound with terminal amino group, make phosphorylcholine and contact lens surface covalent bonding, Profilin matter absorption contact lenses prevent the protein dirt.
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 of anti-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 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, make 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 Profilin 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, but, have amino alkyl or alkoxy etc. by 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 invention provides the manufacture method of ocular lens material, this method 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: the compound that will have terminal amino group imports the surface of ocular lens material, then, import the compound of following formula (2) via above-mentioned compound with terminal amino group.
[changing 5]
Figure A20058001684600061
[changing 6]
N is the natural number of 1-18
(2)
The present invention also provides the manufacture method of ocular lens material, 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: 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 provides the manufacture method of above-mentioned ocular lens material again, 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: import change to the surface of ocular lens material and contain thing with terminal amino group, the then compound by 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 by 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 by amido link or alkanamine key, imports group at interval between the compound with phosphorylcholine of the surface of ocular lens material and the following formula of importing (2) or (3).
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 Profilin 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 by aftertreatment, therefore can in existing contact lenses, easily utilize the present invention.
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, 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 that particularly has the compound of terminal amino group and formula (2) and formula (3) 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 Profilin.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 by 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 describe the present invention in detail.
" 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 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 to ftracture by 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 by 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 by the oxidation cracking of 1-α-choline glycerophosphatide "
1-α-choline glycerophosphatide can carry out the oxidation cracking by periodate and ruthenium trichloride in water, acetonitrile mixed solvent, make carboxyl methyl acid phosphate choline.
That is, as shown in the Examples, 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, stirring is spent the night, filtering precipitate, concentrating under reduced pressure obtains 3.86g (yield 82%) target carboxyl methyl acid phosphate choline by methanol extraction.
" preparation method of the compound of the phosphoric acid choline base of formula (3) "
By 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]
Figure A20058001684600101
" 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 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,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), Ethylene glycol dimethacrylate (EGDMA), allyl methacrylate (AMA), the multipolymer of the polymkeric substance of 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 by 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 by amido link because contact lens surface has carboxyl.
Even there are not the contact lenses of carboxyl, also can import carboxyl by surface modifier or Cement Composite Treated by Plasma.Concrete introduction method by Cement Composite Treated by Plasma is as follows.
<import carboxyl by the surface reaction of Cement Composite Treated by Plasma 〉
Under carbon dioxide atmosphere, import carboxyl 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 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 by Cement Composite Treated by Plasma etc. by conventional method.
Specifically, the contact lenses that poly-HEMA is made are contained in the reaction vessel for plasma (サ system コ イ Application one Na シ ヨ Na Le research institute makes BP-1), air in the container is replaced into carbon dioxide fully, at room temperature carry 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 made active ester or chloride thing, carries out amidation process with the amino surface of contact lenses.
During for the compound of formula (3), (3) compound dissolution in protonic solvent such as water or methyl alcohol or contain in the solvent of these materials, is overflow the stain contact lenses, react 4 hours, add the cyano group sodium borate again, stirring is spent the night, and washs 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 by Cement Composite Treated by Plasma.Known method as shown below.
<import amino by the surface reaction of Cement Composite Treated by Plasma 〉
Under nitrogen atmosphere, import amino to contact lens surface by 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 by glow discharge.Relevant document about Cement Composite Treated by Plasma is as follows.
1.M.Muller,C.oehr
Plasma?aminofunctionalisation?of?PVDF?microfiltration?membranes:comparison?of
the?in?plasma?modifications?with?a?grafting?method?using?ESCA?and?an
amino-selective?fluorescent?probe
Surface?and?Coatings?Technology?116-119(1999)802-807
2.Lidija?Tusek,Mirko?Nitschke,Carsten?Werner,Karin?Stana-Kleinschek,Volker
Ribitsch
Surface?characterization?of?NH3?plasma?treated?polyamide?6foils
Colloids?and?Surfaces?A:Physicoehem.Eng.Aspects?195(2001)81-95
3.Fabienne?Poncin-Epaillard,Jean-Claude?Brosse,Thierry?Falher
Reactivity?of?surface?groups?formed?onto?a?plasma?treated?poly(propylene)film
Macromol.Chem.Phys.200.989-996(1999)
Embodiment
Below, further describe the present invention according to embodiment.The present invention is not subjected to 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 the 80mg ruthenium trichloride of adding down, stirring is spent the night.Filtering precipitate, concentrating under reduced pressure obtains 3.86g (yield 82%) target carboxyl methyl acid phosphate choline by 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 by the methanol extraction target substance.
The contact lenses of " embodiment 1 "<have compound of formula (2) (group at interval: ethylenediamine) 〉
With 1 commercially available soft contact lens EtafilconA (trade name ワ Application デ one ア キ ュ PVC ユ one, J﹠amp; J makes, constitutes monomer: HEMA-MAA) be immersed in the 3ml water, 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.
The contact lenses of " embodiment 2 "<have compound of formula (3) (group at interval: ethylenediamine) 〉
With 1 commercially available soft contact lens EtafilconA (trade name ワ Application デ one ア キ ュ PVC ュ one, J﹠amp; J makes, constitutes monomer: HEMA-MAA) be immersed in the 3ml water, add 30mg ethylenediamine, 10mg 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, 6mgN-N-Hydroxysuccinimide, 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 cyano group sodium borate then, stirring is spent the night, water fully washs, and obtains the contact lenses of target phosphorylcholine and surface chemistry bonding.
The contact lenses of " embodiment 3 "<have compound of formula (2) (group at interval: 1, the 6-diamino hexane) 〉
With 1 commercially available soft contact lens EtafilconA (trade name ワ Application デ one ア キ ユ PVC ユ one, J﹠amp; J makes, constitutes monomer: HEMA-MAA) be immersed in 3ml N, in the dinethylformamide, add 50mg 1,6-diamido hexane, 10mg 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, 6mg N-hydroxy-succinamide at room temperature stirred 3 hours.With contact lenses N, dinethylformamide fully washs, be 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.
The contact lenses of " embodiment 4 "<have compound of formula (2) (isolate group: ethylene glycol bisthioglycolate (2-amino-ethyl) ether) 〉
With 1 commercially available soft contact lens EtafilconA (trade name ワ Application デ one ア キ ュ PVC ュ one, J﹠amp; J makes, constitutes monomer: HEMA-MAA) be immersed in 3ml N, 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.With contact lenses N, dinethylformamide fully washs, be 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 product as a comparison.
Comparative example 1.EtafilconA (trade name: ワ Application デ one ア キ ユ PVC ュ one, J﹠amp; J makes)
Comparative example 2.EtafilconA (trade name: ワ Application デ one ア Network エ ア one, オ キ ュ ラ one サ イ エ Application ス make)
Comparative example 3.NelflconA (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 ュ 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 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 height CKIs matter adsorb contact lenses, significantly prevent albumen The matter dirt.
Method of the present invention preferably is used in the soft stealth that the protein dirt can cause fatal problem In the glasses. Especially preferably be used in the ionic soft contact lens that promotes protein adsorption.

Claims (6)

1. the manufacture method of ocular lens material, 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: the compound that will have terminal amino group imports the surface of ocular lens material, then, import the compound of the phosphoric acid choline base of following formula (2) via above-mentioned compound with terminal amino group
[changing 1]
[changing 2]
2. the manufacture method of ocular lens material, 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: the compound that will have terminal amino group imports the surface of ocular lens material, then import the compound of the phosphoric acid choline base of following formula (3) via above-mentioned compound with terminal amino group
[changing 3]
[changing 4]
Figure A2005800168460003C2
3. the manufacture method of claim 1 or 2 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.
4. prevent the method for 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 of the phosphoric acid choline base by making following formula (2) or (3) 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.
5. prevent the method for ocular lens material adsorbed proteins, it is characterized in that: import amino in the compound of the phosphoric acid choline base of upper quadrant (2) or (3), then by with the processing of the surface reaction of ocular lens material, make the surperficial covalent bonding of phosphorylcholine and ocular lens material, prevent the absorption of protein ocular lens material.
6. ocular lens material, this ocular lens material is by amido link or alkanamine key, imports group at interval between the compound with phosphorylcholine of the surface of ocular lens material and the following formula of importing (2) or (3).
CN2005800168463A 2004-05-24 2005-05-18 Method for producing protein adsorption-preventing ocular lens material Expired - Fee Related CN1957288B (en)

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JP153256/2004 2004-05-24
JP2004153256 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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CN1957288B CN1957288B (en) 2012-01-11

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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
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CN100465700C (en) 2009-03-04
CN1961242A (en) 2007-05-09

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