CN102115515B - Copolymer capable of enhancing wettability of silicone hydrogel, silicone hydrogel composition containing same and ophthalmic item employing silicone hydrogel composition - Google Patents
Copolymer capable of enhancing wettability of silicone hydrogel, silicone hydrogel composition containing same and ophthalmic item employing silicone hydrogel composition Download PDFInfo
- Publication number
- CN102115515B CN102115515B CN201010000220.6A CN201010000220A CN102115515B CN 102115515 B CN102115515 B CN 102115515B CN 201010000220 A CN201010000220 A CN 201010000220A CN 102115515 B CN102115515 B CN 102115515B
- Authority
- CN
- China
- Prior art keywords
- monomer
- silicone
- hydrophilic
- silicone glue
- vinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention provides a kind of reactable hydrophilic copolymers, it is substantially formed by unit by unsaturated ethylene system hydrophilic monomer and the unsaturated ethylene alkene monomer by rolling into a ball containing alkoxysilane-functional is formed by with as the unit of following formula (I) or (II) forms at random, and it has at least 50,000 molecular weight:
Wherein R1, R2 and R3 can be identical or different, be independently selected from H or C1-3 alkyl; R is C1-3 alkyl; X, Y and Z can be identical or different, be independently selected from R ' or OR ', but it is OR ' that restrictive condition, which is at least one of them,; R ' is H or C1-3 alkyl; And described unit and formula (I) are formed by by unsaturated ethylene system hydrophilic monomer or the equivalent proportion of (II) monomeric unit is fallen in the range of 5/1 to 200/1. The present invention also provides a kind of silicone glue composition comprising reactable hydrophilic copolymers according to the present invention and the ophthalmically acceptable articles as obtained by silicone glue composition of the invention.
Description
Technical field
The present invention relates to a kind of being added in the silicone glue formula that is used to form eye object, thus the reactable hydrophilic copolymers of improved materials surface wettability.The invention still further relates to make thus through improving eye article, particularly contact lens or intraocular lens (IOL).
Background technology
Contact lens come out and have so far the history of last 100 years, are considered to one of important application of raw doctor's material, and along with scientific and technological progress, the evolution of its material is also towards high oxygen permeability and high-comfort development.In the 1950's, Czech scientist utilizes poly hydroxy ethyl acrylate (poly (hydroxyethyl methacrylate); HEMA) material is made hydrogel, has invented Soft contact lens.
Generally speaking, contact lens need focus on the characteristics such as the good and high oxygen flow of security, light transmission, wherein promote the important directions that the oxygen transmission rate of eyeglass develops especially.Tradition is improved the method for HEMA hydrogel material oxygen transmission rate for reducing lens thickness, but this method is often accompanied by the shortcoming that eyeglass mechanical properties is lost.In addition, recent two decades comes, and has people that silicone material is added in eyeglass, by the high oxygen permeability of silicon materials itself, makes oxygen molecule arrive cornea through eyeglass smoothly, not only promotes oxygen transmission rate, the comfort level more can promote contact lens wear time.Current modal silicon materials are polysiloxane (polysiloxane) or silicone (silicone), but the wettability of silicone material own is poor and not hydrophilic, therefore the follow-up different methods that just develops is to improve the shortcoming of silicone molecule wettability.
General mode of promoting silicone glue wettability can be divided into two classes haply:
(1) in type eyeglass, carry out the processing of wetting ability post-treatment: for example U.S. the 4th, 214, No. 014 patent discloses and uses Cement Composite Treated by Plasma silicone glue lens surface, and the U.S. the 6th, in 099, No. 852 patent, silane coupling agent (silane coupling agent) is applied to in type silicone glue lens surface, and by its impregnation to hydroaropic substance, by chemical bonded refractory, hydroaropic substance is grafted on to lens surface, to increase lens surface wettability.Though this post-treatment mode can increase degree of wetting, because the course of processing is loaded down with trivial details, in technique, lack efficiency so that improve cost of manufacture, thereby produce in line actually rare in reality.
(2) in silicone glue formula, add hydrophilic molecule: this mode can improve the wettability of lens surface in the situation that not affecting script technique, therefore becomes the current main flow of improving contact lens wettability.
Early stage mode of adding hydrophilic molecule is mainly to import and have reactivity in the main composition of silicone glue, can be directly and the response type hydrophilic molecule of main formula composition copolymerization, with in making eyeglass process, directly cause moistening effect thus.The for example U.S. the 5th, 219, No. 965 patents, the 5th, 364, No. 918 patents and the 5th, 525, No. 691 patents are disclosed in and in hydrophilic molecule structure, introduce ethene serial reaction functional group, its can with silicone glue formula in there is vinyl group material carry out chemical bonded refractory, utilize covalent linkage that hydrophilic segment is connected in whole silicone glue formula, the hydroaropic substance of its use that discloses, mainly that molecular weight is 500 to 10, 000 gather-N-V-Pyrol RC (poly-N-vinylpyrrolidone (PVP)), because of hydrophilic segment curtailment, the effect that causes it can promote lens surface wettability is limited.
The U.S. the 6th, 367, No. 929 patents are disclosed in directly to add in silicone glue formula does not have reactivity but a greatly hydrophilic macromolecule (as PVP) of (being at least greater than 50kDa) of molecular weight, and significantly improves the wettability of eyeglass.But because the whole molecular chain of this molecule is wetting ability, on chain, there is no can be compatible with silicon materials segment, thereby the eyeglass forming can be because of the compatible not enough phenomenon that produce printing opacity inequality.Therefore, the derivative case U.S. the 7th, 052 of described patent, No. 131 patent is disclosed in when using high molecular PVP, the compatible agent of extra introducing (compatibilizingagent), by the effect of compatilizer, makes PVP and silicone glue be able to compatible.But, additionally add a compatible agent, except increasing the complicacy of formula, the design of described compatible agent and the molecular characterization of selecting also must consider original formulation.
On the other hand, the U.S. the 7th, 468, No. 397 patents and the 7th, 528, No. 208 patents disclose and use the main component of making contact lens containing prepolymer (silicone-containing prepolymer) conduct of silicone, its molecule be by the preparation of long-chain siloxanes (siloxane) and hydrophilic quaternary ammonium salt segment (hydrophilic quaternary amine salt) random copolymers (random copolymer), and its end is that ethene is reactive functionality, thus, intermolecular polymerization mutually and form eyeglass, increase its compatibility, and provided the oxygen-permeable of eyeglass by siloxanes segment, structural strength, can provide wettability by hydrophilic quaternary ammonium salt segment in addition.So this molecular designing, not only can directly make eyeglass with described molecule, can also reach simultaneously and improve wettability and compatible object.But while making eyeglass with this concept, the molecular structure of described prepolymer need be through special design, thereby only can be used for specific silicone glue system, comparatively limitation and trouble in use, and lack efficiency.
In sum, industrial community still needs technical solution, in improving the wettability of silicone glue material surface, can also take into account compatibility and process convenience and oxygen transmission rate.This case contriver develop through broad research, by add a kind of molecule in silicone glue formula, described molecule contains hydrophilic segment and the novel polymer wetting agent containing organoalkoxysilane (alkoxysilane) reactive functional groups segment simultaneously, can effectively address the above problem.
Summary of the invention
So object of the present invention is for providing a kind of reactable hydrophilic copolymers, it is the unit that forms of hydrophilic monomer by unsaturated ethylene in fact and is made up of at random having as shown in the formula (I) or unit (II) of forming containing the unsaturated ethylene alkene monomer of alkoxysilane-functional group, and it has at least 50,000 molecular weight:
Wherein R
1, R
2and R
3can be identical or differently, be independently selected from H or C
1-3alkyl; R is C
1-3alkyl; X, Y and Z can be identical or different, are independently selected from R ' or OR ', but restricted condition is for wherein at least one is OR '; R ' is H or C
1-3alkyl; And described by unsaturated ethylene be the unit that forms of hydrophilic monomer and formula (I) or (II) equivalence ratio of monomeric unit fall within 5/1 to 200/1 scope.
Another object of the present invention is for providing a kind of silicone glue composition, and it comprises:
(a) be used to form the monomer mixture of silicone glue, described mixture comprises at least one silicone monomer containing alkoxysilane-functional group; And
(b) according to reactable hydrophilic copolymers of the present invention.
A further object of the present invention is for providing a kind of by the prepared eye article of silicone glue composition of the present invention.
Accompanying drawing explanation
Fig. 1 is the NMR collection of illustrative plates that shows the chemical bonded refractory test result of reactable hydrophilic copolymers of the present invention.
Embodiment
Known techniques is for can significantly improve silicone glue wettability of the surface, need to add the hydrophilic compounds of high molecular, but for avoiding the incompatible optical property that affects eyeglass of described hydrophilic compounds and silicone glue, generally need in described formula, additionally add compatible agent.
Compared to prior art, the present invention, by a kind of hydrophilic segment and reactable hydrophilic copolymers containing organoalkoxysilane reactive functional groups segment of containing is provided, reaches simultaneously and promotes surface wettability and compatible effect.Specifically, when reactable hydrophilic copolymers of the present invention is added in silicone glue formula, the hydrophilic segment in multipolymer can promote the surface wettability of silicone glue material.On the other hand, because affinity between the silicone molecule containing organoalkoxysilane reactive functional groups segment and in filling a prescription in multipolymer is high, and can carry out chemical bonded refractory with the silicone molecule in formula via alkoxysilane-functional group, related hydrophilic segment and silicone glue main body in multipolymer are connected, thereby improve the compatibility of integral formula.Therefore, add the silicone glue formula of reactable hydrophilic copolymers of the present invention, can be by direct curing molding, and do not need to add extra compatible agent or other complicated loaded down with trivial details surface working treatment step, can make prepared eye article (for example contact lens) there is good optical characteristic and surface moist.Moreover, owing to thering is covalency bond between reactable hydrophilic copolymers of the present invention and silicone glue main body, do not have the doubt of release, thereby can improve wearer's security.
Reactable hydrophilic copolymers of the present invention is the unit that forms of hydrophilic monomer by unsaturated ethylene in fact and is made up of at random having as shown in the formula (I) or unit (II) of forming containing the unsaturated ethylene alkene monomer of alkoxysilane-functional group:
Wherein R
1, R
2and R
3can be identical or differently, be independently selected from H or C
1-3alkyl; R is C
1-3alkyl; X, Y and Z can be identical or different, are independently selected from R ' or OR ', but restricted condition is for wherein at least one is OR '; R ' is H or C
1-3alkyl.
Reactable hydrophilic copolymers of the present invention is had hydrophilic monomer that unsaturated ethylene is functional group and one or more unsaturated ethylene alkene monomer institute's copolymerization containing alkoxysilane-functional group and obtained by one or more.Copolyreaction is preferably carried out under the existence of initiator, the initiator that is suitable for preparing reactable hydrophilic copolymers of the present invention comprises, but be not limited to, azo based compound (for example, but be not limited to, two (isopropyl cyanide) (2, the 2 '-Azobis (isobutyronitrile) of 2,2 '-azo, AIBN), 2, 2 '-azo two (2, 4-methyl pentane nitrile) (2, 2 '-azobis (2, 4-dimethylpentanenitrile)), 2, two (the 2-methyl propionitrile) (2 of 2 '-azo, 2 '-azobis (2-methylpropanenitrile)), 2, two (the 2-methylbutyronitriles) (2 of 2 '-azo, 2 '-azobis (2-methylbutanenitrile))), superoxide (for example, but be not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, stearoyl, benzoyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, peroxy dicarbonate) and analogue and mixture.Preferably use azo based compound (for example: AIBN) as initiator.
Hydrophilic monomer unit in reactable hydrophilic copolymers of the present invention is to have derived from one or more hydrophilic monomer that unsaturated ethylene is functional group.In prior art, announcement all can be used as hydrophilic monomer material for the manufacture of any known hydrophilic monomer of silicone glue material, for example, and the U.S. the 5th, 219, No. 965 patents, the 5th, 364, No. 918 patents, the 5th, 525, No. 691 patents, the 6th, 367, No. 929 patents and the 7th, those disclosed herein in 052, No. 131 patent, it is all incorporated in full in the present invention as a reference.
According to an enforcement aspect of the present invention, be suitable for that of the present invention to have unsaturated ethylene be that the hydrophilic monomer of functional group comprises, but be not limited to, unsaturated ethylene is carboxylic acid, for example: methacrylic acid (methacrylic acid; And vinylformic acid (acrylic acid) MA); Hydrophilic carbon vinyl acetate, for example: vinyl-acetic ester (vinyl acetate); Acrylate, for example: ethylene glycol dimethacrylate (EGDMA), HEMA (2-hydroxyethyl methacrylate; HEMA), HEA (2-hydroxyethyl acrylate), glyceral methacrylate (glycerol methacrylate) and vinylformic acid 2-dimethylaminoethyl ester (2-dimethylaminoethyl acrylate); Vinylamide, for example, N-vinyl-N-methylacetamide (N-vinyl-N-methyl acetamide) and N-vinyl-methane amide (N-vinyl-formamide); Vinyl lactam, for example, NVP (N-vinyl pyrrolidone; And acryloyl morpholine (acryloylmorpholine) NVP); Acrylamide, for example, Methacrylamide (methacrylamide), N,N-DMAA (N, N-dimethylacrylamide; DMA), N, N-diethyl acrylamide (N, N-diethylacrylamide), 2-hydroxyethyl methacrylamide (2-hydroxyethyl methacrylamide) and NIPA (N-isopropylacrylamide); And composition thereof.
According to an enforcement aspect of the present invention, the unsaturated ethylene alkene monomer containing alkoxysilane-functional group that is suitable for preparing reactable hydrophilic copolymers of the present invention comprises, but be not limited to, vinyltrimethoxy silane (vinyltrimethoxysilane), vinyltriethoxysilane (vinyltriethoxysilane), diethoxy (methyl) vinyl silanes (diethoxy (methyl) vinylsilane), 3-(methacryloxypropyl) methyl dimethoxysilane (3-methacryloxypropyl-methyldimethoxysilane), 3-(methacryloxypropyl) methyldiethoxysilane (3-methacryloxypropyl-methyldiethoxysilane), 3-(methacryloxypropyl) Trimethoxy silane (3-methacryloxypropyl-trimethoxysilane), 3-(methacryloxypropyl) triethoxyl silane (3-methacryloxypropyl-triethoxysilane), vinyl three (isopropoxy) silane (vinyltri (isopropoxy) silane), vinyl tripropoxy silane (vinyltripropoxysilane) and composition thereof.
By unsaturated ethylene be the unit that forms of hydrophilic monomer and formula (I) or (II) equivalence ratio of monomeric unit in reactable hydrophilic copolymers of the present invention reflect the close hydrophobic segment ratio of whole reactable hydrophilic copolymers, particularly, in the time that molecular weight is higher, the degree of ratio relative effect eyeglass character is just larger.When ratio is too high, (formula (I) or (II) monomeric unit is very few) easily produces incompatible situation, just cannot bring into play effect of wettability if ratio is too low relatively (being that the unit that forms of hydrophilic monomer is very few by unsaturated ethylene).Therefore, in the time of synthetic reactable hydrophilic copolymers of the present invention, in gained multipolymer by unsaturated ethylene be the unit that forms of hydrophilic monomer and formula (I) or (II) equivalence ratio of monomeric unit be preferably 5/1 to 200/1, more preferably 10/1 to 150/1, most preferably be between 20/1 to 100/1.Gained reactable hydrophilic copolymers preferably has at least 50,000 molecular weight, more preferably has 80,000 to 1,300,000 molecular weight.
As previously mentioned, reactable hydrophilic copolymers provided by the present invention contains hydrophilic segment simultaneously and contains organoalkoxysilane reactive functional groups segment.In the time being added in the monomer mixture that is used to form silicone glue, by the hydrophilic segment of described multipolymer, to promote outside silicone glue material surface wettability, further utilize described multipolymer containing organoalkoxysilane reactive functional groups segment, under the existence of initiator, with the monomer reaction bond of silicone glue, and then promote compatible.Therefore in silicone glue monomer mixture, add reactable hydrophilic copolymers provided by the present invention, can be in the situation that not adding extra compatible agent, make there is good light permeability, the silicone glue material of oxygen-permeable and wettability.
Accordingly, the present invention also provides a kind of silicone glue composition, and it comprises:
(a) be used to form the monomer mixture of silicone glue, described mixture comprises at least one silicone monomer containing alkoxysilane-functional group; And
(b) according to reactable hydrophilic copolymers of the present invention;
Wherein the usage quantity of reactable hydrophilic copolymers is 100 weight part meters for the monomer mixture gross weight that forms silicone glue, is preferably 1 to 20 weight part, more preferably 3 to 15 weight parts.
In herein, polymerisable low-molecular weight compound (conventionally having the number-average molecular weight lower than 700) contained in term " monomer ", and in polymerisable to high-molecular weight compounds or polymkeric substance, sometimes also referred to as macromonomer (conventionally thering is the number-average molecular weight that is greater than 700).Therefore " silicone monomer " and " hydrophilic monomer " word that, should understand herein comprise monomer, macromonomer and prepolymer.Prepolymer is partially polymerized monomer or the further monomer of polymerization.
In herein, it is the silicone (OSi-key) that comprises at least 5 % by weight that term " polysiloxane (polysiloxane) or silicone (silicone) " means material, be preferably 10 to 100 % by weight silicone, the material of the organic polymer of 30 to 90 % by weight silicone more preferably.The hydration of glue, crosslinking polymerization system is containing the water of equilibrium state.Conventionally the water-content of glue is greater than 5 % by weight, and more generally between 10 to 80 % by weight.Prepared by the monomer mixture that silicone glue (, containing silicone glue) normally contains at least one siliceous one monomers and at least one hydrophilic monomer by polymerization.
The suitable siliceous one monomers that can be used to form silicon hydrogel is all known in this field, for example, but be not limited to, the U.S. the 4th, 136, No. 250 patents, the 4th, 153, No. 641 patents, the 4th, 740, No. 533 patents, the 4th, 954, No. 587 patents, the 5th, 010, No. 141 patents, the 5th, 034, No. 461 patents, the 5th, 070, No. 215 patents, the 5th, 079, No. 319 patents, the 5th, 115, No. 056 patent, the 5th, 260, No. 000 patent, the 5th, 310, No. 779 patents, the 5th, 336, No. 797 patents, the 5th, 358, No. 995 patents, the 5th, 387, No. 632 patents, the 5th, 451, No. 617 patents, the 5th, 486, No. 579 patents and WO 96/31792, it is all incorporated herein as a reference in full.
According to an enforcement aspect of the present invention, the silicone monomer that is suitable for silicone glue composition of the present invention comprises, but be not limited to, methacrylic acid three (trimethylsiloxy) silyl propyl diester (tris (trimethylsiloxy) silylpropyl methacrylate), two (trimethylsiloxy) methyl-silicane base propyl diesters (bis (trimethylsiloxy) methylsilylpropyl methacrylate) of methacrylic acid, methacrylic acid pentamethyl disiloxane propyl diester (pentamethyldisiloxanepropyl methacrylate), methacrylic acid three (trimethylsiloxy) silyl propoxy-ethyl ester (tris (trimethylsiloxy) silylpropyloxyethyl methacrylate), methylacrylic acid three (polydimethyl siloxy-) silyl propyl diester (tris (polydimethylsiloxy) silylpropylmethacrylate), (trimethylsiloxy)-3-methacryloxypropyl silane ((trimethylsiloxy)-3-methacryloxypropylsilane, TRIS), unsaturated ethylene is organo-siloxane prepolymer, for example: the oligomer of acrylic acid series siloxanes polyalkylene oxide multipolymer (acrylated siloxane polyalkyleneoxide copolymer) kenel (for example, but be not limited to CoatOsil 3509) and composition thereof.
For thereby the polyreaction that makes reactable hydrophilic copolymers of the present invention be participated in silicone glue promotes compatiblely, be used to form in the monomer mixture of silicone glue and must comprise at least one silicone monomer containing alkoxysilane-functional group.The suitable silicone monomer containing alkoxysilane-functional group includes, but not limited to methacrylic acid 3-(trimethoxysilyl) propyl diester (3-(trimethoxysilyl) propyl methacrylate; TPM), methacrylic acid 3-(triethoxysilyl) propyl diester (3-(triethoxysilyl) propyl methacrylate), methacrylic acid 3-(diethoxymethyl silyl) propyl diester (3-diethoxymethylsilyl)-propyl methacrylate), vinyltrimethoxy silane (vinyltrimethoxysilane), vinyltriethoxysilane (vinyltriethoxysilane), diethoxy (methyl) vinyl silanes (diethoxy (methyl) vinylsilane), 3-(methacryloxypropyl) methyl dimethoxysilane (3-methacryloxypropyl-methyldimethoxysilane), 3-(methacryloxypropyl) methyldiethoxysilane (3-methacryloxypropyl-methyldiethoxysilane), 3-(methacryloxypropyl) Trimethoxy silane (3-methacryloxypropyl-trimethoxysilane), 3-(methacryloxypropyl) triethoxyl silane (3-methacryloxypropyl-triethoxysilane), vinyl three (isopropoxy) silane (vinyltri (isopropoxy) silane), vinyl tripropoxy silane (vinyltripropoxysilane) and composition thereof.
According to the present invention, the usage quantity of silicone monomer is 100 weight part meters for the monomer mixture gross weight that forms silicone glue, is preferably 10 to 70 weight parts, more preferably 20 to 60 weight parts.In addition, take silicone monomer gross weight contained in monomer mixture as 100 weight parts, more than the usage quantity of the silicone monomer of wherein rolling into a ball containing alkoxysilane-functional is preferably at least 5 weight parts, more preferably more than 10 weight parts.According to an enforcement aspect of the present invention, the silicone monomer in monomer mixture also can all be the silicone monomer containing alkoxysilane-functional group.
Comprise in prior art that for being used in suitable hydrophilic monomer in silicone glue composition of the present invention announcement is for the manufacture of any known hydrophilic monomer of silicone glue material, for example, the U.S. the 5th, 219, No. 965 patents, the 5th, 364, No. 918 patents the 5th, 525, No. 691 patents, the 6th, 367, No. 929 patents and the 7th, those disclosed herein in 052, No. 131 patent, it is all incorporated in full in the present invention as a reference.Applicable hydrophilic monomer comprises, but is not limited to, and unsaturated ethylene is carboxylic acid, for example: methacrylic acid (methacrylic acid; And vinylformic acid (acrylic acid) MA); Hydrophilic carbon vinyl acetate, for example: vinyl-acetic ester (vinyl acetate); Acrylate, for example: ethylene glycol dimethacrylate (EGDMA), HEMA (2-hydroxyethyl methacrylate; HEMA), HEA (2-hydroxyethyl acrylate), glyceral methacrylate (glycerol methacrylate) and vinylformic acid 2-dimethylaminoethyl ester (2-dimethylaminoethyl acrylate); Vinylamide, for example, N-vinyl-N-methylacetamide (N-vinyl-N-methyl acetamide) and N-vinyl-methane amide (N-vinyl-formamide); Vinyl lactam, for example, NVP (N-vinyl pyrrolidone; And acryloyl morpholine (acryloylmorpholine) NVP); Acrylamide, for example, Methacrylamide (methacrylamide), N,N-DMAA (N, N-dimethylacrylamide; DMA), N, N-diethyl acrylamide (N, N-diethylacrylamide), 2-hydroxyethyl methacrylamide (2-hydroxyethylmethacrylamide) and NIPA (N-isopropylacrylamide); And composition thereof.The usage quantity of hydrophilic monomer is 100 weight part meters for the monomer mixture gross weight that forms silicone glue, is preferably 30 to 90 weight parts, more preferably 40 to 80 weight parts.
In the time of copolymerization, can there is sclerosis and casting forming by the method such as UV polymerization, use free radical thermal initiator and heat or its combination in silicone glue composition of the present invention.Representative free radical thermal polymerization is organo-peroxide, for example acetyl peroxide, lauroyl peroxide, decanoyl peroxide, stearoyl, benzoyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, peroxy dicarbonate and such as
256,225 (chemical companies of Atofina (Atofina Chemical), philadelphia, pa (Philadelphia, PA) commercially available thermal initiator and analogue thereof), described initiator uses with the concentration that accounts for total monomer mixture approximately 0.01 to 2 % by weight.Representative UV initiator is initiator known in this field, such as, but be not limited to, benzil methyl ether, benzil ether,
1173,1164,2273,1116,2959,3331,
651 and 184 (Ciba (Ciba Specialty Chemicals), New York A Zili (Ardsley, New York)).
As those skilled in the art understand, except above-mentioned polymerization starter, in silicone glue composition of the present invention, optionally also can comprise other component, for example, extra tinting material, UV absorption agent and extra processing aid etc., such as those known persons in contact lenses technology.
There is the effects such as high oxygen permeability, low sticking property of lipid, excellent surface wettability and high light transmittance by adding the silicon hydrogel that reactable hydrophilic copolymers of the present invention produces, therefore be suitable as very much eye article, particularly contact lens or intraocular lens (IOL).
Can be by be disclosed in the U.S. the 3rd such as those, 408, No. 429 patents and the 3rd, 496, rotated mold filing moulding (spin cast molding) technique in No. 254 patents, such as being disclosed in the U.S. the 5th, 271, fixing cast molding (cast molding) technique in No. 875 patents and such as being disclosed in the U.S. the 4th, 084, No. 459 patents and the 4th, other prior art method of compression moulding in 197, No. 266 patents, makes to form contact lenses by silicone glue composition gained multipolymer of the present invention.The polymerization of monomer mixture can be carried out in the rotating mold corresponding to wanted contact lenses shape or fixed mould.If desired, the contact lenses so obtaining can further stand machine finish.Polymerization also can carry out obtaining being the ocular lens material of button shaped, dish type or rod in suitable mould or container, its then can treated (for example, via lathe or laser cutting or polishing) to obtain having the contact lenses of wanted shape.
Following examples are for the invention will be further described, but not in order to limit the scope of the invention.The modification that any those skilled in the art can reach easily and change are included in the scope of this case specification sheets disclosure and appended claims.
Embodiment
synthetic chemistry medicine
1. vinyltrimethoxy silane (vinyl trimethoxysilane (be called for short VTMOS)): purchased from Chongyue Dentsu Co., Ltd; Product designation is KBM1003.
2.N-vinyl pyrrolidone (be called for short NVP): purchased from ALDRICH; Product designation is CAS:88-12-0.
3. acrylic acid series siloxanes polyalkylene oxide multipolymer (acrylated siloxane polyalkyleneoxidecopolymer): purchased from GE organosilicon (GE silicones); Product are by name
3509.
4. (trimethylsiloxy)-3-methacryloxypropyl silane ((trimethylsiloxy)-3-methacryloxypropylsilane; TRIS): purchased from lid Le Site (Gelest); Product designation is CAS:17096-07-0.
5. HEMA (be called for short HEMA): purchased from ACROS; Product designation is CAS:868-77-9.
6. methacrylic acid 3-(trimethoxysilyl) propyl diester (3-(trimethoxysilyl) propylmethacrylate (be called for short TPM)): purchased from aldrich (ALDRICH); Product designation is CAS:2530-85-0.
7.2,2 '-azo two (isopropyl cyanides) (2,2 '-azobis-isobutyronitrile (being called for short AIBN)): purchased from clear and chemical; Product designation is CAS:78-67-1.
8. methacrylic acid (methacrylic acid (MA)): purchased from two key chemical industry; Product designation is 79-41-4.
9.DAROCUR 1173 (2-hydroxy-2-methyl-1-phenyl-1-acetone (2-hydroxy-2-methyl-1-phenyl-1-propanone)): purchased from (Ciba (CibaSpecialty Chemicals); Product designation is CAS:7473-98-5.
10. ethylene glycol dimethacrylate (EGDMA): purchased from A Faaisha (Alfa Aesar); Product designation is CAS:97-90-5.
the preparation of reactable hydrophilic copolymers
Embodiment 1:
Get 30g NVP and be placed in reaction flask, add 0.4g vinyltrimethoxy silane (VTMOS) and 50mL methyl alcohol.Temperature is controlled in 60 ℃, back flow reaction 1 hour under condition of nitrogen gas.Then be warming up to 90 ℃, add 30mgAIBN, back flow reaction, after 2 hours, is got back to room temperature termination reaction.Add 100mL methyl alcohol dilution, and be placed in 60 ℃ of vacuum drying ovens solvent is drained, obtain transparent products.Product is solidified so that liquid nitrogen is cooling, and ground with pulverizer, obtain transparent powdery reactable hydrophilic copolymers, recording its molecular-weight average through gel permeation chromatography (Gel-permeationchromatography) is 83422g/mol.
Embodiment 2:
With the when reaction conditions of charging of embodiment 1, just AIBN addition changes to 10mg and return time extends to 4.5 hours, obtain transparent powdery reactable hydrophilic copolymers, recording its molecular-weight average through gel permeation chromatography (Gel-permeationchromatography) is 249063g/mol.
Embodiment 3:
With the when reaction conditions of charging of embodiment 1, just AIBN addition changes to 5mg and return time extends to 15 hours, obtain transparent powdery reactable hydrophilic copolymers, recording its molecular-weight average through gel permeation chromatography (Gel-permeationchromatography) is 499557g/mol.
Embodiment 4:
With the when reaction conditions of charging of embodiment 1, just AIBN addition changes to 2mg and return time extends to 24 hours, obtain transparent powdery reactable hydrophilic copolymers, recording its molecular-weight average through gel permeation chromatography (Gel-permeationchromatography) is 1244112g/mol.
Embodiment 5:
With the when reaction conditions of charging of embodiment 1, just vinyltrimethoxy silane addition changes to 4g, obtain transparent powdery reactable hydrophilic copolymers, recording its molecular-weight average through gel permeation chromatography (Gel-permeation chromatography) is 93356g/mol.
Embodiment 6:
With the when reaction conditions of charging of embodiment 1, just vinyltrimethoxy silane addition changes to 2g, obtain transparent powdery reactable hydrophilic copolymers, recording its molecular-weight average through gel permeation chromatography (Gel-permeation chromatography) is 87802g/mol.
the preparation of silicone glue material
Embodiment 7:
Configuration silicone glue compositing formula, include following monomer: TPM, TRIS, CoatOsil, NVP, HEMA and MA, and its part by weight is respectively 7.3/32.83/14.62/31.66/12.25/1.34, finally add 30% Virahol of total monomer weight as dispersion agent.After mixing, do uniform stirring with magnetite again, stir simultaneously and slowly add the prepared reactable hydrophilic copolymers of embodiment 1 (part by weight be total monomer heavy 6.5%), it is dissolved completely and dispersed.Afterwards this solution is kept to whipped state and is warming up to 60 ℃ maintaining 2-4 hour.After this formula solution is completely cooling, then add light trigger D1173 (0.2-1%).The clamping plate that the PP of this solution injection known thickness is configured to, and carry out subsequently Photoinitiated reactions, illumination condition is controlled at 2-5mw/cm
2continue 30 minutes to 2 hours.Reaction finishes film to remove in clamping plate, soaks to put at 70/30 (ethanol/water) Peng Run to extract about 1-2 hour, then in physiological saline, replys 1-2 hour, obtains a slice flatted membrane.
Embodiment 8:
With the formula main body ratio of embodiment 7, but change into add embodiment 2 prepared reactable hydrophilic copolymers (part by weight be all total monomer heavy 6.5%), after in being dissolved in whole formula completely, keep whipped state and be warming up to 60 ℃ maintaining 2-4 hour equally.And with identical film forming demoulding program, obtain a slice flatted membrane.
Embodiment 9:
With the formula main body ratio of embodiment 7, but change into add embodiment 3 prepared reactable hydrophilic copolymers (part by weight be all total monomer heavy 6.5%), after in being dissolved in whole formula completely, keep whipped state and be warming up to 60 ℃ maintaining 2-4 hour equally.And with identical film forming demoulding program, obtain a slice flatted membrane.
Embodiment 10:
With the formula main body ratio of embodiment 7, but change into add embodiment 4 prepared reactable hydrophilic copolymers (part by weight be all total monomer heavy 6.5%), after in being dissolved in whole formula completely, keep whipped state and be warming up to 60 ℃ maintaining 2-4 hour equally.And with identical film forming demoulding program, obtain a slice flatted membrane.
Embodiment 11:
With the formula main body ratio of embodiment 7, but change into add embodiment 5 prepared reactable hydrophilic copolymers (part by weight be all total monomer heavy 6.5%), after in being dissolved in whole formula completely, keep whipped state and be warming up to 60 ℃ maintaining 2-4 hour equally.And with identical film forming demoulding program, obtain a slice flatted membrane.
Embodiment 12:
With the formula main body ratio of embodiment 7, but change into add embodiment 6 prepared reactable hydrophilic copolymers (part by weight be all total monomer heavy 6.5%), after in being dissolved in whole formula completely, keep whipped state and be warming up to 60 ℃ maintaining 2-4 hour equally.And with identical film forming demoulding program, obtain a slice flatted membrane.
Embodiment 13:
Get the prepared reactable hydrophilic copolymers of embodiment 1, itself and TPM, HEMA, EGDMA and hexanol are uniformly mixed into homogeneous phase solution (the first solution), and wherein the weight ratio of TPM/HEMA/EGDMA/ hexanol/reactable hydrophilic copolymers is 29.9/70/0.1/3/5.This first solution is placed at 60 ℃ again and is mixed 1 hour, and this measure can make the prepared reactable hydrophilic copolymers of TPM and embodiment 1 carry out complete hydrolysis to react.The final formula solution that waits is down to room temperature, then adds initiator D1173, the part by weight of its interpolation account for all monomers heavy 0.5 to 1%, become the second solution.The clamping plate that the PP of the second solution injection known thickness is configured to, and carry out subsequently Photoinitiated reactions, illumination condition is controlled at 2-5mw/cm
2continue 30 minutes to 2 hours.Reaction finishes film to remove in clamping plate, soaks to put at 70/30 (ethanol/water) Peng Run to extract about 1-2 hour, then in physiological saline, replys 1-2 hour, obtains a slice flatted membrane.
Embodiment 14:
With the formula main body ratio of embodiment 7, after mixing, do uniform stirring with magnetite again, stir simultaneously and slowly add the prepared reactable hydrophilic copolymers of embodiment 4 (add part by weight be silicone glue monomer mixture gross weight 10%), making it completely dissolve and be uniformly dispersed.Afterwards this solution is kept to whipped state and is warming up to 60 ℃ maintaining 2-4 hour.After this formula solution is completely cooling, then add light trigger D1173 (0.7 % by weight).Again through photocuring reaction and the demoulding aftertreatment identical with aforementioned multinomial embodiment, obtain a slice flatted membrane afterwards.
Comparative example 1:
With the formula main body ratio of embodiment 7, after mixing, do uniform stirring with magnetite again, do not add reaction hydrophilic copolymers of the present invention, directly add the light trigger D1173 of 0.7 % by weight.The clamping plate that the PP of described formula solution injection known thickness is configured to, and carry out subsequently Photoinitiated reactions, illumination condition is controlled at 2-5mw/cm
2continue 30 minutes to 2 hours.Reaction finishes film to remove in clamping plate, soaks to put at 70/30 (ethanol/water) Peng Run to extract about 1-2 hour, then in physiological saline, replys 1-2 hour, obtains a slice flatted membrane.
Comparative example 2:
With the formula main body ratio of embodiment 7, after mixing, do uniform stirring with magnetite again, stir simultaneously and slowly add the PVP (molecular weight approximately 1,300,000) (add part by weight be silicone glue monomer mixture gross weight 10%) of K90.Treat that PVP completely dissolves and is uniformly dispersed, then add the light trigger D1173 of 0.7 % by weight.Again through photocuring reaction and the demoulding aftertreatment identical with aforementioned multinomial embodiment, obtain a slice flatted membrane afterwards.
the EDX test of different feeds ratio gained wetting agent
The reactable hydrophilic copolymers of embodiment 1, embodiment 5, embodiment 6 synthesizeds is carried out to x-ray fluorescence analysis (EDX) test, and assessment is according to charge ratio difference, and wherein contained elements Si/O is than also thereupon different.
Table 1
| Embodiment 1 | Embodiment 5 | Embodiment 6 | |
| NVP charging grams | 30g | 30g | 30g |
| VTMOS charging grams | 0.4g | 4g | 2g |
| NVP/VTMOS equivalence ratio (m/n ratio) | 100/1 | 10/1 | 20/1 |
| Product element O/Si theoretical value | 103/1 | 13/1 | 23/1 |
| EDX records Si content (atom %) | 0.45 | 1.7 | 0.7 |
| EDX records O content (atom %) | 13.91 | 17.24 | 16.72 |
Take embodiment 6 as example, shown in the following diagram 1 of its reaction formula, NVP and VTMOS charge ratio are 20: 1, products therefrom wetting agent (the right-hand structural formula of diagram 1) its m: n=20 in theory: 1, therefore the element O/Si theoretical value of product should be 23: 1.Therefore the different wetting agents that obtain different m/n from VTMOS charge ratio according to NVP.
Diagram 1
the chemical bonded refractory test of reactable hydrophilic copolymers
Get 4g TPM and the hydrophilic polymerized powder of the prepared reactable of 1g embodiment 1 is placed in reaction flask, add 20mL ethanol, temperature was controlled to 60 ℃ of reactions after 6 hours, utilize concentrating under reduced pressure machine that ethanol is removed.Resistates extracts three times with normal hexane and water, collects water layer, removes moisture with freeze drier freeze-drying, obtains white plates, with D
2o dissolves, and carries out NMR evaluation.
Be dissolved in normal hexane because TPM is water insoluble, therefore after extraction, unreacted TPM monomer can be placed in to organic layer and remove, and in water layer, will obtain two kinds of compounds, i.e. unreacted reactable hydrophilic copolymers and reactable hydrophilic copolymers and the reacted product of TPM.If therefore there is the signal of two keys to occur in the NMR of water layer collection of illustrative plates, provable reactable hydrophilic copolymers really with TPM generation chemical bonded refractory.
From the NMR result of Fig. 1, the spectrum of simple reactable hydrophilic copolymers is between 5～6ppm and the signal of unparalleled key, and the water layer spectrum that product has extracted, can observe and between 5～6ppm, have two key signals to produce (being the part of arrow indication), therefore generation chemical bonded refractory really between provable reactable hydrophilic copolymers and silicone monomer (TPM) containing alkoxysilane-functional group.
transmittance test
1. using DU 800UV/ visible spectrophotometer (Spectrophotometer) as the instrument that detects transmittance, first, first set the pattern of " sweeping all-wave long ", and limit wavelength region in 400～700nm interval.
2. before detecting sample penetration rate, inject quartz cell with deionized water, be placed in sample detection groove, make background deduction by " blank "!
3. sample is cut into the size that meets quartz cell transparent surface, tries one's best smooth in cell wall, the deionized water that reinjects, this step will be avoided Bubble formation and residual.Be placed in sample detection groove, start to detect the penetration coefficient of visible wavelength by " SCAN ".
4. data processing: for more on the same group between the transmittance of film, the preliminary index using 600nm as sample room comparison.
contact angle test
1. carry out the moistened surface character of test material with DSA10.First confirm to begin to start to detect after image focal length arrives optimum value.
2. material is cut into suitable film size, is placed on the microscope carrier that contact angle measures, tiling and by its surface-moisture wipe dry after.With syringe needle, drop is dropped to sample surfaces.
3. capture after image the contact angle numerical value of software analysis liquid/fixed interface.
Following table 2 is surface contact angle and the transmittance take off data of embodiment 7 to 14 and comparative example 1 and 2 obtained silicone glue films.
Table 2
The formula main body of comparative example 1 is identical with embodiment 7 to 12 and 14, but embodiment 7 to 12 and 14 has added the reactable hydrophilic copolymers of embodiment 1 to 6 synthesized compared to comparative example more than 1.From the contact angle data of table 2, its wettability of the surface of silicone glue material of adding reactable hydrophilic copolymers of the present invention obviously improves, and the interpolation of described reactable hydrophilic copolymers does not almost affect for the light transmission of silicone glue material, this has proved to have excellent compatibility between itself and silicone glue material.
And the formula main body of comparative example 2 is identical with embodiment 14.Both deviations are that the wetting agent that comparative example 2 adds is that molecular weight is up to 1,300, the PVP molecule of 000g/mol, its do not have can react between main body with formula containing organoalkoxysilane reactive functional groups, the wetting agent that embodiment 14 adds is the reactable hydrophilic copolymers of embodiment 4 synthesizeds, and its molecular-weight average is 1244112g/mol.Transmittance from table 2 detects data, between reactable hydrophilic copolymers of the present invention and formula main body, obviously has comparatively superior compatibility.In addition, also can be found out by contact angle data, in the time that molecular weight ranges is close, reactable hydrophilic copolymers of the present invention also has the wetting effect superior compared with PVP.This result it is believed that inferring is to have the effect that chemical bond presents between reactable hydrophilic copolymers of the present invention and formula main body.
Should easily to understand various improvement of the present invention be feasible and be that those skilled in the art easily associates and expects.
Claims (14)
1. a silicone glue composition, it comprises:
(a) be used to form the monomer mixture of silicone glue, the silicone monomer that described mixture comprises hydrophilic monomer, contains the silicone monomer of alkoxysilane-functional group and do not roll into a ball containing alkoxysilane-functional, it is the group that carboxylic acid, hydrophilic carbon vinyl acetate, acrylate, vinylamide, vinyl lactam, acrylamide and composition thereof form that wherein said hydrophilic monomer selects free unsaturated ethylene; And
(b) a kind of reactable hydrophilic copolymers, it is the unit that forms of hydrophilic monomer by unsaturated ethylene in fact and is made up of at random having as shown in the formula (I) or unit (II) of forming containing the unsaturated ethylene alkene monomer of alkoxysilane-functional group, and wherein said reactable hydrophilic copolymers has 80,000 to 1,300,000 molecular weight:
Wherein R
1, R
2and R
3can be identical or differently, be independently selected from H or C
1-3alkyl; R is C
1-3alkyl; X, Y and Z can be identical or different, are independently selected from R ' or OR ', but restricted condition be wherein at least one for OR ' and wherein the R ' at least one OR ' be not H; R ' is H or C
1-3alkyl; And described by unsaturated ethylene be the unit that forms of hydrophilic monomer and formula (I) or (II) equivalence ratio of monomeric unit fall within 5/1 to 200/1 scope;
Wherein, the usage quantity of described reactable hydrophilic copolymers is 100 weight part meters for the monomer mixture gross weight that forms silicone glue, is 1 to 20 weight part;
The wherein said monomer mixture that is used to form silicone glue is take its gross weight as 100 weight parts, the silicone monomer that contains 10 to 70 weight parts, and wherein the silicone monomer of at least 5 weight parts contains alkoxysilane-functional group; And
The wherein said monomer mixture that is used to form silicone glue comprises the not silicone monomer containing alkoxysilane-functional group, it selects free methacrylic acid three (trimethylsiloxy) silyl propyl diester, two (trimethylsiloxy) methyl-silicane base propyl diesters of methacrylic acid, methacrylic acid pentamethyl disiloxane propyl diester, methacrylic acid three (polydimethyl siloxy-) silyl propyl diester, (trimethylsiloxy)-3-methacryloxypropyl silane, unsaturated ethylene is the group that organo-siloxane prepolymer and composition thereof forms.
2. silicone glue composition as claimed in claim 1, wherein said reactable hydrophilic copolymers is to have the institute's copolymerization and obtaining under the existence of initiator of hydrophilic monomer that unsaturated ethylene is functional group and one or more unsaturated ethylene alkene monomer containing alkoxysilane-functional group by one or more, wherein said initiator choosing free 2, 2 '-azo two (isopropyl cyanide), 2, 2 '-azo two (2, 4-methyl pentane nitrile), 2, 2 '-azo two (2-methyl propionitrile), 2, 2 '-azo two (2-methylbutyronitrile), benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, stearoyl, benzoyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, the group that peroxy dicarbonate and mixture form.
3. silicone glue composition as claimed in claim 1, wherein said unsaturated ethylene is that to select free unsaturated ethylene be the group that carboxylic acid, hydrophilic carbon vinyl acetate, acrylate, vinylamide, vinyl lactam, acrylamide and composition thereof form to hydrophilic monomer.
4. silicone glue composition as claimed in claim 1, wherein said unsaturated ethylene is that hydrophilic monomer selects free methacrylic acid, vinylformic acid, vinyl-acetic ester, ethylene glycol dimethacrylate, HEMA, HEA, glyceral methacrylate, vinylformic acid 2-dimethylaminoethyl ester, N-vinyl-N-methylacetamide, N-vinyl-methane amide, NVP, acryloyl morpholine, Methacrylamide, N, N-DMAA, N, N-diethyl acrylamide, the group that 2-hydroxyethyl methacrylamide and NIPA and composition thereof form.
5. silicone glue composition as claimed in claim 1, the wherein said unsaturated ethylene alkene monomer containing alkoxysilane-functional group selects free vinyltrimethoxy silane, vinyltriethoxysilane, diethoxy (methyl) vinyl silanes, 3-(methacryloxypropyl) methyl dimethoxysilane, 3-(methacryloxypropyl) methyldiethoxysilane, 3-(methacryloxypropyl) Trimethoxy silane, 3-(methacryloxypropyl) triethoxyl silane, vinyl three (isopropoxy) silane, the group that vinyl tripropoxy silane and composition thereof forms.
6. silicone glue composition as claimed in claim 1, wherein said by unsaturated ethylene be the unit that forms of hydrophilic monomer and formula (I) or (II) equivalence ratio of monomeric unit fall within 10/1 to 150/1 scope.
7. silicone glue composition as claimed in claim 6, wherein said by unsaturated ethylene be the unit that forms of hydrophilic monomer and formula (I) or (II) equivalence ratio of monomeric unit fall within 20/1 to 100/1 scope.
8. the silicone glue composition as described in arbitrary claim in claim 1-7, the usage quantity of wherein said reactable hydrophilic copolymers is 100 weight part meters for the monomer mixture gross weight that forms silicone glue, is 3 to 15 weight parts.
9. the silicone glue composition as described in arbitrary claim in claim 1-7, the wherein said monomer mixture that is used to form silicone glue is take its gross weight as 100 weight parts, the silicone monomer that contains 20 to 60 weight parts, and wherein the silicone monomer of at least 10 weight parts contains alkoxysilane-functional group.
10. the silicone glue composition as described in arbitrary claim in claim 1 to 7, the wherein said silicone monomer containing alkoxysilane-functional group selects free methacrylic acid 3-(trimethoxysilyl) propyl diester, methacrylic acid 3-(triethoxysilyl) propyl diester, methacrylic acid 3-(diethoxymethyl silyl) propyl diester, vinyltrimethoxy silane, vinyltriethoxysilane, diethoxy (methyl) vinyl silanes, 3-(methacryloxypropyl) methyl dimethoxysilane, vinyl three (isopropoxy) silane, the group that vinyl tripropoxy silane and composition thereof forms.
11. silicone glue compositions as described in arbitrary claim in claim 1 to 7, the wherein said monomer mixture that is used to form silicone glue comprises and selects free methacrylic acid, vinylformic acid, vinyl-acetic ester, ethylene glycol dimethacrylate, HEMA, HEA, glyceral methacrylate, vinylformic acid 2-dimethylaminoethyl ester, N-vinyl-N-methylacetamide, N-vinyl-methane amide, NVP, acryloyl morpholine, Methacrylamide, N, N-DMAA, N, N-diethyl acrylamide, the hydrophilic monomer of the group that 2-hydroxyethyl methacrylamide and NIPA and composition thereof form.
12. silicone glue compositions as claimed in claim 11, the usage quantity of wherein said hydrophilic monomer is 100 weight part meters for the monomer mixture gross weight that forms silicone glue, is 30 to 90 weight parts.
13. silicone glue compositions as claimed in claim 12, the usage quantity of wherein said hydrophilic monomer is 100 weight part meters for the monomer mixture gross weight that forms silicone glue, is 40 to 80 weight parts.
14. 1 kinds by the prepared eye article of silicone glue composition as described in arbitrary claim in claim 1 to 13, and it is contact lens or intraocular lens.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010000220.6A CN102115515B (en) | 2010-01-05 | 2010-01-05 | Copolymer capable of enhancing wettability of silicone hydrogel, silicone hydrogel composition containing same and ophthalmic item employing silicone hydrogel composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010000220.6A CN102115515B (en) | 2010-01-05 | 2010-01-05 | Copolymer capable of enhancing wettability of silicone hydrogel, silicone hydrogel composition containing same and ophthalmic item employing silicone hydrogel composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102115515A CN102115515A (en) | 2011-07-06 |
| CN102115515B true CN102115515B (en) | 2014-06-18 |
Family
ID=44214453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010000220.6A Expired - Fee Related CN102115515B (en) | 2010-01-05 | 2010-01-05 | Copolymer capable of enhancing wettability of silicone hydrogel, silicone hydrogel composition containing same and ophthalmic item employing silicone hydrogel composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102115515B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104877068B (en) * | 2015-05-21 | 2017-08-25 | 爱生华(苏州)光学有限公司 | A kind of preparation method of practical silicone hydrogel contact mirror |
| TWI609701B (en) | 2016-01-05 | 2018-01-01 | 國立交通大學 | Compound prescription colloidal eyedrop gel and methods of making the same |
| CN108192551A (en) * | 2017-12-30 | 2018-06-22 | 广州市白云化工实业有限公司 | Transparent, high adhesiveness silane-modified adhesive and preparation method thereof |
| CN113136012A (en) * | 2020-01-20 | 2021-07-20 | 爱博诺德(北京)医疗科技股份有限公司 | Medical device and manufacturing method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074450A (en) * | 1991-11-05 | 1993-07-21 | 博士伦有限公司 | Wettable silicone hydrogel compositions and method for making thereof |
| EP0640221A1 (en) * | 1992-05-15 | 1995-03-01 | Bausch & Lomb | Surface wettable silicone hydrogels. |
| CN1441814A (en) * | 2000-03-22 | 2003-09-10 | 庄臣及庄臣视力保护公司 | Hydrogel with internal wetting agent |
| CN1681862A (en) * | 2002-09-18 | 2005-10-12 | 博士伦公司 | Elastomeric, expandable hydrogel compositions |
| CN1842559A (en) * | 2003-06-30 | 2006-10-04 | 庄臣及庄臣视力保护公司 | Silicone hydrogels having consistent concentrations of multi-functional polysiloxanes |
| EP2077292A1 (en) * | 2007-12-28 | 2009-07-08 | Far Eastern Texile Ltd. | Polysiloxane-based prepolymer and hydrogel |
| CN101490121A (en) * | 2006-08-09 | 2009-07-22 | 瓦克化学有限公司 | Crosslinkable reactive silicone organic copolymers and method for the production and use thereof |
| WO2009096531A1 (en) * | 2008-02-01 | 2009-08-06 | Fujifilm Corporation | Hydrophilic members |
| JP2009179797A (en) * | 2009-01-26 | 2009-08-13 | Shiseido Co Ltd | Composition comprising reactive silyl group-containing copolymer |
| CN101535353A (en) * | 2005-08-09 | 2009-09-16 | 库柏维景国际控股公司 | Compositions and methods for producing silicone hydrogel contact lenses |
-
2010
- 2010-01-05 CN CN201010000220.6A patent/CN102115515B/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074450A (en) * | 1991-11-05 | 1993-07-21 | 博士伦有限公司 | Wettable silicone hydrogel compositions and method for making thereof |
| EP0640221A1 (en) * | 1992-05-15 | 1995-03-01 | Bausch & Lomb | Surface wettable silicone hydrogels. |
| CN1441814A (en) * | 2000-03-22 | 2003-09-10 | 庄臣及庄臣视力保护公司 | Hydrogel with internal wetting agent |
| CN1681862A (en) * | 2002-09-18 | 2005-10-12 | 博士伦公司 | Elastomeric, expandable hydrogel compositions |
| CN1842559A (en) * | 2003-06-30 | 2006-10-04 | 庄臣及庄臣视力保护公司 | Silicone hydrogels having consistent concentrations of multi-functional polysiloxanes |
| CN101535353A (en) * | 2005-08-09 | 2009-09-16 | 库柏维景国际控股公司 | Compositions and methods for producing silicone hydrogel contact lenses |
| CN101490121A (en) * | 2006-08-09 | 2009-07-22 | 瓦克化学有限公司 | Crosslinkable reactive silicone organic copolymers and method for the production and use thereof |
| EP2077292A1 (en) * | 2007-12-28 | 2009-07-08 | Far Eastern Texile Ltd. | Polysiloxane-based prepolymer and hydrogel |
| WO2009096531A1 (en) * | 2008-02-01 | 2009-08-06 | Fujifilm Corporation | Hydrophilic members |
| JP2009179797A (en) * | 2009-01-26 | 2009-08-13 | Shiseido Co Ltd | Composition comprising reactive silyl group-containing copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102115515A (en) | 2011-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI401263B (en) | Copolymer enhancing the wettability of silicone hydrogel, silicone hydrogel composition comprising the same and ocular article made therefrom | |
| KR100703583B1 (en) | A silicone hydrogel, a method for preparing the same and contact lenses comprising the same | |
| JP5568310B2 (en) | contact lens | |
| KR101084932B1 (en) | Polysiloxane-based prepolymer and hydrogel | |
| CA2518108C (en) | Diluents for forming clear, wettable silicone hydrogel articles | |
| CN105418858A (en) | Silicon hydrogel material having high oxygen permeability, corneal contact lens, and preparation method thereof | |
| US20070155851A1 (en) | Silicone containing polymers formed from non-reactive silicone containing prepolymers | |
| KR20020016922A (en) | Contact Lens Material | |
| TWI813663B (en) | Phosphocholine-containing polysiloxane monomer | |
| AU2004256111B2 (en) | Silicone hydrogels having consistent concentrations of multi-functional polysiloxanes | |
| TW201420678A (en) | Silicone hydrogel composition and silicone hydrogel contact lenses made of the composition | |
| WO2012064538A1 (en) | Silicone hydrogel reactive mixtures comprising borates | |
| CN102115515B (en) | Copolymer capable of enhancing wettability of silicone hydrogel, silicone hydrogel composition containing same and ophthalmic item employing silicone hydrogel composition | |
| CN102464744A (en) | Chlorinated polymers that enhance wettability of silicone hydrogels, silicone hydrogels comprising the same, and ophthalmic articles made therefrom | |
| CN102675561B (en) | silicone hydrogel with high water content | |
| TWI813875B (en) | Monomer composition for contact lens, polymer for contact lens and production method thereof, and contact lens and production method thereof | |
| JP5806282B2 (en) | Fluorine-containing ether monomer for contact lens production, contact lens material, and contact lens produced by this material | |
| KR101863823B1 (en) | Hydrogel contact lenses composition, including copolymerized hydrophilic terpolymers and silicones |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140618 Termination date: 20180105 |