CN1842559A - Silicone hydrogels having consistent concentrations of multi-functional polysiloxanes - Google Patents

Silicone hydrogels having consistent concentrations of multi-functional polysiloxanes Download PDF

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CN1842559A
CN1842559A CN 200480024550 CN200480024550A CN1842559A CN 1842559 A CN1842559 A CN 1842559A CN 200480024550 CN200480024550 CN 200480024550 CN 200480024550 A CN200480024550 A CN 200480024550A CN 1842559 A CN1842559 A CN 1842559A
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alkyl
group
methyl
hydroxyl
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G·A·希尔
J·C·赫顿
M·R·克拉克
C·L·凯森
F·F·莫洛克
S·马哈德文
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Johnson and Johnson Vision Care Inc
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Abstract

The present invention relates to a process comprising forming a monomer mixture comprising at least one monofunctional silicone containing component which comprises at least one difunctional byproduct and adding to said monomer mixture a normalizing amount of said at least one difunctional byproduct and curing said monomer mixture to form a biomedical device.

Description

The silicone hydrogel that contains the polyfunctional poly siloxanes of steady concentration
Related application
The right of priority of the provisional application that No. the 60/483rd, 847, the United States Patent (USP) sequence of present patent application requirement submission on June 30th, 2003.
Invention field
The present invention relates to contain the multifunctional component of steady concentration, more specifically for containing the silicone hydrogel of polyfunctional poly silicone components.The invention also discloses the method for the silicone hydrogel for preparing the multifunctional component that contains steady concentration.
Background of invention
Cornea does not have the level of obvious swelling to do many effort for the oxygen permeability that increases contact lens extremely can wear these lens for a long time.A kind of method that increases oxygen permeability is that silicone monomers is covered in the material that is used to form contact lens., these silicone monomers tend to form macromole, and this may bring many by products.
Have been found that the various monomers that contain polysiloxane as the raw materials of producing medical treatment device, described medical treatment device such as device for eyes and particularly have the soft-contact lens of the oxygen permeability of improvement.The monomer that one class is fit to comprises various three and two (trimethylsiloxy) silyl alkyl glycerine methacrylic esters (" SiAGMA ").During synthetic SiAGMA, also produce some diester acrylates impurity.This diester acrylates or free radical activity double functional group are used as linking agent between the component polymerization period of SiAGMA and other formation polymkeric substance.Regrettably, be difficult to the amount of the difunctionality by product of control formation.The difunctionality by product influences many character of lens, comprises the content and the elongation of modulus, equilibrium water.Therefore, the concentration that must control the difunctionality by product does not change to unacceptable degree with the mechanical properties of the medical treatment device guaranteeing to obtain.
Summary of the invention
The present invention relates to control the parameter and the character of contact lens by regulating the concentration that contains difunctionality polysiloxane by product that forms between synthesis phase at raw material in the monomer mixture.More particularly, the present invention relates to a kind of method, described method comprises the formation monomer mixture, described monomer mixture comprise at least a contain at least a difunctionality by product contain the monofunctional silicone component, the described at least a difunctionality by product of normal content (normalizing amount) is added in the described monomer mixture, solidify described monomer mixture and form bio-medical instrument.
Description of drawings
Fig. 1 is the graph of a relation of the % weight of modulus and dimethacrylate.
Invention is described
The present invention relates to contain at least a composition that contains difunctionality polysiloxanes accessory substance of at least a hydrophilic component, at least a monofunctional silicone component and standard volume.
" by product " used herein refers to the composition that forms as by product during containing the monofunctional silicone component synthetic.
" bio-medical instrument " used herein be designed within mammalian tissues or the liquid or on, and within preferred tissue or the liquid or on any goods.The example of these devices includes but not limited to conduit, implant, stent and device for eyes (for example ophthalmic lens and contact lens).Preferred bio-medical instrument is device for eyes, particularly contact lens, the most particularly the contact lens made from silicone hydrogel.
Term used herein " lens " and " device for eyes " are meant the device that is positioned on intraocular part or the eye.These devices can provide the combination of optical correction, trauma care, drug conveying, diagnostic functions, cosmetic reinforced effects or these performances.Term " lens " includes but not limited to soft contact lens, hard contact lens, intraocular lens, cover type lens (overlaylenses), ocular implant and optics implant.
Term used herein " contains the polysiloxane compatible components " and is meant the active ingredient that comprises at least a polysiloxane and at least one hydroxyl.This type of component has been disclosed in WO03/022321 and WO 03/022322.
One or more that are used for preparing polymkeric substance of the present invention contain the polysiloxane component and one or more hydrophilic components can be any known component that prior art is used to prepare silicone hydrogel.These terms " contain the polysiloxane component " and " hydrophilic component " is not to repel mutually, contain that the polysiloxane component can what be hydrophilic and hydrophilic component can comprise some polysiloxane, hydrophilic component can have polysiloxane group because contain that the polysiloxane component can have hydrophilic radical.
Term used herein " monomer " refers to polymerisable low-molecular weight compound (promptly having the number-average molecular weight that is lower than 1100G/mol usually).
Contain the monofunctional silicone monomer for only containing the monomer an of polymerizable groups and at least one [Si-O-Si] group.Preferred Si and the amount of the O that is connected in containing the polysiloxane component be greater than 20% weight that contains the silicone monomers total molecular weight, and more preferably greater than 30% weight." polymerisable group " used herein means any group of energy free radical or ionic polymerization.Preferred polymerizable groups comprises that the free radical activity group is (as acrylate-based (acrylate), styryl, vinyl, vinyl ether group, methylene-succinic acid ester group, C 1-6Alkyl acrylic ester group, acrylamido, C 1-6Amido, N-vinyl amido, C in alkyl acrylamido, the N-vinyl 2-12Alkenyl (alkenyl), C 2-12Alkenyl phenyl, C 2-12Alkenyl naphthyl or C 2-6Alkenyl phenyl C 1-6Alkyl) or cationically polymerizable group (as vinyl ether group or epoxy group(ing)).Methacrylate based is preferred polymerizable groups.
The useful monofunctional silicone monomer that contains preferably comprises amido, N-vinyl amido and styryl functional group in polymerisable functional group such as acrylate-based, methacrylate based, acrylamido, methacrylamido, the N-vinyl.Be used for the visible United States Patent (USP) 3,808,178,4,120,570,4,740,533,5,070 of example that contains the polysiloxane component of the present invention, in No. 215 and EP 080539.All these patents are attached to herein by reference.These documents disclose many examples that contain the olefinic silicone monomers.
One class preferably contains the monofunctional silicone component and comprises " hydroxyl functional polysiloxane monomer ", it contains at least one polymerisable group, measure and the refractive index detection through gel permeation chromatography, it has less than 5000 daltonian molecular-weight average, and, contain at least one hydroxyl and at least one " Si-O-Si " group preferably less than about 3000 dalton.
Hydroxyl functional polysiloxane monomer comprises the monomer of formula I:
Wherein:
R 1Be hydrogen and C 1-6Alkyl;
R 2, R 3And R 4Independent is C 1-6Alkyl, three C 1-6The C of alkyl siloxy, phenyl, naphthyl, replacement 1-6The phenyl of alkyl, replacement or the naphthyl of replacement,
Wherein said alkyl substituent is selected from one or more following groups: C 1-6Alkoxy carbonyl, C 1-6Alkyl, C 1-6Alkoxyl group, amido, halogen, hydroxyl, carboxyl, C 1-6Alkyl-carbonyl and formyl radical and
Wherein said aromatic substituent is selected from one or more following groups: C 1-6Alkoxy carbonyl, C 1-6Alkyl, C 1-6Alkoxyl group, amido, halogen, hydroxyl, carboxyl, C 1-6Alkyl-carbonyl and formyl radical;
R 5For hydroxyl, contain the alkyl of one or more hydroxyls; Or (CH 2(CR 9R 10) yO) x-R 11, wherein y is 1 to 5, and is preferred 1 to 3, x is 1 to 100 integer, and is preferred 2 to 90, and more preferably 10 to 25; R 9-R 11Independently be selected from H, have the alkyl that is up to 10 carbon atoms and have an alkyl that is up to 10 carbon atoms with what at least one polar functional group replaced;
R 6For comprising the divalent group that is up to 20 carbon atoms;
R 7For carrying out the polymeric univalent perssad by radical polymerization and/or cationic polymerization, comprise being up to 20 carbon atoms;
R 8For comprising divalence or the trivalent group that is up to 20 carbon atoms.
Reaction mixture of the present invention can comprise more than a kind of hydroxyl functional polysiloxane monomer.
For containing monofunctional hydroxyl functional polysiloxane monomer, preferred R 1Be hydrogen, preferred R 2, R 3And R 4Be C 1-6Alkyl and three C 1-6Alkyl siloxy most preferably is methyl and trimethylsiloxy.
Preferred R 5For hydroxyl ,-CH 2OH or CH 2CHOHCH 2OH, most preferably hydroxyl.
Preferred R 6C for divalence 1-6Alkyl, C 1-6Alkoxyl group (alkyloxy), C 1-6Alkoxy C 1-6Alkyl, phenylene, naphthylidene, C 1-12Cycloalkyl, C 1-6Alkoxy carbonyl, amido, carboxyl, C 1-6Alkyl-carbonyl, carbonyl, C 1-6Alkoxyl group (alkoxy), the C that replaces 1-6The C of alkyl, replacement 1-6The C of alkoxyl group, replacement 1-6Alkoxy C 1-6The C of the phenylene of alkyl, replacement, the naphthylidene of replacement, replacement 1-12Cycloalkyl, wherein said substituting group are selected from one or more following groups: C 1-6Alkoxy carbonyl, C 1-6Alkyl, C 1-6Alkoxyl group, amido, halogen, hydroxyl, carboxyl, C 1-6Alkyl-carbonyl and formyl radical.Preferred especially R 6Methyl (methylene radical) for divalence.
Preferred R 7Comprise that the free radical activity group is (as acrylate-based, styryl, vinyl, vinyl ether group, methylene-succinic acid ester group, C 1-6Alkyl acrylic ester group, acrylamido, C 1-6Amido, N-vinyl amido, C in alkyl acrylamido, the N-vinyl 2-12Alkenyl, C 2-12Alkenyl phenyl, C 2-12Alkenyl naphthyl or C 2-6Alkenyl phenyl C 1-6Alkyl) or cation activity group (as vinyl ether group or epoxy group(ing)).Preferred especially R 7For methacrylate based.
Preferred R 8C for divalence 1-6Alkyl, C 1-6Alkoxyl group, C 1-6Alkoxy C 1-6Alkyl, phenylene, naphthylidene, C 1-12Cycloalkyl, C 1-6Alkoxy carbonyl, amido, carboxyl, C 1-6Alkyl-carbonyl, carbonyl, C 1-6The C of alkoxyl group, replacement 1-6The C of alkyl, replacement 1-6The C of alkoxyl group, replacement 1-6Alkoxy C 1-6The C of the phenylene of alkyl, replacement, the naphthylidene of replacement, replacement 1-12Cycloalkyl, wherein said substituting group are selected from one or more following groups: C 1-6Alkoxy carbonyl, C 1-6Alkyl, C 1-6Alkoxyl group, amido, halogen, hydroxyl, carboxyl, C 1-6Alkyl-carbonyl and formyl radical.Preferred especially R 8Be C 1-6Alkoxy C 1-6Alkyl.
The hydroxyl functional polysiloxane monomer of particularly preferred formula I is methacrylic acid 2-hydroxyl-3-[3-[1,3,3,3-tetramethyl--1-[(trimethyl silyl) oxygen base] the sily oxide base] propoxy-] propyl ester (but also two (trimethylsiloxy) methyl-monosilanes of called after (3-methacryloxy-2-hydroxyl propoxy-) propyl group).
Form two (trimethylsiloxy) methyl-monosilanes of above-claimed cpd (3-methacryloxy-2-hydroxyl propoxy-) propyl group by epoxide, the ratio that obtains two (trimethylsiloxy) methyl-monosilanes of above compound and (2-methacryloxy-3-hydroxyl propoxy-) propyl group is 80: 20 a mixture.In some embodiments of the present invention, preferably there is a certain amount of primary hydroxyl, is preferably greater than about 10% weight and more preferably is at least about 20% weight.
Other hydroxyl functional polysiloxane monomers that are fit to comprise (3-methacryloxy-2-hydroxyl propoxy-) propyl group three (trimethylsiloxy) silane:
Two (trimethylsiloxy) methyl-monosilanes of (3-methacryloxy-2-(2-hydroxyl-oxethyl) propoxy-) propyl group:
The reaction product of glycidyl methacrylate and amino-functional polydimethylsiloxane also can be used as hydroxyl functional silicone monomer.Other hydroxyl functional silicone monomers that are fit to comprise those at US 5,994,488 the 6th, 7 and 8 disclosed monomers of row and those are 4,259,467,4,260,725,4,261,875,4,649,184,4,139,513,4,139,692, US 2002/0016383,4,139,513 and 4,139,692 disclosed monomers.These patents or application and other patents of quoting thereof or application are attached to herein by reference.
The another kind of suitable monofunctional silicone monomer that contains is polysiloxane group alkyl (methyl) acrylic monomer (polysiloxanylalkyl (meth) acrylicmonomers) that Formula Il is represented:
Formula II
Figure A20048002455000121
Wherein:
R 12Expression H or low alkyl group; X represents O or NR 16R 16Independent separately expression hydrogen or low alkyl group,
R 13-R 15Independent separately expression low alkyl group or phenyl, b is 1 or 3 to 10.
The example of these polysiloxane group alkyl (methyl) acrylic monomers comprises methacryloxypropyl three (trimethylsiloxy) silane, methacrylic acid pentamethyl disiloxane base methyl esters and methyl two (trimethylsiloxy) methacryloxy methyl-monosilane.Most preferable acryloxy propyl group three (trimethylsiloxy) silane.
The another kind of monofunctional silicone component that preferably contains is the organopolysiloxane prepolymer that formula III is represented:
Formula III
Figure A20048002455000122
Wherein A independently represents active unsaturated group (for example ester of acrylic or methacrylic acid or acid amides) or alkyl or aryl (condition is that at least one A comprises the active unsaturated group that can carry out Raolical polymerizable); R 17, R 18, R 19And R 20Independently be selected from following group separately: have the monovalence alkyl of 1 to 18 carbon atom or the monovalence alkyl that halogen replaces, between carbon atom, can have ehter bond and connect;
R 21The expression have 1 to 22 carbon atom bivalent hydrocarbon radical and
M is 0 or more than or equal to 1 integer, is preferably 5 to 400, more preferably 10 to 300.A concrete example is that monomethyl acryloxy propyl group end-blocking list normal-butyl is end capped polydimethylsiloxane (mPDMS).
Another kind of useful contain that the polysiloxane component comprises that following formula represents contain polysiloxane NSC 11801 or carboxylamine vinyl acetate monomer:
Formula IV
Figure A20048002455000131
Wherein Y represents O, S or NH; R SiExpression contains the organic group of polysiloxane; R represents hydrogen or methyl; D is 1,2,3 or 4; Q is 0 or 1.What be fit to contains polysiloxane organic group R SiComprise following group:
-(CH 2) pSi[(CH 2) sCH 3] 3
-(CH 2) pSi[OSi(CH 2) sCH 3] 3
Wherein: p is 1,2,3 or 4; S is 0,1,2,3,4 or 5.
Describedly contain the polysiloxane NSC 11801 or the carboxylamine vinyl acetate monomer specifically comprises: 3-(ethylene oxy carbonyl sulfenyl) propyl group-[three (trimethylsiloxy silane)], 3-[three (trimethylsiloxy) silyl] propyl carbamic acid allyl ester, 3-[three (trimethylsiloxy) silyl] propyl carbamic acid vinyl acetate, trimethyl silyl ethyl carbonate vinyl acetate, trimethyl silyl methyl carbonic acid vinyl acetate.
Being suitable for of the present invention other contains the monofunctional silicone component and comprises that those are described in United States Patent (USP) 5,321,108,5,387,662 and 5,539,016 component, these patents have been described on the carbon atom with terminal difluoro replacement and have been connected with the polar fluorinated grafting group of hydrogen atom or the polysiloxane of side group.
At least be similar at least a monofunctional silicone component that contains described containing on the difunctionality polysiloxane by product structure.Similar meaning contained identical polysiloxane group and preferably contained all identical functional groups on the structure used herein, except increasing at least one extra polymerizable groups.The difunctionality polysiloxane by product that contains that is fit to comprises two (trimethylsiloxy) methyl-silicane bases-1,2-propylene glycol dimethacrylate (bis (trimethylsiloxy) methylsilylpropyl-1,2-dimethacrylate) with 1, two (3-methacryloxypropyl) four (trimethylsiloxy) sily oxide of 3-, α, ω-two methacryloxies (bismethacryloy) propyl group polydimethylsiloxane and composition thereof etc.Being similar to the examples for compounds that contains the polyfunctional poly siloxanes that contains the monofunctional silicone component on the structure comprises: two (trimethylsiloxy) methyl-silicane bases-1 when using SiMAA, 2-propylene glycol dimethacrylate, when using TRIS 1, two (3-methacryloxypropyl) four (trimethylsiloxy) sily oxide of 3-, α when using mPDMS, ω-two methacryloxypropyl polydimethylsiloxanes etc.
Have been found that at least a difunctionality polysiloxane by product that contains that comprises as component in reactive monomer mix, and do not comprise that containing difunctionality polysiloxane by product compares, then the silicone hydrogel that is produced has more isostatic physical properties.Usually, contain the monofunctional silicone component and contain a certain amount of difunctionality polysiloxane by product that contains., can form many by products synthetic during containing the monofunctional silicone component, and its concentration in containing the monofunctional silicone component need be reduced to minimum usually., the preparation of known purification process contains the concentration that contains difunctionality polysiloxane by product in the monofunctional silicone component and can change and reach more than 5% weight.Regrettably, even the subtle change of difunctionality impurity (as containing difunctionality polysiloxane by product) can cause the noticeable change of the physical properties of the lens of making.The present invention adds and has solved this problem in the described monomer mixture by normal content described being contained difunctionality polysiloxane by product.Therefore, according to the present invention, the amount that contains difunctionality polysiloxane by product in the described monomer mixture is stipulated, be present in the basis that contains difunctionality polysiloxane by product that contains in the monofunctional silicone component with impurity on, added a certain amount of difunctionality polysiloxane by product to satisfy the amount (" normal content ") of regulation.Do not need a large amount of difunctionality polysiloxane by products that contain.Can realize purpose of the present invention by the difunctionality polysiloxane by product that contains that adding is up to about 5% weight (calculating based on the weight that contains the monofunctional silicone component that exists), and preferably be contained in about 0.1 and about 5% weight between, and more preferably about 1 and about 3% weight between contain difunctionality polysiloxane by product (calculating) based on the weight that contains the monofunctional silicone component.Add single difunctionality by product according to normal content in one embodiment.
The described difunctionality polysiloxane by product that contains can be prepared by several different methods.For example; can be higher than two (trimethylsiloxy) methyl-silicane bases-1 of reaction preparation at least 4 hours under about 60 ℃, 2-propylene glycol dimethacrylate by glycidyl oxygen base propyl group seven methyl trisiloxanes and at least a epoxide open chain catalyzer, at least a carboxylic acid, at least a protective material and at least a stopper.
Hydrophilic component comprise those can be when combining with remaining active ingredient for the lens of gained provide at least about 20%, preferably at least about the hydrophilic component of 25% water content.The amount of the suitable hydrophilic component that can exist accounts for about 10 to about 60% of all active ingredient weight.Preferred about 15 to about 50% weight, and more preferably from about 20 to about 40% weight.The hydrophilic monomer that can be used for preparing polymkeric substance of the present invention has at least one polymerizable double bond and at least one hydrophilic functional groups.The example of polymerizable double bond comprises acrylic acid or the like, methacrylic, acrylamido, methacrylamido, fumaric acid class, Malaysia acids, styryl, pseudoallyl phenyl, NSC 11801, carboxylamine ethene ester, allyl class, O-vinyl ethanoyl (O-vinylacetyl) and N-vinyl lactam and the two keys of N-vinyl amido.This class hydrophilic monomer itself can be used as linking agent." acrylic acid or the like " or " containing acrylic acid or the like " monomer is those monomers that comprises acryl (CR ' H=CRCOX), and wherein R is H or CH 3R ' is H, alkyl or carbonyl, and X is O or N, the easy polymerization of known described monomer, N for example, N-DMAA (DMA), vinylformic acid 2-hydroxyl ethyl ester, glyceral methacrylate, N-(2-hydroxyethyl) Methacrylamide, polyethylene glycol monomethacrylate, methacrylic acid, vinylformic acid and composition thereof.
The wetting ability vinyl-containing monomers that can mix hydrogel of the present invention comprises for example monomer of N-vinyl lactam (for example N-vinyl pyrrolidone (NVP)), N-vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl-formamide, N-vinyl formamide, N-(2-hydroxyethyl) carboxylamine ethene ester, N-carboxyl-Beta-alanine N-vinyl ester (N-carboxy-β-alanine N-vinyl ester), preferred NVP.
Other can be used for hydrophilic monomer of the present invention and comprise that one or more terminal hydroxy group are replaced into the polyoxyethylene polyols of the functional group that contains polymerizable double bond.Example comprises and the polyoxyethylene glycol with one or more polymerisable ends position ethylenic group of capping group (for example methacrylic acid isocyanato ethyl ester (" IEM "), methacrylic anhydride, methacrylic chloride, the vinyl benzene formyl chloride etc.) prepared in reaction of a mole or many molar equivalents that described ethylenic group is connected in polyoxyethylene glycol by connection portion (for example carbamate or ester group).
Other examples are for being disclosed in United States Patent (USP) 5,070 in addition, 215 hydrophilic carbon vinyl acetate or carboxylamine vinyl acetate monomer and be disclosed in United States Patent (USP) 4,190,277 hydrophilic  oxazolone monomer.Other suitable hydrophilic monomers are conspicuous for those skilled in the art.
The preferred hydrophilic monomer that is incorporated in the polymkeric substance of the present invention comprises for example hydrophilic monomer of N,N-DMAA (DMA), vinylformic acid 2-hydroxyl ethyl ester, glyceral methacrylate, N-(2-hydroxyethyl) Methacrylamide, N-vinyl pyrrolidone (NVP) and polyethylene glycol monomethacrylate.
Most preferred hydrophilic monomer comprises DMA, NVP and composition thereof.
In certain embodiments, need to add the high-molecular weight hydrophilic polymer." high molecular hydrophilic polymer " used herein is meant that weight-average molecular weight is not less than about 100,000 daltonian materials, and in a single day wherein said material is incorporated in the silicone hydrogel preparation can improve the wettability of having solidified silicone hydrogel.The preferred weight-average molecular weight of these high molecular hydrophilic polymers is greater than about 150,000, and more preferably from about 150,000 to about 2,000,000 dalton, more preferably from about 300,000 to about 1,800,000 dalton, most preferably from about 500,000 to about 1,500,000 dalton.
Perhaps, the also available K value representation of measuring based on kinematic viscosity of the molecular weight of hydrophilic polymer of the present invention, as see and be set forth in Encyclopedia of Polymer Science andEngiBeering (polymer science and engineering encyclopedia) (N-vinyl amide polymer, second edition, the 17th volume, the 198-257 page or leaf, John Wiley ﹠amp; Sons Inc).When representing in this way, the K value of hydrophilic monomer is greater than about 46 and be preferably about 46 to about 150.The amount of the high molecular hydrophilic polymer that exists in the preparation of these devices is enough to make the wettability of contact lens (not carrying out surface modification) to improve at least 10%, and wettable lens preferably are provided.For contact lens, " wettable " is meant the dynamic contact angle that advances of lens less than about 100 °, preferably less than 80 ° and be more preferably less than about 60 °.
The appropriate vol of high molecular hydrophilic polymer be all active ingredient gross weights about 1 to about 15%, more preferably from about 3 to about 15%, most preferably from about 3 to about 12%.
The example of high molecular hydrophilic polymer includes but not limited to polymeric amide, polylactone, polyimide, poly-lactam and functionalized polymeric amide, the DMA of functionalization by the following method for example: with hydroxy functional monomers (for example HEMA) copolymerization of DMA and less molar weight, subsequently with the hydroxyl and material (for example methacrylic acid isocyanato ethyl ester or the methacrylic chloride) reaction that comprises the free redical polymerization group of gained multipolymer.Also can use the hydrophilic prepolymer that makes from DMA or N-vinyl pyrrolidone and glycidyl methacrylate reaction.The glycidyl methacrylate ring can be opened obtaining glycol, and described glycol can other hydrophilic prepolymers in mixed system be used for improving high molecular hydrophilic polymer, hydroxyl functional polysiloxane monomer and any other gives the consistency of the group of consistency.Preferred high molecular hydrophilic polymer is that main chain comprises those of circular part, more preferably cyclic amide or cyclic imide.The high molecular hydrophilic polymer includes but not limited to poly N-vinyl pyrrolidone, poly N-vinyl-2-piperidone, poly N-vinyl-2-hexanolactam, poly N-vinyl-3-methyl-2-hexanolactam, poly N-vinyl-3-methyl-2-piperidone, poly N-vinyl-4-methyl-2-piperidone, poly N-vinyl-4-methyl-2-hexanolactam, poly N-vinyl-3-ethyl-2-pyrrolidone, poly N-vinyl-4,5-dimethyl-2-Pyrrolidone, polyvinyl imidazol, poly-N, the N-DMAA, polyvinyl alcohol, polyacrylic acid, polyoxyethylene, poly-2-ethyl  azoles quinoline, heparin polysaccharide (heparin polysaccharide), polysaccharide and composition thereof and multipolymer (comprise block or random, branch, multichain, comb shape or star), wherein preferred especially poly N-vinyl pyrrolidone (PVP).Also can use multipolymer (for example graft copolymer of PVP).
Except the high molecular hydrophilic polymer of clearly name, can be contemplated that any high-molecular weight polymer can be used for the present invention, condition is when described polymkeric substance adds in the silicone hydrogel preparation, the wettability of cure polymer that this hydrophilic polymer (a) is not separated from reaction mixture basically and (b) gives gained.In some embodiments, preferred high molecular hydrophilic polymer is dissolved in thinner under service temperature.
In certain embodiments, also can comprise hydroxy-containing component.The hydroxy-containing component that can be used for preparing polymkeric substance of the present invention has at least one polymerizable double bond and at least one hydrophilic functional groups.The example of polymerizable double bond comprises acrylic acid or the like, methacrylic, acrylamido, methacrylamido, fumaric acid, toxilic acid, styryl, pseudoallyl phenyl, NSC 11801, carboxylamine ethene ester, allyl class, O-vinyl ethanoyl and N-vinyl lactam and the two keys of N-vinyl amido.Hydroxy-containing component also can be used as linking agent.Hydroxy-containing component comprises hydroxyl in addition.This hydroxyl can be primary, the second month in a season or tert-hydroxyl, and can be positioned on the alkyl or aryl.The monomeric example of available hydroxyl includes but not limited to methacrylic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxyl ethyl ester, N-(2-hydroxyethyl) Methacrylamide, N-(2-hydroxyethyl) acrylamide, N-2-hydroxyethylamino vinyl formate (N-2-hydroxyethyl vinylcarbamate), carbonic acid 2-hydroxyl ethyl ester vinyl acetate (2-hydroxyethyl vinyl carbonate), methacrylic acid 2-hydroxypropyl acrylate, the own ester of hydroxyethyl methacrylate, the hydroxyethyl methacrylate monooctyl ester and as be disclosed in United States Patent (USP) 5,006,622,5,070,215,5,256,751 and 5, other hydroxy functional monomers of 311,223.Preferred hydrophilic component comprises methacrylic acid 2-hydroxyl ethyl ester.
The present invention also comprises at least a method that silicone hydrogel with stable mechanical property and water-content is provided, described method comprises: (a) form monomer mixture, described mixture comprises and at least aly contains at least a of monofunctional silicone component, at least a hydrophilic component and normal content and contain difunctionality polysiloxane component, and step (b) is solidified described monomer mixture and formed described silicone hydrogel.The difunctionality polysiloxane component that contains of choice criteria amount makes described silicone hydrogel have required isostatic mechanical properties.Change the described amount that contains the polyfunctional poly silicone components and prepare a plurality of hydrogels, measuring required physical properties and selecting provides the level of required balance of properties, thereby is determined by experiment normal content.
Bio-medical instrument of the present invention, particularly eye-use lens have isostatic character, and this makes them particularly useful.This type of character comprises water-content, modulus, elongation and oxygen flow degree.Therefore, in one embodiment, described bio-medical instrument is a contact lens, and the water-content of these lens is greater than about 20%, be preferably greater than about 25%, and more preferably greater than about 30%.
Suitable oxygen flow degree is preferably greater than about 40barrer, more preferably greater than about 60barrer.The modulus that is fit to about 40 and about 100psi between, and preferably about 50 and about 90psi between.The percentage elongation that is fit to is between about 50 and about 400%, preferably between about 100 and about 300%.Producing medical apparatus, particularly producing in the contact lens, the present invention can select and effectively control mechanical properties.Can prepare each goods by the monomer mixture that contains difunctionality polysiloxane by product that contains a series of different contents, analyze the character of each goods that makes, select to contain difunctionality polysiloxane by product according to goods character, thereby can select normal content.Therefore,, can keep in touch the required character of lens easily, not be present in the concentration that contains other impurity in the monofunctional silicone component and do not need to change according to the present invention.
Equally, bio-medical instrument particularly the advancing contact angle of device for eyes and contact lens less than about 80 °, preferably less than about 70 ° and be more preferably less than about 65 °.In preferred embodiments, goods of the present invention have the combination of above-mentioned character.All combinations of above-mentioned scope all are contained in the present invention.
Except at least a at least a difunctionality polysiloxane component that contains that contains monofunctional silicone monomer, at least a hydrophilic component and normal content, monomer mixture of the present invention also comprises well known in the art other and forms the component of hydrogel, for example linking agent, initiator, tinting material, ultraviolet absorber compounds etc.
The linking agent that is fit to is known in this field, comprise ethylene glycol dimethacrylate (" EGDMA "), TEG dimethacrylate (" TEGDMA "), trimethylolpropane trimethacrylate (" TMPTMA "), glycerine trimethacrylate, polyethylene glycol dimethacrylate (wherein the molecular weight of polyoxyethylene glycol preferably is up to for example about 5000) and other polyacrylic ester and polymethacrylate, for example above-mentioned end-blocking polyoxyethylene polyols that comprises two or more terminal methyl group acrylate parts.Linking agent consumption routinely uses, and the active ingredient in for example per 100 gram reaction mixtures uses about 0.0004 to about 0.02 mole of linking agent.(active ingredient is all substances except that thinner and any other do not become the processing aid of a part of polymer architecture in the reaction mixture.) or, if hydrophilic monomer and/or contain silicone monomers as linking agent then optionally adds reaction mixture with linking agent.The example that can be used as linking agent and do not need in reaction mixture to add the hydrophilic monomer of other linking agent when existing comprises the above-mentioned polyoxyethylene polyols that comprises two or more terminal methyl group acrylate parts.
The example that contains silicone monomers that can be used as linking agent and do not need to add other linking agent when existing in reaction mixture comprises α, ω-two methacryloxypropyl polydimethylsiloxanes.
Preferably comprise polymerisation catalysts in the described reaction mixture.Initiators for polymerization is included in compound (for example lauryl peroxide, benzoyl peroxide, isopropyl percarbonate, Diisopropyl azodicarboxylate etc.) and the photoinitiator system (for example aromatics alpha-alcohol ketone, alkoxyl group oxygen base bitter almond oil camphor, methyl phenyl ketone, acylphosphine oxide, two acylphosphine oxide and tertiary amine add diketone and their mixture etc.) that produces free radical under the temperature of suitable rising.The illustrative example of light trigger is 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-third-1-ketone, two (2; 6-dimethoxy benzoyl)-2; 4; 4-tri-methyl-amyl phosphine oxide (DMBAPO), two (2; 4; the 6-trimethylbenzoyl)-phenyl phosphine oxide (Irgacure 819), 2; 4; 6-trimethyl benzyl diphenyl phosphine oxide and 2; 4; the combination of 6-trimethylbenzoyl diphenyl phosphine oxide, bitter almond oil camphor methyl ester (benzoin methyl ester) and camphorquinone and 4-(N, N-dimethylamino) ethyl benzoate.Commercially available visible light initiator system comprises Irgacure 819, Irgacure 1700, Irgacure1800, Irgacure 819, Irgacure 1850 (all deriving from Ciba Specialty Chemicals) and Lucirin TPO initiator (deriving from BASF).Commercially available UV light trigger comprises Darocur 1173 and Darocur 2959 (Ciba Specialty Chemicals).Operable these and other light triggers are disclosed in the Photoinitiators for Free RadicalCationic ﹠amp that G.Bradley writes; Anionic Photopolymerization (light trigger of radical cation and negatively charged ion photopolymerization reaction) (J.V.Crivello ﹠amp; K.Dietliker, second edition, the 3rd volume, JohnWiley and Sons, New York, 1998), the document is attached to herein by reference.Initiator is used for the photopolymerization reaction that reaction mixture comes the initiation reaction mixture with significant quantity, and for example per 100 parts of reactive monomers about 0.1 are to about 2 weight parts.According to employed initiators for polymerization, can be by using the suitable heat of selecting or the polyreaction of visible light or UV-light or additive method initiation reaction mixture.Perhaps, for example electron beam initiation can had to utilize under the situation of light trigger.Yet; when using light trigger; preferred initiator is two acylphosphine oxides; for example two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxides (Irgacure819 ) or 1-hydroxycyclohexylphenylketone and two (2; 6-dimethoxy benzoyl)-2; 4, the combination of 4-tri-methyl-amyl phosphine oxide (DMBAPO), and the initiating method of preferred polymeric reaction is a visible light.Most preferably two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxides (Irgacure 819 ).
Described monomer mixture can comprise other components, such as but not limited to UV absorption agent, medicinal reagent, antimicrobial compounds, active tinting material (reactive tint) but, pigment copolymerization and non-polymerizable dyes, releasing agent and combination thereof.
The monofunctional silicone monomer that contains in the preferred monomers mixture is active ingredient weight about 5 to 95% in the monomer mixture, more preferably from about 30 to 85%, and most preferably from about 45 to 75%.Hydrophilic monomer in the preferred foregoing invention is active ingredient weight about 5 to 80% in the monomer mixture, more preferably from about 10 to 60%, and most preferably from about 20 to 50%.Thinner in the preferred foregoing invention is the about 2 to 70% of reaction mixture gross weight (comprising activity and inactive ingredients), more preferably from about 5 to 50%, most preferably from about 15 to 40%.
Preferred active ingredient and thinner be combined as such combination, this combination comprises about 25 and contains the monofunctional silicone component to about 60% weight; about 20 hydrophilic monomers to about 40% weight; 0.1 contain difunctionality polysiloxane component to about 5% weight; about 5 hydroxy-containing components to about 20% weight; about 0.2 cross-linking monomer to about 3% weight; about 0 UV to about 3% weight absorbs monomer; the about 2 high molecular hydrophilic polymers to the about 10% weight total weight of active ingredient (all based on) and about 20 are to about 50% weight one or more claimed thinners of (comprising the total weight of active and inactive ingredients based on all).
Reaction mixture of the present invention can make by any method known to those skilled in the art, for example shake or stirring, and be used to form polymer product or device by currently known methods.
For example, bio-medical instrument of the present invention can be by mixing active ingredient and one or more thinners with initiators for polymerization, solidify in appropriate condition and to form product, and subsequently this product is made by suitable shapes of formation such as grinding machine processing, cuttings.Perhaps, reaction mixture can be placed mould also to be cured as suitable goods subsequently.
The known various method that is used at the described reaction mixture of manufacturing processing of contact lens comprises rotational casting and static casting.The rotational casting method is disclosed in United States Patent (USP) 3,408, and 429 and 3,660,545, static casting process is disclosed in United States Patent (USP) 4,113, and 224 and 4,197,266.The method that preferred preparation comprises the contact lens of polymkeric substance of the present invention is the moulding method of silicone hydrogel, this method economy and can accurately controlling the net shape of hydrated lens.To this method, reaction mixture is placed the mould of the shape with final required silicone hydrogel (being water-swelling polymer), and the condition that reaction mixture is in monomer polymerization gets off to prepare the polymkeric substance/diluent mixture of final desired product shape.Subsequently, this polymkeric substance/diluent mixture is removed thinner and final water with solvent treatment and is replaced and prepare the silicone hydrogel with final size and shape, and described final size and shape are closely similar with the size and dimension of the original polymkeric substance/thinner goods of molding.This method can be used for making contact lens and further is disclosed in United States Patent (USP) 4,495, and 313,4,680,336,4,889,664 and 5,039,459, these patents are attached to herein by reference.
Use following method to measure mist degree: the hydration test lens in the BBS are placed transparent 20 * 40 * 10mm aquarium, described pond is under the envrionment temperature and is positioned on the black background of plane, from the below with fibre optics lamp (fiber optic lamp) (diameter that has that derives from Titan Tool Supply Co. is 0.5 " photoconduction and power set up be the fibre optics lamp of 4-5.4) become 66 ° of angles irradiations with lens pond vertical direction; also with pick up camera (DVC 1300C:19130 RGB camera) with NavitarTV Zoom 7000 zoom lens perpendicular to the image of lens pond from top seizure lens, described position for video camera is 14mm above the lens plane.Adopt the image of EPLX XCAP V 1.0 softwares deduction blank pool and background correction scattering from the scattering of lens.Scattered light image through deducting is by also comparing and quantitative analysis with-1.00 dioptric CSI Thin Lens  subsequently in the lens 10mm of central authorities upper integral, the haze value of described CSIThin Lens  is set at 100 arbitrarily, is set at 0 without any the haze value of lens.Analyze 5 lens, the result is averaged the haze value of representing as with the percentage ratio of standard C SI lens.
The moisture determination of contact lens is as follows: (three every group) placed packaging solution 24 hours with three groups of lens.Each lens blots with wet rag and weighs.These lens are under 60 ℃, and 0.4 inch of mercury or littler pressure descended dry 4 hours.The exsiccant lens are weighed.Water content is calculated as follows:
% water content=(weight in wet base-dry weight) * 100/ weight in wet base
The mean value and the standard deviation of the sample moisture content after record calculates.
Modulus is measured by the constant speed pinblock (crosshead) that adopts the mobile model tension testing machine, and described trier is equipped with the load unit that is reduced to initial absolute altitude.Suitable trier comprises Instron model 1122.With the dumbbell shaped sample (0.522 inch is long, 0.276 inch " ear " wide and 0.213 inch " neck " wide) be loaded on the anchor clamps, and stretch with the constant speed pulling force of 2in/min and to destroy up to sample.Sample length (Lf) when the initial gauge length (Lo) of measure sample and destruction.12 samples of every kind of composition measuring also write down mean value.Elongation=[(Lf-Lo)/Lo] * 100.Tensile modulus is partly measured in the initial linear of stress/strain curves.
The following measurement of advancing contact angle.Every group prepares four samples, each sample by from lens, cut out a width and be about the center band of 5mm and in packaging solution balance make.At 23 ℃ of wetting powers that when sample immerses salt solution or pulls out from salt solution, use down between Wilhelmy microbalance measurement lens surface and the BBS.Establish an equation under using:
F=2 γ pcos θ or θ=cos -1(F/2 γ p)
Wherein F is a wetting power, and γ is for surveying the surface tension of liquid, and p is the girth of sample at meniscus, and θ is a contact angle.Advancing contact angle partly obtains by the wetting experiment that sample immerses packaging solution.Each sample carries out four times, and the result is averaged the advancing contact angle that obtains these lens.
The following measurement of Dk.Lens are placed on the polarography oxygen sensor of being made up of the au cathode of 4mm diameter and silver ring anode, subsequently overlay mesh support (mesh support) in the above.Lens are exposed in the atmosphere of moist 2.1%O2.Utilize sensor determination to diffuse through the oxygen of lens.Stacked a plurality of lens increase thickness, or use thicker lens.Measure the L/Dk of 4 significantly different samples of one-tenth-value thickness 1/10 and thickness is drawn.The inverse of regression slope is the Dk of sample.On commercially available contact lens, measure and the acquisition reference value in this way.Derive from Bausch ﹠amp; The Balafilcon A lens of Lomb are measured as about 79barrer.The Etafilcon lens are measured as 20 to 25barrer (1barrer=10 -10(cm 3Gas * cm 2)/(cm 3Polymkeric substance * second * cmHg)).
Following examples have further described the present invention, but the present invention without limits.They only mean and propose to put into practice method of the present invention.The technician in contact lens field and other experts can find putting into practice of other method of the present invention.Yet those methods are deemed to be within the scope of the present invention.
Some material signs that adopted among the embodiment are as follows:
DMA:N, the N-DMAA
HEMA: methacrylic acid 2-hydroxyl ethyl ester
MPDMS: molecular weight (M n) be the end capped polydimethylsiloxane of monomethyl acryloxy propyl group end-blocking list normal-butyl of 800-1000
Norbloc:2-(2 '-hydroxy-5-methyl base acryloxy ethylphenyl)-2H-benzotriazole
PVP: poly N-vinyl pyrrolidone (K value 90)
D3O:3,7-dimethyl-3-octanol
EGDMA: ethylene glycol dimethacrylate
CGI 819: two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxides
DVE: two (trimethylsiloxy) methyl-silicane base-1,2-propylene glycol dimethacrylate
Two (trimethylsiloxy) methyl-silicane bases-1 of embodiment-preparation, 2-propylene glycol dimethacrylate
According to following order of listing and amount following reactant is packed in the exsiccant 100ml three neck round-bottomed flasks that assembled magnetic stirring apparatus, thermopair and drying tube:
1.47g methacrylic acid lithium (0.016 mole)
12.9mg butylated hydroxytoluene
16.17g methacrylic anhydride (0.105 mole)
17.20g methacrylic acid (0.2 mole)
33.60g glycidyl oxygen base propyl group seven methyl trisiloxanes (0.1 mole)
This mixture of vigorous stirring also heated 7.5 hours under 100 ℃.In case reaction is finished, and allows it be cooled to room temperature and is transferred in the separating funnel of 500ml.
Dilute this organic phase with the 100ml hexane,, use the NaCl solution washing organic phase of 3 * 100ml 2.5% subsequently with the NaOH aqueous solution of 3 * 200ml 0.5N.With this organic phase of 5.0g dried over sodium sulfate, and filter this material by the sintered glass funnel.
Also ground (trituated) this system 3 hours with 15g silica gel treatment filtrate.Filter this organic phase with the sintered glass funnel, and add 15g silica gel again and repeated to grind 3 hours.Filter by the sintered glass funnel, under 55 ℃, the vacuum of pf<10mbar, after the evaporating volatile component, separate needed product subsequently.Two (trimethylsiloxy) methyl-silicane bases-1 of synthetic, the purity of 2-propylene glycol dimethacrylate is 89.9%.
Embodiment 1-4
Adopt following method, prepare monomer mixture with the component of listing in table 1.
Merge each component and under about 30 ℃ temperature, mixed about 4 hours.The thinner that the ratio adding of 40% thinner is contained 72.5% tertiary amyl alcohol and 27.5%PVP K-12 with 60% monomer mixture.This reaction monomers mixture is assigned among the preceding Qu Mo, then the back song is embossed in the top of monomer mixture.Subsequently with this assembly by the tunnel of three heating zone is arranged, be heated to 67 ℃ in the 1st zone, the 2nd zone is heated to 65 ℃ and the 3rd zone is heated to 61 ℃, at visible light (intensity 600,800 and 800mW/cm 2) initiation lens curing down.Be 3.75 minutes total set time.After curing, remove the back bent mould that has cured lens and at room temperature put into about 60 minutes of the hydration solution of 70: 30 IPA/ deionized water, put into deionized water then about 120 minutes, lens demoulding from this after fixing mould is also removed it with swab (swab) from the Qu Mo of back during this period.These lens are put into the blister packaging that contains the salt packaging solution, sealing and 121 ℃ of sterilizations 29 minutes.
Table 1
Monomer 1 2 3 4
MPDMS 22 22 22 22
SiMAA 30 29.73 29.13 28.53
DVE 0 0.27 0.87 1.47
DMA 31 31 31 31
HEMA 8.5 8.5 8.5 8.5
PVP 6 6 6. 6
EGDMA 0.75 0.75 0.75 0.75
Norbloc 1.5 1.5 1.5 1.5
CGI 819 0.23 0.23 0.23 0.23
Blue Hema 0.02 0.02 0.02 0.02
Measure the modulus and the elongation of lens and will the results are shown in table 2.
Table 2
Embodiment %DVE * Modulus (psi) Elongation (%)
1 1.1 55 150
2 2 60 169
3 4 74 131
4 6 83 130
*Calculate based on SiMAA2 weight
Fig. 1 has shown the funtcional relationship of modulus and sense dimethacrylate concentration.Therefore, Fig. 1 and each embodiment have obviously shown by adding at least a difunctionality polysiloxane by product may command mechanical properties that contains of normal content.

Claims (21)

1. method, described method comprises the formation monomer mixture, described monomer mixture comprise at least a contain at least a difunctionality by product contain the monofunctional silicone component, the described at least a difunctionality by product of normal content is added in the described monomer mixture, solidify described monomer mixture and form bio-medical instrument.
2. the process of claim 1 wherein described normal content be the described weight that contains the monofunctional silicone component about 0.1 and about 5% between.
3. the process of claim 1 wherein described normal content be the described weight that contains the monofunctional silicone component about 1 and about 3% between.
4. the process of claim 1 wherein that the described monofunctional silicone component that contains is selected from: polysiloxane group alkyl (methyl) acrylic monomer, hydroxyl functional polysiloxane monomer, organopolysiloxane prepolymer, NSC 11801 monomer, carboxylamine vinyl acetate monomer, have on the carbon atom that terminal difluoro replaces and be connected with the polar fluorinated grafting group of hydrogen atom or polysiloxane of side group and composition thereof.
5. the process of claim 1 wherein described polysiloxane group alkyl (methyl) acrylic monomer that the monofunctional silicone component comprises formula I that contains:
Wherein:
R 12Be H or low alkyl group;
X is O or NR 16R 16Independently be selected from hydrogen or low alkyl group,
R 13-R 15Independently be selected from low alkyl group or phenyl separately, b is 1 or 3 to 10.
6. the process of claim 1 wherein that the described monofunctional silicone component that contains is selected from methacryloxypropyl three (trimethylsiloxy) silane, methacrylic acid pentamethyl disiloxane base methyl esters and methyl two (trimethylsiloxy) methacryloxy methyl-monosilane.
7. the process of claim 1 wherein that the described monofunctional silicone component that contains comprises methacryloxypropyl three (trimethylsiloxy) silane.
8. each method in the claim 1,6,7 and 8, the wherein said difunctionality polysiloxane by product that contains comprises two (trimethylsiloxy) methyl-silicane bases-1,2-propylene glycol dimethacrylate.
9. the process of claim 1 wherein the described hydroxyl functional polysiloxane that the monofunctional silicone component is formula I that contains:
Figure A2004800245500003C1
Wherein:
R 1Be selected from hydrogen and C 1-6Alkyl;
R 2, R 3And R 4Independently be selected from C 1-6Alkyl, three C 1-6The C of alkyl siloxy, phenyl, naphthyl, replacement 1-6The phenyl of alkyl, replacement or the naphthyl of replacement;
R 5For hydroxyl, contain the alkyl of one or more hydroxyls; Or (CH 2(CR 9R 10) yO) x)-R 11, wherein y is 1 to 5, x is 1 to 100 integer; R 9-R 11Independently be selected from H, have the alkyl that is up to 10 carbon atoms and had an alkyl that is up to 10 carbon atoms by what at least one polar functional group replaced;
R 6For comprising the divalent group that is up to 20 carbon atoms;
R 7For carrying out the polymeric univalent perssad by radical polymerization and/or cationic polymerization, comprise being up to 20 carbon atoms; With
R 8For comprising the divalent group that is up to 20 carbon atoms.
10. the method for claim 9, wherein R 1Be H,
R 2, R 3And R 4Independently be selected from C 1-6Alkyl and three C 1-6Alkyl siloxy;
R 4Be selected from hydroxyl ,-CH 2OH or CH 2CHOHCH 2OH;
R 6Be selected from the C of divalence 1-6Alkyl, C 1-6Alkoxyl group, C 1-6Alkoxy C 1-6Alkyl, phenylene, naphthylidene, C 1-12Cycloalkyl, C 1-6Alkoxy carbonyl, amido, carboxyl, C 1-6Alkyl-carbonyl, carbonyl, C 1-6The C of alkoxyl group, replacement 1-6The C of alkyl, replacement 1-6The C of alkoxyl group, replacement 1-6Alkoxy C 1-6The C of the phenylene of alkyl, replacement, the naphthylidene of replacement, replacement 1-12Cycloalkyl, wherein said substituting group are selected from one or more following groups: C 1-6Alkoxy carbonyl, C 1-6Alkyl, C 1-6Alkoxyl group, amido, halogen, hydroxyl, carboxyl, C 1-6Alkyl-carbonyl and formyl radical;
R 7Be selected from acrylate-based, styryl, vinyl, vinyl ether group, methylene-succinic acid ester group, C 1-6Alkyl acrylic ester group, acrylamido, C 1-6Amido, N-vinyl amido, C in alkyl acrylamido, the N-vinyl 2-12Alkenyl, C 2-12Alkenyl phenyl, C 2-12Alkenyl naphthyl, C 2-6Alkenyl phenyl C 1-6Alkyl, vinyl ether group and epoxy group(ing);
R 8Be selected from the C of divalence 1-6Alkyl, C 1-6Alkoxyl group, C 1-6Alkoxy C 1-6Alkyl, phenylene, naphthylidene, C 1-12Cycloalkyl, C 1-6Alkoxy carbonyl, amido, carboxyl, C 1-6Alkyl-carbonyl, carbonyl, C 1-6The C of alkoxyl group, replacement 1-6The C of alkyl, replacement 1-6The C of alkoxyl group, replacement 1-6Alkoxy C 1-6The C of the phenylene of alkyl, replacement, the naphthylidene of replacement, replacement 1-12Cycloalkyl, wherein said substituting group are selected from one or more following groups: C 1-6Alkoxy carbonyl, C 1-6Alkyl, C 1-6Alkoxyl group, amido, halogen, hydroxyl, carboxyl, C 1-6Alkyl-carbonyl and formyl radical.
11. the process of claim 1 wherein that the described monofunctional silicone component that contains is selected from two (trimethylsiloxy) methyl-monosilanes of (3-methacryloxy-2-hydroxyl propoxy-) propyl group, two (trimethylsiloxy) methyl-monosilanes of (2-methacryloxy-3-hydroxyl propoxy-) propyl group, (3-methacryloxy-2-hydroxyl propoxy-) propyl group three (trimethylsiloxy) silane, 3-methacryloxy-2-(2-hydroxyl-oxethyl) propoxy-) two (trimethylsiloxy) methyl-monosilanes of propyl group, end capped polydimethylsiloxane of monomethyl acryloxy propyl group end-blocking list normal-butyl and composition thereof.
12. the process of claim 1 wherein that the described monofunctional silicone component that contains is selected from two (trimethylsiloxy) methyl-monosilanes of (3-methacryloxy-2-hydroxyl propoxy-) propyl group, two (trimethylsiloxy) methyl-monosilanes of (2-methacryloxy-3-hydroxyl propoxy-) propyl group, the end capped polydimethylsiloxane of monomethyl acryloxy propyl group end-blocking list normal-butyl and composition thereof.
13. each method in the claim 9,10,11 or 12, the wherein said difunctionality polysiloxane by product that contains comprises two (trimethylsiloxy) methyl-silicane bases-1,2-propylene glycol dimethacrylate.
14. the process of claim 1 wherein described about 25% to about 60% of the described active ingredient weight of monofunctional silicone ingredients constitute that contains.
15. the process of claim 1 wherein that described hydrophilic component accounts for about 10 to about 60% of described active ingredient weight.
16. the method for claim 1, wherein said hydrophilic component is selected from N,N-DMAA, vinylformic acid 2-hydroxyl ethyl ester, glyceral methacrylate, N-(2-hydroxyethyl) Methacrylamide, N-vinyl pyrrolidone, polyethylene glycol monomethacrylate and composition thereof.
17. the process of claim 1 wherein that described hydrophilic component is selected from N,N-DMAA, vinylformic acid 2-hydroxyl ethyl ester and composition thereof.
18. the method for claim 1, the wherein said monofunctional silicone component that contains comprises two (trimethylsiloxy) methyl-monosilanes of (3-methacryloxy-2-hydroxyl propoxy-) propyl group, end capped polydimethylsiloxane of monomethyl acryloxy propyl group end-blocking list normal-butyl and composition thereof, described at least a difunctionality by product comprises two (trimethylsiloxy) methyl-silicane bases-1,2-propylene glycol dimethacrylate, and described monomer mixture also comprises at least a high molecular hydrophilic polymer, and at least a hydrophilic component is selected from N,N-DMAA, vinylformic acid 2-hydroxyl ethyl ester and composition thereof.
19. the process of claim 1 wherein that described bio-medical instrument is a device for eyes.
20. the process of claim 1 wherein that described bio-medical instrument is a contact lens.
21. the process of claim 1 wherein that described at least a difunctionality by product is single by product.
CN 200480024550 2003-06-30 2004-06-29 Silicone hydrogels having consistent concentrations of multi-functional polysiloxanes Pending CN1842559A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101883799B (en) * 2007-12-03 2013-03-27 博士伦公司 High water content silicone hydrogels
CN102115515B (en) * 2010-01-05 2014-06-18 远东新世纪股份有限公司 Copolymer capable of enhancing wettability of silicone hydrogel, silicone hydrogel composition containing same and ophthalmic item employing silicone hydrogel composition
CN104945570A (en) * 2015-07-03 2015-09-30 东南大学 Silica gel contact lens and surface reversal processing method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101883799B (en) * 2007-12-03 2013-03-27 博士伦公司 High water content silicone hydrogels
CN102115515B (en) * 2010-01-05 2014-06-18 远东新世纪股份有限公司 Copolymer capable of enhancing wettability of silicone hydrogel, silicone hydrogel composition containing same and ophthalmic item employing silicone hydrogel composition
CN104945570A (en) * 2015-07-03 2015-09-30 东南大学 Silica gel contact lens and surface reversal processing method thereof
CN104945570B (en) * 2015-07-03 2017-06-09 东南大学 A kind of Silica hydrogel contact lens and its surface reversion processing method

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