CN100519124C - Molds for producing contact lenses - Google Patents

Molds for producing contact lenses Download PDF

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CN100519124C
CN100519124C CNB038239752A CN03823975A CN100519124C CN 100519124 C CN100519124 C CN 100519124C CN B038239752 A CNB038239752 A CN B038239752A CN 03823975 A CN03823975 A CN 03823975A CN 100519124 C CN100519124 C CN 100519124C
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alicyclic
group
polymer
alkyl
eyeglass
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CN1688426A (en
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D·K·杜贝
D·C·图尔纳
L·L·科珀
T·A·马蒂亚茨奥
R·W·阿布拉姆斯
K·P·麦凯布
S·F·安塞尔
R·J·福热尔
D·吉尔德
T·R·罗尼
宋旭
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Johnson and Johnson Vision Care Inc
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Johnson and Johnson Vision Care Inc
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Abstract

This invention describes molds made from alicyclic co-polymers that are useful in the production of contact lenses and methods for their use.

Description

Produce the mould of contact lenses
The present invention describes and is used to produce the mould of contact lenses and their using method.
Related application
The application is the part continuation application of Application No. 10/395,755, and 10/395, No. 755 application is again the part continuation application of Application No. 10/222,373.
Background technology
Improved people's eyesight at commercial use contact lenses from generation nineteen fifty.First contact lenses are made with hard material.Although also using these glasses at present, because their comfortableness is not so well in beginning, oxygen permeability is also low relatively, thus they and be not suitable for all patients.Afterwards, there had been some progress in this field, and having occurred is the Soft contact lens of base with the hydrogel, and these contact lenses are also very popular up to today.These eyeglasses are than the contact lenses made from hard material, and it is high that oxygen permeability is wanted, and usually has on more comfortable.Machined into hard plastic sheet manufacturing hard lenses is different with adopting, and the Soft contact lens of ductility usually is to use two parts mould to form this eyeglass and produced, and described mould all has and the consistent profile of the last eyeglass of require for per half.Some moulds and production method thereof can be referring to following document: US 4,565,348,4,640 like this, and 489,4,495,313, JP 08025378 and JP0726644, this paper is quoted them with it as a reference in full.
These two parts moulds have formpiston and former, and the convex surfaces of formpiston is corresponding to the back flexure plane of finished product glasses, and the concave surface of former is corresponding to the antecurvature curved surface of finished product glasses.In order to use these moulds to prepare eyeglass, uncured eyeglass preparaton is placed between the convex surfaces and concave surface of mold half, then solidify.Handle this curing eyeglass and mould with a kind of liquid medium again, so that take off this curing eyeglass from die surface.Although this method is very simple, produces a kind of spendable eyeglass and just should satisfy ask for something.At first, make material and the uncured eyeglass preparaton that this mould uses and to have chemical compatibility.Secondly, this mold materials should be able to withstand these conditions of cure, also should be able to be with some conditions are compatible like this.For example, these eyeglasses can adopt heat or light or its both are cured.When eyeglass was solidified, then importantly lens mold allowed the light transmission of suitable wavelength.Three, mold materials can not hinder the degree of solidifying eyeglass of taking off with sticking mutually should not the reaching of curing eyeglass.These eyeglasses are usually produced under a kind of like this production environment, promptly importantly with a kind of repeatably, when foreseeable mode is separated, these eyeglasses stick to described in this lens mold on the mould movably.Therefore, select suitable material to make these moulds and be still the problem that people were concerned about that those wish to make Soft contact lens.
Other people once used some materials, for example polypropylene, polystyrene, polyethylene, polymethyl methacrylate, with and main chain contain the improved polyalkene of alicyclic part, prepare two parts lens mold.Although these materials are spendable, owing to found different eyeglass preparatons, particularly silicone hydrogel lens preparaton, so need other useful mold materials.
In addition, some new results of study have obtained the contact lenses with hydrogel and silicon hydrogel production in this field, and these contact lenses have been coated with and have improved the polymer that these eyeglasses have on comfortableness.Often when handle solidifying eyeglass with polymer-coated these eyeglasses.Recently, the production method of coated polymeric eyeglass is with polymer-coated two parts die surface, adds uncured preparaton, eyeglass is solidified, then take off these curing eyeglasses from mould again toward the lens mold that is coated with, and wherein said curing lens surface has been coated with the polymer that sticks to originally on this molded side.The Application No. 09/921,192, the denomination of invention " that propose in August 8 calendar year 2001 adopt mould to shift among the method " that proofreaies and correct article and have described this method in detail, and this paper is quoted it with it as a reference in full.When adopting this method of coating eyeglass, it is crucial more when producing uncoated eyeglass to select mold materials.
Therefore, still there are not to satisfy the needs of the lens mold can be used to produce many dissimilar Soft contact lens.This needs are just being satisfied in following invention.
Detailed description of the present invention
The present invention includes a kind of mould of producing eyeglass, this eyeglass contains a kind of alicyclic co-polymer, basically form by a kind of alicyclic co-polymer, or form by a kind of alicyclic co-polymer, wherein said alicyclic co-polymer polymerization is from least two kinds of alicyclic monomers with different chemical structures, basically form by at least two kinds of alicyclic monomers, or form by at least two kinds of alicyclic monomers with different chemical structures with different chemical structures." eyeglass " used herein means any ophthalmic device of staying in the eyes or on the eyes.These devices can provide optical correction, maybe can be cosmetic.The term eyeglass includes, without being limited to Soft contact lens, intraocular lens, covering eyeglass, eye insert and optics insert.Preferred eyeglass of the present invention is a Soft contact lens, and they are made with silicone elastomer or hydrogel, and they include, without being limited to silicon hydrogel, and the fluorine hydrogel.Disclosing in following file in the United States Patent (USP) that proposes on some Soft contact lens preparaton: US 5 710 302, WO 9 421 698, EP 406 161, JP 2000016905, US 5 998 498, calendar year 2001 September 20 please number 09/957299, Application No. 09/532943, US 6 087 415, US 5 760 100, US 5 776 999, US 5 789 461, US 5 849 811 and US 5 965 631.Following file discloses other polymer that can be used to make Soft contact lens: US 6 419 858,6 308 314 and 6 416690.This paper is quoted aforementioned documents with it as a reference in full.The particularly preferred eyeglass of the present invention is as at US 5 998 498, Application No. 09/532943, the part continuation application of an Application No. 09/532943 that proposed August 30 in 2000, the etafilcon A of preparation in the Application No. 09/957299 that propose September 20 calendar year 2001, genfilcon A, lenefilcon A, polymacon, acquafilcon A, balafilcon A, lotrafilcon A, galyfilcon A, senofilcon A, silicon hydrogel, as the Application No. 60/318536 that proposes in September 10 calendar year 2001, denomination of invention " contains the biomedical articles " of internal wetting agent, and the non-interim copy of the same denomination of invention that proposed on September 6th, 2002, US 6 087 415, US 5 760 100, US 5 776 999, US 5 789 461, the Soft contact lens of preparation among US 5 849 811 and the US 5 965 631.These patents (and application) and disclosed in this application other patent all will be quoted with it as a reference in full.
Term " alicyclic monomer " used herein means the polymerizable compound that wherein contains at least one saturated carbon ring.Saturated carbon ring can be by one or more hydrogen, C of being selected from 1-10Alkyl, halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10Alkoxyl, cyano group, amide groups, imino group, silicyl and the C that replaces 1-10The base of alkyl replaces, and wherein these substituting groups are to be selected from following one group: halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10One or more bases in alkoxyl, cyano group, amide groups, imino group and the silicyl.The alicyclic monomer example includes, but are not limited to polymerisable cyclobutane, cyclopentanes, cyclohexanes, cycloheptane class, cyclooctane class, dicyclo butanes, dicyclo pentane class, dicyclic hexane, norbornane class, double-octane class and norborneol alkanes.Preferably by the open loop metathesis, then hydrogenization makes at least two alicyclic monomer polymerizations.Because some copolymers are very expensive, the mould that preferably uses these copolymers to make can repeatedly be used to prepare eyeglass, once is that representational mould then is not like this.For preferred mold of the present invention, can repeatedly use them to produce eyeglass.
More particularly, the alicyclic monomer that contains saturated carbon ring includes, without being limited to following structure:
Figure C03823975D00201
R in the formula 1-6Be independently selected from hydrogen, C 1-10Alkyl, halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10The C of alkoxyl, cyano group, amide groups, imino group, silicyl and replacement 1-10One or more groups in the alkyl, substituting group wherein are to be selected from following one group: halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10One or more groups in alkoxyl, cyano group, amide groups, imino group and the silicyl.Two other or plural R 1-6Can constitute unsaturated bond, carbocyclic ring, the carbocyclic ring that contains one or more unsaturated bonds or aromatic ring together.Preferred R 1-6Be selected from C 1-10The C of alkyl and replacement 1-10Alkyl, wherein these substituting groups are selected from following one group: halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10Alkoxyl, cyano group, amide groups, imino group and silicyl.
These alicyclic co-polymer are made up of at least two different alicyclic monomers.Preferred alicyclic co-polymer polymerization is from two or three different alicyclic monomers, and they are selected from following one group:
Figure C03823975D00202
With
Figure C03823975D00203
Particularly preferred alicyclic co-polymer polymerization is from two different alicyclic monomers, and wherein the general structural formula of the saturated carbon ring of these alicyclic monomers is as follows:
Figure C03823975D00211
And R 1-R 4Be C 1-10Alkyl.
Typically, the surface of alicyclic co-polymer can be 30-45 dyne/cm under 25 ℃.More particularly preferred alicyclic co-polymer polymerization is from two different alicyclic monomers, and they are commodity that ZeonChemicals L.P. company sells with trade name ZEONOR.ZEONOR has several different grades, and its glass transition temperature is 105-160 ℃.Particularly preferred ZEONOR is ZEONOR 1060R, and according to the ZEON Chemicals L.P. of production firm, its melt flow rate (MFR) (" MFR ") is 11.0-18.0g/10min (as JISK 6719 (230 ℃) test), proportion (H 2O=1) be 1.01, and glass transition temperature it is 105 ℃.
Term " mould " used herein means a kind of hard article, and it can be used for uncured preparaton is made some eyeglasses.Preferred mould is two parts mould as described previously, and wherein make with alicyclic co-polymer of the present invention the front curved part of mould or rear bending part, and other sweep is made with polypropylene.The polypropylene example includes, without being limited to the polypropylene of metallocene catalyst, and it has nuclear, clarification, for example be and be not limited to the Achieve 1615 of Exxon and ATOFINA EOD 00-11.The preferred production process of mould of the present invention is to adopt the injection moulding of known technology, but also can adopt other technology, for example produces these moulds with machined into, diamond turning or laser cutting technology.
Typically, some eyeglasses are to form at least one surface of two mould parts.But, if desired, can form a face of these eyeglasses with a mould, can adopt the other face of machined into method or other method processing.
Except that these alicyclic co-polymer, mould of the present invention can contain some additives, and they help with these surfaces that forms eyeglasses separately reducing the adhesion of this curing eyeglass and molded side, or its both.Before described polymer cure was made mould, alicyclic co-polymer was added for example additive in the past, as stearic acid metal or ammonium salt, amide waxe, polyethylene or polypropylene wax, organophosphorus ester, glyceride or alcohol ester.Some example additives include, without being limited to Dow Siloxane MB50-321 (silicone dispersion), Nurcrel 535 ﹠amp like this; 932 (ethylene-methacrylic acid copolymer resin number of registration 25053-53-6), Eruc acid amides (fatty acid amide number of registration 112-84-5), Ole acid amides (fatty acid amide number of registration 301-02-0), Mica (number of registration 12001-26-2), Atmer 163 (fatty alkyl diethanol amine number of registration 107043-84-5), Pluronic (PPOX-polyethylene oxide block copolymer number of registration 106392-12-5), Tetronic (alkoxylated amines 110617-70-4), Flura (number of registration 7681-49-4), calcium stearate, zinc stearate, Super-Floss anti-block (slip/anti-blocking agent, number of registration 61790-53-2), Zeospheres anti-block (slip/anti-blocking agent); Ampacet 40604 (fatty acid amide), Kemamide (fatty acid amide), the Licowax fatty acid amide, Hypermer B246SF, XNAP, polyethylene glycol monolaurate (anlistatig) epoxidised soybean oil, talcum (hydrated magnesium silicate), calcium carbonate behenic acid, pentaerythritol tetrastearate, butanedioic acid, epolene E43-Wax, methylcellulose, cocamide (anti-blocking agent number of registration 61789-19-3), PVP (360000MW) and US5,690, disclosed additive in 865, this paper is quoted them with it as a reference in full.Preferred additives is PVP, zinc stearate and glycerin monostearate, wherein the percetage by weight in these total polymer weight additives is about 0.05-10.0 percetage by weight, preferably about 0.05-3.0, most preferably about 2.0 percetages by weight.
Except that additive,, have to be beneficial to and separate the surface that these form eyeglass toward these surface applied surfactants that forms eyeglass.Suitable surfactant example comprises tween surfactants, and US 5,837 especially, the Tween 80 of describing in 314, and this paper is quoted it with it as a reference in full.US 5,264, and 161 disclose other surfactant example, and this paper is quoted it with it as a reference in full.
Except these alicyclic co-polymer, mould of the present invention can also contain other polymer, for example polypropylene, polyethylene, polystyrene, polymethyl methacrylate, and the improved polyalkene that contains alicyclic part in main chain.For example can use these alicyclic co-polymer and polyacrylic admixture (the metallocene catalyst agent method that nucleation is arranged, ATOFINAEOD 00-11 wherein), wherein by weight percentage alicyclic co-polymer be respectively that about 99:1 is to about 20:80 with polyacrylic ratio.Both can use this admixture arbitrary half module tool or its, and wherein preferably this admixture is used in the rear bending part, and the front curved part is made up of these alicyclic co-polymer.
In addition, the present invention includes a kind of production method of eyeglass, this method comprises the steps, basically form by following step, or form: 1) uncured eyeglass preparaton is distributed to molded side by following step, this preparaton contains a kind of alicyclic co-polymer, substantially form by a kind of alicyclic co-polymer, or form by a kind of alicyclic co-polymer, wherein said alicyclic co-polymer polymerization is from least two kinds of alicyclic monomers with different chemical structures, basically form by at least two kinds of alicyclic monomers with different chemical structures, or form 2 by at least two kinds of alicyclic monomers with different chemical structures) under some suitable conditions, solidify described eyeglass preparaton.Term eyeglass, alicyclic monomer and mould have described in front meaning and preferable range.
The uncured " of term " used herein means and in the end solidify to form eyeglass a kind of physical state of eyeglass preparaton before.Some eyeglass preparatons contain some monomer mixtures, and they solidify and only carry out once.Other eyeglass preparaton contains some monomers, partly solidified monomer, macromonomer and other component.At US 6,419, disclose such some parts in 858,6,308,314 and 6,416,690 and solidified the preparaton example.The present invention will use wherein these preparatons.
Phrase " used herein solidifies " and means any known eyeglass preparaton curing under some suitable conditions, for example adopt light, heat and produce the suitable catalyst of solidifying eyeglass.In the Soft contact lens preparaton list of references that this paper lists, can see some condition of cure examples like this.
In addition, the present invention includes the eyeglass that adopts a kind of method to produce, this method comprises the steps, basically form by following step, or form: 1) uncured eyeglass preparaton is distributed to die surface by following step, this preparaton contains a kind of alicyclic co-polymer, substantially form by a kind of alicyclic co-polymer, or form by a kind of alicyclic co-polymer, wherein said alicyclic co-polymer polymerization is from least two kinds of alicyclic monomers with different chemical structures, basically form by at least two kinds of alicyclic monomers with different chemical structures, or form 2 by at least two kinds of alicyclic monomers with different chemical structures) under some suitable conditions, solidify described eyeglass preparaton.Term eyeglass, alicyclic monomer and mould have described in front meaning and preferable range.
The present invention also comprises a kind of mould, it contains a kind of alicyclic co-polymer and comprises that at least one forms the surface of eyeglass, basically form the surface composition of eyeglass by a kind of alicyclic co-polymer and at least one, or form the surface composition of eyeglass by a kind of alicyclic co-polymer and at least one:
Wherein said alicyclic co-polymer polymerization is from least two kinds of alicyclic monomers with different chemical structures, basically form by at least two kinds of alicyclic monomers with different chemical structures, or form by at least two kinds of alicyclic monomers with different chemical structures, and
The surface of wherein said at least a formation eyeglass comprises the HMW coating composition that is coated with effective dose, basically comprise that by the described at least a surface that forms eyeglass the HMW coating composition that is coated with effective dose forms, or comprise that by the described at least a surface that forms eyeglass the HMW coating composition that is coated with effective dose forms.Term eyeglass, alicyclic monomer, uncured and mould have described in front meaning and preferable range.
The surperficial " that " used herein forms eyeglass means the surface that is used for the molding eyeglass.Such surface has the surface smoothness of optical quality, and unexpected it is enough smooth, so that the formation lens materials that contacts with molded side is that optics is acceptable through the resultant lens surface of polymerization.In addition, described surface has a kind of geometry, this geometry is absolutely necessary for making this lens surface have desired optical characteristics, in these optical characteristics non-limiting comprise spherical power, aspheric surface sum of powers face of cylinder power, wave front aberration correction, corneal topography correction etc. with and the combination.
Term " HMW " means that mean molecule quantity (" MW ") is enough high and this coating can not be dissolved in this eyeglass preparaton or the mold materials.For the present invention, preferably adopt gel permeation chromatography (" GPC "), use light scattering detector and high sensitivity refractive index measurement detector molecular weight, for example use the model PL-RI that obtains from Polymer Labs.Use phenogel 5 μ m linear gel posts, its is equipped with the solution of lithium bromide in dimethyl formamide of guard column with same component and 0.5 percetage by weight as diluent, carries out gpc analysis.Flow velocity is per minute 0.5mL, injects the about 10-20 μ of volume L.The accurate MW that uses will depend on the coating of selection and the monomer mixture of use.In a kind of preferred specific embodiment, the molecular weight of this coating is greater than about 300kD.
The " coating composition " that the present invention uses contains various known monomers and polymer.Polyvinyl alcohol preferably, PEO, polymethylacrylic acid 2-hydroxy methacrylate, polymethyl methacrylate, polyacrylic acid, polymethylacrylic acid, poly, poly-itaconic acid, polyacrylamide, PMAm, polydimethylacrylamiin, the polymethyl acid glyceride, polystyrolsulfon acid, polysulfonates or salt polymer, PVP, the carboxy methylation polymer, carboxymethyl cellulose for example, polysaccharide, the Glucoamino glycan, PLA, polyglycolic acid, the block of above-mentioned polymer or random copolymer etc., and composition thereof.Preferably use polymethylacrylic acid 2-hydroxy methacrylate, PVP, polyacrylic acid, polymethylacrylic acid, poly-(methyl) acrylamide or polyacrylamide.More preferably, use polymethylacrylic acid 2-hydroxy methacrylate.
Except these heavy polymers, this coating composition can contain low boiling (about below 100 ℃) solvent and higher boiling (about more than 100 ℃) solvent.Suitable low boiling point solvent includes, without being limited to acetone, chloroform and alcohol, for example methyl alcohol, ethanol, isopropyl alcohol, uncle-butanols etc.Useful high boiling solvent include, without being limited to methyl-, ethyl-and isopropyl lactate, ethylene glycol and (gathering) ethylene glycol, propane diols, just-methyl pyrrolidone, dimethyl formamide, tetrahydrogeraniol, 1-butanols, 1-amylalcohol, 1-hexanol, 1-octanol, 3-methyl-3-amylalcohol, dimethyl-3-octanol, 3-methoxyl group-1-butanols, 1,2 and 1,4-butanediol, 1,3-hexylene glycol, water etc.Typically, when being coated with down for 15-45 ℃, low boiling point solvent is about 10:90 to 90:10 with the ratio of high boiling solvent.When adopting this coating composition of spin-coating method (following discussion) coating, this coating composition contains low boiling point solvent or high boiling solvent or both.
In addition, this coating composition can contain at least a surfactant.Suitable surfactant comprises and is not limited to anion surfactant, carboxylate for example, sulfonate, sulfate, phosphoric acid and polyphosphate, cationic surfactant, for example long-chain amine and salt thereof, diamines and polyamines and salt thereof, quaternary ammonium salt, amine oxide, non-ionic surface active agent, PEO alkyl phenol for example, alkylphenol ethoxylate, the PEO straight chain alcohol, polyethoxylated polyoxygenated trimethylene glycol, the polyethoxylated polydimethylsiloxanecopolymer copolymer, fluoridize alkane ethoxylated copolymer and long-chain carboxylic acid's ester, zwitterionic surfactant, for example responsive and to the insensitive surfactant of pH etc. to pH, and their combination.Use the particular type and the amount of surfactant will depend on other component and the molded side of using this coating composition.Typically, in the gross weight of this coating composition, use more than or equal to about 0.001 percetage by weight to being less than or equal to about 5 percetages by weight.
Can adopt any suitable method that this coating composition is applied to molded side, comprising and be not limited to compression, brush, spraying, ink jet printing, aerosolized, nebulization, dipping, spin coating etc. and combination thereof.Preferably, use spin coating.In addition, preferably, use it for the system eyeglass and want dry this coating before, or make it sticking.Can adopt any suitable method to carry out drying, but preferably at air or under vacuum, under the about glass transition temperature of mold materials (" Tg "), carry out drying in temperature, then under any temperature of mold materials Tg, carrying out balance being full of under the nitrogen.In being exposed to the process of vacuum, preferably use cold-trap or other filter, to prevent to pollute mould.
When adopting spin coating method, the surface tension of this coating composition is preferably lower than molded side surface energy.More preferably, the surface tension of this coating composition is greater than about 3 dyne/cm, and is lower than the surface energy of the molded side that is coated with when measuring under this coating coating temperature.Most preferably, the surface tension of this coating composition is greater than 8 dyne/cm, and is lower than the surface energy of this molded side.
When preferred spin coating method is used to produce contact lenses, adopt spin-coating method that coating is deposited on the molded side of mould, reach the about 5-70nm of the dried thickness of coating.Under this coating coating temperature, measure, if the difference of the surface of the surface tension of this coating and mould energy is higher than about 8 dyne/cm, use is not more than about 20 μ l coating compositions at least about 2 μ l, and spin coating is during at least about 3 seconds, suitable spin coating distribution curve is at least about 6,000RPM, and be not higher than about 8,000RPM.If the surface tension difference is less than about 8 dyne/cm, use is not more than about 10 μ l coating compositions at least about 2 μ l, and spin coating is during at least about 3 seconds, and this mould rotation is up at least about 3,000RPM, and be not higher than about 5,000RPM, this then mould rotation is up at least about 7,000RPM, and be not higher than about 10,000RPM, rotation stopped after 3 seconds again.
Should remove the excess coating material that is accumulated on the die edge, can adopt any method easily, wherein comprise without limitation and wipe excess coating material, utilization vacuum, solvent, washing or injection compressed air are removed excess coating material.Preferably, adopt injection compressed air to remove excessive coating.Adopt when spraying compressed air, key is to begin to adopt spin coating, forwards it then to and sprays compressed air, and preferably, the pressure of injection air is equal to or greater than about 3 pounds/inch 2
Term " coating effective dose " means that this coating composition forms the lip-deep thickness and the degree of roughness of eyeglass at it.For the hydration contact lenses, preferably, hydration contact lenses peak-to-peak surface roughness is preferred less than about 500nm.Therefore, use the effective scale of coating to show, the amount of this coating composition is enough to provide the build of this coating composition on the surface that forms eyeglass, obtain the hydration article by this thickness and should have acceptable surface roughness, should have less than the positive and negative surface roughness of the eyeglass of about 500nm and obtain contact lenses.More preferably, use the amount of coating composition can be enough to obtain build, and be not more than about 70nm,, and be not more than about 50nm,, and be not more than about 40nm more preferably at least about 20nm preferably at least about 5nm at least about 5nm.
Also more preferably, described coating effective dose has covered all or has all formed basically the surface of eyeglass.Can be added to coating additive in the HMW coating composition of the present invention.Coating additive can include, without being limited to diluent, pigment and bactericidal composition.The bactericidal composition example that can use by this way: US6,218,492,6 are disclosed in patent and the patent application below, 248,811,6,160,056 and the Application No. 10/028 that proposes December 20 calendar year 2001,400, contact lenses that denomination of invention is antibiotic and production method thereof, the Application No. 10/029,526 that propose December 21 calendar year 2001, denomination of invention antimicrobial contact lenses and using method thereof, this paper is quoted it with it as a reference in full.
In addition, the present invention also comprises a kind of production method that is coated with eyeglass, and this method comprises the steps, is made up of following step basically, or is made up of following step:
(1) use the HMW coating composition that is coated with effective dose to be coated with at least one formation lens surface of lens mold, wherein said lens mold contains alicyclic co-polymer and comprises that at least one forms the surface of eyeglass;
Wherein said alicyclic co-polymer polymerization is from least two kinds of alicyclic monomers with different chemical structures;
(2) uncured eyeglass preparaton is distributed on the surface of described at least one formation eyeglass; And
(3) under the condition that is suitable for forming the coating eyeglass, described eyeglass preparaton and described coating composition are solidified, it solidifies below about 5min of the time of staying.
Term eyeglass, alicyclic monomer, uncured, mould, HMW, coating composition and coating effective dose all have described in front meaning and preferable range.
For the present invention is described, following embodiment has been proposed.These embodiment do not limit the present invention.Their meaning just explanation is implemented method of the present invention.Be engaged in the knowledgeable people and other expert that produce lens and all may find other method of the present invention of implementing.But these methods all are considered within the scope of the present invention.
Embodiment
In these embodiments, adopted following abbreviation:
The BC rear bending part
Blue-HEMA replaces Reactive Blue with the short alkali of methacrylic acid hydroxyl ethyl ester
The product of #4dye monochloride
CIP is pre--solidifies
CGI 1850 1-hydroxycyclohexylphenylketones with two (2,6-dimethoxy benzoyl
Base)-2,4, the 1:1 (weight) of 4-tri-methyl-amyl phosphine oxide mixes
Compound
819 pairs of (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxides of CGI
D3O 3,7-dimethyl-3-octanol
The UV light trigger of Darocurl173 Ciba Speciality Chemicals
The DMA N,N-DMAA
The FC front curved part
ATOFINA EOD 00-11 metallocene and isotactic polypropylene, its melt flows
Speed is 14-18g/10min, ASTM D1238
The HEMA 2-hydroxyethyl methacrylate
The IPA isopropyl alcohol
The Application No. that Macromer proposes on December calendar year 2001 20
10/028400, contact lenses that denomination of invention is antibiotic and production thereof
This product that embodiment describes in the method
MPDMS is with the dimethyl silicone polymer of monomethyl propenyloxy group propyl group end-blocking
M-PDMS-OH list-(3-metacryloxy-2-hydroxyl propoxyl group) propyl group end-blocking
, the dimethyl silicone polymer of list-butyl end-capping (MW1100)
Norbloc 2-(2 '-hydroxy-5-methyl base propenyloxy group ethylphenyl)-2H-benzene
And triazole
PVP gathers (N-vinyl pyrrolidone)
Poly-Hema polymethylacrylic acid hydroxy methacrylate, its molecular weight is higher than 1MM
Dalton
SIGMA 2-acrylic acid, the 2-methyl-, 2-hydroxyl-3-[3-[1,3,3, the 3-tetramethyl
-1-[(trimethyl silyl) oxygen] the disiloxane base] propoxyl group]
Propyl ester
TEGDMA dimethacrylate four sweet esters
TrEGDMA dimethacrylate triglyceride
TBACB TBuA-m-chlorobenzoic acid ester
The THF oxolane
TMI 3-isopropenyl-α, the α-Er Jiajibianji isocyanates
TRIS 3-metacryloxy propyl group three (trimethyl silicane alcoxyl base) silane
Embodiment 1
Use alicyclic co-polymer to prepare mould
Alicyclic co-polymer ZEONOR
Figure C03823975D0028185921QIETU
The 1060R pelletized product is placed in 90 ℃ of driers that dry about 1-4 hour.This material is more then heating, adopts by Nan NostrandReinhold Company again and delivers in 1986, Dominick ﹠amp; The technology of general description in " injection moulding handbook (INJECTION MOLDING HANDBOOK) " that Donald Rosato edits purifies by injection machine.Purified about three (3) pounds of materials, molding 10-15min again obtains the front curved part and the rear bending part of eyeglass, and its power is-1.00D.Covered normally used lens mold, and be used for producing eyeglass according to the method for embodiment 2.
Embodiment 2
The preparaton that Table A is listed is used to prepare some silicone hydrogel lens.The Application No. 09/957,299 that propose September 20 calendar year 2001 discloses relevant accurately other details of mixed method.
Table A
Percetage by weight
Macromer2 17.98
TRIS 14.00
DMA 26.00
MPDMS 28.00
TEGDMA 1.00
HEMA 5.00
PVP 5.00
NORBLOC 2.00
Blue HEMA 0.02
CGI1850 1.00
The remaining part of this preparaton is additive and diluent.Monomer is 100:20 with the ratio of diluent, and this diluent is 3,7-dimethyl-3-octanol.Acetic acid, 1% final mixture is used to stablize this monomer.
The front curved part of the method preparation of employing embodiment 1 and rear bending part mould have been coated with high MW and have gathered-HEMA coating.Adopt spin coating method with 8000rpm in 8 seconds with poly--HEMA of about 6 microlitres, 1.3 percetages by weight at 70:30 ethanol: the solution coat in the ethyl lactate is to front curved part die surface (concave surface).During spin coating circulated last two seconds, air is ejected into spin coating edge partly, remove excessive coating.Adopt spin coating method, earlier with 6000rpm spin coating 2 seconds, again with 8000rpm spin coating 6 seconds, with poly--HEMA of about 8.5 microlitres, 1.1 percetages by weight at 70:30 ethanol: the solution coat in the ethyl lactate is to rear bending part die surface (projection).During spin coating circulated last two seconds, air is ejected into spin coating edge partly, remove excessive coating.Above-mentioned eyeglass preparaton is distributed in these lens molds, closes these parts, under visible light,, then under visible light, solidified about 7 minutes in 70 ℃, produce eyeglass like this in 45 ℃ of precuring 45 seconds.In all cases, in adding 30 seconds of this mould, lens monomer dosage just begins this precuring.
Clinically these eyeglasses are tested, find they on glasses wettable, to tear aspect time and the anti-deposition property with ACUVUEX etafilcon A eyeglass be suitable, therefore proved this coating is applied to have obtained the compatible eyeglass of a kind of physiology on this eyeglass.
Embodiment 3
Preparation polypropylene lens mold
Adopt the method for embodiment 1,, prepare the FC and the BC of lens mold with the alicyclic co-polymer of polypropylene (Atofina EOD 00-11 produces) replacement embodiment 1.
Embodiment 4
Use the mould of embodiment 3 to prepare eyeglass
Use preparaton and the method for embodiment 2 to make eyeglass, but replace the mould of embodiment 1 with the mould of embodiment 3.The defective in these finished product lens coatings that adopted visualization equipment inspection.Do not having on the finished product lens surface of coating composition, defective is the zone of dispersing.In following table B, calculated and write down the percentage of some defectives.This embodiment proved, can be used for producing the coating eyeglass with the mould of some alicyclic co-polymer manufacturings, and its coating defects reduces significantly.
Table B
FC and BC moulding material Check the eyeglass number The coating defects ratio
Embodiment 3 1200 39.1%
Embodiment 3 1200 45.5%
Embodiment 3 1200 50.0%
Embodiment 1 1600 2.0%
Embodiment 1 1600 6.3%
Embodiment 1 4800 4.4%
Embodiment 1 400 0.3%
Embodiment 5
Use the eyeglass of different FC and BC mold materials preparation
Adopt the method for embodiment 2, use FC and BC mould to prepare some eyeglasses according to embodiment 1 and 3 method manufacturings.According to table C, use different mold materials to make some eyeglasses.Holiday ratio and mist value have been measured.The measuring method of pointing out the mist value is, transparent pond is placed on the black background, and the test eyeglass is put in the salt solution in this pond, use the optical fiber lamp with perpendicular to 66 ° of angles in this eyeglass pond from following illumination, use video camera from top shooting eyeglass image.To carrying out integration in these center of lens 10mm, then with-1.00 diopter CSI Thin eyeglasses (Wesley Jessen 33 East Tower A, Des Planes, the commodity eyeglass that IL produces) compares, like this quantitative analysis the scattered light image after the background correction, at random setting described commodity eyeglass mist value is 100, and not having any eyeglass setting mist value is zero.These data show, when making FC and BC mould with alicyclic co-polymer, obtain minimum number of defects.
Table C
The FC mold materials The BC mold materials The CIP time The holiday ratio Mist value (%CSI)
ZEONOR ZEONOR 60 0.7% 24.7
ZEONOR ZEONOR 30 0% 20.5
ZEONOR PP 60 1.4% 31.2
ZEONOR PP 30 8.5% 53.8
Embodiment 6
Use Examples of alicyclic polymers to prepare lens mold
Examples of alicyclic polymers ZEONEX
Figure C03823975D0028185921QIETU
The 480R pelletized product is placed in 100 ℃ of driers that dry about four (4) hours.Attempt to adopt the method for embodiment 1 to prepare mould.Use this material can not produce spendable lens mold.Only cover the curing materials thin slice, do not form the lens mold chamber.The temperature (being elevated to the highest level of security of machine) and the mold materials temperature that improve molding machinery can not address this problem.Make otiose mould.This embodiment has proved in the difference that does not have with some alicyclic co-polymer success production moulds and with some Examples of alicyclic polymers to exist between the production mould.
Embodiment 7
Preparation fusion mould
In mixing rotary drum, allow a certain amount of polypropylene (ATOFINA EOD-0011,50%) and Zeonor 1060R (50%) blending handle 15min.This mixture adopts extrusion molding or pelletizing (palletizing) method to handle and obtains uniform material.The material of this blending is added in the injection machine, extrudes half former and the half light mould of lens mold, then solidify.This curing mold is put into before use and reaches 30min in the nitrogen environment.
Embodiment 8
Preparation silicone hydrogel lens B-
Under about 23 ℃, the reactive component that table is listed among the D and diluent (D30) stirs or tumble mixed at least about 3 hours, all dissolve up to all components.These reactive components are to represent with the percetage by weight of all reactive components, and diluent is to represent with the percetage by weight of final reaction mixture.This reactant mixture is added in these lens molds of embodiment 7, in N2, uses Philips TL20W/03T fluorescent lamp to carry out irradiation down again at 45 ℃.Condition of cure in the glove box is about 6.5min under about 0.2mW/c2, then about 12min under 2.5mWw/c2.Oxygen content is<1.5% O 2Strike the die sinking tool with the hand, estimate these eyeglasses, with determine these solidify eyeglasses whether still with the front curved part of mould or rear bending part together.Table E has listed Zeonor and the percentage of polypropylene (pp) and the eyeglass number of category-B eyeglass in per half lens mold, and described category-B eyeglass is their to be separated still together eyeglass of back it and front curved part or rear bending part.
Table D
Type of lenses B C D E F G H I J K
Form
SIGMA 28 30 28.6 28 31 32 29 39.4 20 68
PVP(K90) 7 10 7.1 7 7 7 6 6.7 3 7
DMA 24 17 24.5 23.5 20 20 24 16.4 37 22
mPDMS 31 32 0 31 31 34 31 29.8 15 0
TRIS 0 0 0 0 0 0 0 0 15 0
HEMA 6 6 6.1 6 6.5 3 5.5 2.9 8 0
Norbloc 2 2 0 2.0 2 2 2 1.9 0 0
CGI 1850 0.48 1 1.02 1 1 1 1 1 1 0
TEGDMA 1.5 2 1.02 1.5 1.5 1 1.5 1.9 0 2
TrEGDMA 0 0 0 0 0 0 0 0 1 0
Blue HEMA 0.02 0 0 0 0 0 0 0 0 0
mPDMS-OH 0 0 31.6 0 0 0 0 0 0 0
Darocur1173 0 0 0 0 0 0 0 0 0 1
D30% 23 26 17 23 23 29 32 28 17 27
Table E
The rear bending part The front curved part The % eyeglass is in FC The overall test number
5%pp 95%Zeonor 100%Zeonor 29 24
25%pp 75%Zeonor 100%Zeonor 71 24
35%pp 65%Zeonor 100%Zeonor 88 24
35%pp 65%Zeonor 100%Zeonor 91 32
40%pp 60%Zeonor 100%Zeonor 97 32
40%pp 60%Zeonor 100%Zeonor 100 24
45%pp 55%Zeonor 100%Zeonor 100 32
50%pp 50%Zeonor 100%Zeonor 100 32
75%pp 25%Zeonor 100%Zeonor 100 32
This embodiment has illustrated the situation that these eyeglasses increase along with polypropylene amount in this admixture.

Claims (80)

1. mould that is used to produce eyeglass, it contains a kind of alicyclic co-polymer, and wherein said alicyclic co-polymer polymerization is from least two kinds of alicyclic monomers with different chemical structures.
2. mould according to claim 1, wherein said alicyclic monomer comprise polymerisable cyclobutane, cyclopentanes, cyclohexanes, cycloheptane class, cyclooctane class, dicyclo butanes, dicyclo pentane class, dicyclic hexane, norbornane class, double-octane class or norborneol alkanes.
3. mould according to claim 1, described alicyclic co-polymer polymerization is from two kinds of alicyclic monomers, and wherein these alicyclic monomers contain saturated carbon ring.
4. mould according to claim 1, wherein said alicyclic monomer are selected from following one group:
Figure C03823975C00021
Figure C03823975C00022
With
Figure C03823975C00023
R in the formula 1-6Be independently selected from hydrogen, C 1-10Alkyl, halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10The C of alkoxyl, cyano group, amide groups, imino group, silicyl and replacement 1-10One or more in the alkyl are wherein at the C of described replacement 1-10In the alkyl substituting group be selected from following one group: halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10Alkoxyl, cyano group, amide groups, imino group and silicyl.
5. mould according to claim 1, wherein said alicyclic monomer are selected from following one group:
Figure C03823975C00031
Figure C03823975C00032
With
R in the formula 1-6In two or more constitute unsaturated bond or carbocyclic ring together.
6. mould according to claim 1, wherein said alicyclic monomer are selected from following one group:
Figure C03823975C00034
With
Figure C03823975C00035
R in the formula 1-6Be independently selected from hydrogen, C 1-10Alkyl, halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10The C of alkoxyl, cyano group, amide groups, imino group, silicyl and replacement 1-10One or more in the alkyl are wherein at the C of described replacement 1-10In the alkyl substituting group be selected from following one group: halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10One or more in alkoxyl, cyano group, amide groups, imino group and the silicyl.
7. mould according to claim 4, wherein R 1-6Be C 1-10Alkyl, or the C that replaces 1-10Alkyl, wherein said substituting group are selected from following one group: halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10Alkoxyl, cyano group, amide groups, imino group and silicyl.
8. mould according to claim 1, wherein said alicyclic monomer is:
Figure C03823975C00041
R wherein 1-4Be independently selected from C 1-10Alkyl.
9. mould according to claim 1, the MFR of wherein said alicyclic co-polymer are 11.0-18.0g/10min, and proportion is 1.01, and glass transition temperature is 105 ℃.
10. mould according to claim 1, wherein said mould also contains additive.
11. mould according to claim 10, wherein this additive is the zinc stearate of 2.0 percetages by weight.
12. mould according to claim 10, wherein this additive is the glycerin monostearate of 2.0 percetages by weight.
13. mould according to claim 1, wherein a kind of alicyclic co-polymer is contained in front curved part and rear bending part, and the MFR of this alicyclic co-polymer is 11.0-18.0g/10min, and proportion is 1.01, and glass transition temperature is 105 ℃.
14. mould according to claim 1, wherein a kind of alicyclic co-polymer is contained in the front curved part, and the MFR of this alicyclic co-polymer is 11.0-18.0g/10min, and proportion is 1.01, and glass transition temperature is 105 ℃, and polypropylene is contained in the rear bending part.
15. mould according to claim 1, wherein a kind of alicyclic co-polymer is contained in the rear bending part, and the MFR of this alicyclic co-polymer is 11.0-18.0g/10min, and proportion is 1.01, and glass transition temperature is 105 ℃, and polypropylene is contained in the front curved part.
16. mould according to claim 1, wherein a kind of alicyclic co-polymer is contained in the front curved part, the MFR of this alicyclic co-polymer is 11.0-18.0g/10min, proportion is 1.01, glass transition temperature is 105 ℃, and polypropylene and a kind of alicyclic co-polymer are contained in the rear bending part, and the MFR of this alicyclic co-polymer is 14g/10min, proportion is 1.01, and glass transition temperature is 105 ℃.
17. mould according to claim 1, wherein a kind of alicyclic co-polymer is contained in the rear bending part, the MFR of this alicyclic co-polymer is 11.0-18.0g/10min, proportion is 1.01, glass transition temperature is 105 ℃, and polypropylene and a kind of alicyclic co-polymer are contained in the front curved part, and the MFR of this alicyclic co-polymer is 11.0-18.0g/10min, proportion is 1.01, and glass transition temperature is 105 ℃.
18. mould according to claim 16, wherein alicyclic co-polymer is 5:95 to 95:5 with polyacrylic ratio.
19. mould according to claim 16, wherein alicyclic co-polymer is 20:80 to 80:20 with polyacrylic ratio.
20. an eyeglass production method, this method comprises the steps:
1) uncured eyeglass preparaton is distributed on 1 die surface, wherein said die surface contains a kind of alicyclic co-polymer, wherein said alicyclic co-polymer polymerization from least two kinds of alicyclic monomers with different chemical structures and
2) described eyeglass preparaton is solidified.
21. method according to claim 20, described alicyclic co-polymer polymerization is from two kinds of alicyclic monomers, and wherein these alicyclic monomers contain saturated carbon ring.
22. method according to claim 20, wherein said alicyclic monomer are selected from following one group:
With
Figure C03823975C00053
R in the formula 1-6Be independently selected from hydrogen, C 1-10Alkyl, halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10The C of alkoxyl, cyano group, amide groups, imino group, silicyl and replacement 1-10One or more in the alkyl are wherein at the C of described replacement 1-10In the alkyl substituting group be selected from following one group: halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10Alkoxyl, cyano group, amide groups, imino group and silicyl.
23. method according to claim 20, wherein said alicyclic monomer are selected from following one group:
Figure C03823975C00061
Figure C03823975C00062
With
Figure C03823975C00063
R in the formula 1-6In two or more constitute unsaturated bond or carbocyclic ring together.
24. method according to claim 20, wherein said alicyclic monomer are selected from following one group:
Figure C03823975C00064
With
Figure C03823975C00065
R in the formula 1-6Be independently selected from hydrogen, C 1-10Alkyl, halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10The C of alkoxyl, cyano group, amide groups, imino group, silicyl and replacement 1-10One or more in the alkyl are wherein at the C of described replacement 1-10In the alkyl substituting group be selected from following one group: halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10One or more in alkoxyl, cyano group, amide groups, imino group and the silicyl.
25. method according to claim 22, wherein R 1-6Be C 1-10Alkyl, or the C that replaces 1-10Alkyl, wherein said substituting group are selected from following one group: halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10Alkoxyl, cyano group, amide groups, imino group and silicyl.
26. method according to claim 20, wherein said alicyclic monomer are selected from following one group:
R wherein 1-4Be independently selected from C 1-10Alkyl.
27. method according to claim 20, wherein this die surface comprises front curved part and rear bending part, and this method also comprises the steps:
3) rear bending part with described lens mold, the front curved part of described lens mold is separated, wherein should the bending eyeglass and this front curved part movably adhere to.
28. method according to claim 20, wherein a kind of alicyclic co-polymer is contained in this front curved part, and the MFR of this alicyclic co-polymer is 11.0-18.0g/10min, and proportion is 1.01, glass transition temperature is 105 ℃, and polypropylene is contained in the rear bending part.
29. method according to claim 26, wherein a kind of alicyclic co-polymer is contained in the front curved part, the MFR of this alicyclic co-polymer is 11.0-18.0g/10min, proportion is 1.01, glass transition temperature is 105 ℃, and polypropylene and a kind of alicyclic co-polymer are contained in the rear bending part, and the MFR of this alicyclic co-polymer is 11.0-18.0g/10min, proportion is 1.01, and glass transition temperature is 105 ℃.
30. method according to claim 28, wherein alicyclic co-polymer is 20:80 to 80:20 with polyacrylic ratio in this rear bending part.
31. method according to claim 28, wherein alicyclic co-polymer is 55:45 with polyacrylic ratio in this rear bending part.
32. a mould, it contains a kind of alicyclic co-polymer and at least one forms the surface of eyeglass,
Wherein said alicyclic co-polymer polymerization is at least two kinds of alicyclic monomers with different chemical structures certainly, and
The surface of wherein said at least one formation eyeglass comprises the HMW coating composition that is coated with effective dose.
33. mould according to claim 32, described alicyclic co-polymer polymerization is from two kinds of alicyclic monomers, and wherein this alicyclic monomer contains saturated carbon ring.
34. mould according to claim 32, wherein said alicyclic monomer are selected from following one group:
Figure C03823975C00081
Figure C03823975C00082
With
Figure C03823975C00083
R in the formula 1-6Be independently selected from hydrogen, C 1-10Alkyl, halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10The C of alkoxyl, cyano group, amide groups, imino group, silicyl and replacement 1-10One or more in the alkyl are wherein at the C of described replacement 1-10In the alkyl substituting group be selected from following one group: halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10Alkoxyl, cyano group, amide groups, imino group and silicyl.
35. mould according to claim 32, wherein said alicyclic monomer are selected from following one group:
Figure C03823975C00091
With
Figure C03823975C00093
R in the formula 1-6In two or more constitute unsaturated bond or carbocyclic ring together.
36. mould according to claim 32, wherein said alicyclic monomer are selected from following one group:
Figure C03823975C00094
With
Figure C03823975C00095
R in the formula 1-6Be independently selected from hydrogen, C 1-10Alkyl, halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10The C of alkoxyl, cyano group, amide groups, imino group, silicyl and replacement 1-10One or more in the alkyl are wherein at the C of described replacement 1-10In the alkyl substituting group be selected from following one group: halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10One or more in alkoxyl, cyano group, amide groups, imino group and the silicyl.
37. mould according to claim 34, wherein R 1-6Be C 1-10Alkyl, or the C that replaces 1-10Alkyl, wherein said substituting group are selected from following one group: halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10Alkoxyl, cyano group, amide groups, imino group and silicyl.
38. mould according to claim 32, wherein said alicyclic monomer are selected from following one group:
Figure C03823975C00101
R wherein 1-4Be independently selected from C 1-10Alkyl.
39. mould according to claim 32, wherein this mould also contains a kind of additive.
40. according to the described mould of claim 39, wherein this additive is 2.0 percetage by weight zinc stearates.
41. according to the described mould of claim 39, wherein this additive is 2.0 percetage by weight glycerin monostearates.
42. according to the described mould of claim 39, wherein this coating composition contains a kind of coating additive.
43. according to the described mould of claim 39, wherein this additive is a kind of bactericidal composition.
44. the eyeglass that adopts a kind of method to produce, this method comprises 1) uncured eyeglass preparaton is distributed on the die surface, die surface contains a kind of alicyclic co-polymer, wherein said alicyclic co-polymer polymerization is at least two kinds of alicyclic monomers with different chemical structures certainly, and 2) described eyeglass preparaton is solidified.
45. according to the described eyeglass of claim 44, described alicyclic co-polymer polymerization is from two kinds of alicyclic monomers, wherein these alicyclic monomers contain saturated carbon ring.
46. according to the described method of claim 44, wherein said alicyclic monomer is selected from following one group:
Figure C03823975C00111
With
Figure C03823975C00113
R in the formula 1-6Be independently selected from hydrogen, C 1-10Alkyl, halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10The C of alkoxyl, cyano group, amide groups, imino group, silicyl and replacement 1-10One or more in the alkyl are wherein at the C of described replacement 1-10In the alkyl substituting group be selected from following one group: halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10Alkoxyl, cyano group, amide groups, imino group and silicyl.
47. according to the described eyeglass of claim 44, wherein said alicyclic monomer is selected from following one group:
Figure C03823975C00114
With
R in the formula 1-6Be independently selected from hydrogen, C 1-10Alkyl, halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10The C of alkoxyl, cyano group, amide groups, imino group, silicyl and replacement 1-10One or more in the alkyl are wherein at the C of described replacement 1-10In the alkyl substituting group be selected from following one group: halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10One or more in alkoxyl, cyano group, amide groups, imino group and the silicyl.
48. according to the described eyeglass of claim 46, wherein R 1-6Be C 1-10Alkyl, or the C that replaces 1-10Alkyl, wherein said substituting group are selected from following one group: halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10Alkoxyl, cyano group, amide groups, imino group and silicyl.
49. according to the described eyeglass of claim 44, wherein said alicyclic monomer is selected from following one group:
Figure C03823975C00121
R wherein 1-4Be independently selected from C 1-10Alkyl.
50. according to the described eyeglass of claim 44, wherein this uncured eyeglass preparaton contains the silicon hydrogel preparation.
51. according to the described eyeglass of claim 44, wherein this uncured eyeglass preparaton contains aqueogel.
52. according to the described eyeglass of claim 44, wherein this uncured eyeglass preparaton contains acquafilcon A, balafilcon A or lotrafilcon A preparation.
53. according to the described eyeglass of claim 44, wherein this uncured eyeglass preparaton contains etafilcon A, genfilcon A, lenefilcon A, polymacon, acquafilcon A, balafilconA, galyfilcon A, senofilcon A or lotrafilcon A preparation.
54. according to the described eyeglass of claim 44, wherein this uncured eyeglass preparaton contains acquafilcon A, balafilcon A, lotrafilcon A, galyfilcon A or senofilcon A preparation.
55. according to the described eyeglass of claim 44, wherein this die surface comprises front curved part and rear bending part.
56. according to the described eyeglass of claim 55, a kind of alicyclic co-polymer is contained in wherein said front curved part, and the MFR of this alicyclic co-polymer is 11.0-18.0g/10min, and proportion is 1.01, glass transition temperature is 105 ℃, and polypropylene is contained in the rear bending part.
57. according to the described eyeglass of claim 55, wherein a kind of alicyclic co-polymer is contained in the front curved part, the MFR of this alicyclic co-polymer is 11.0-18.0g/10min, proportion is 1.01, glass transition temperature is 105 ℃, and polypropylene and a kind of alicyclic co-polymer are contained in the rear bending part, and the MFR of this alicyclic co-polymer is 11.0-18.0g/10min, proportion is 1.01, and glass transition temperature is 105 ℃.
58. according to the described eyeglass of claim 55, wherein alicyclic co-polymer is 20:80 to 80:20 with polyacrylic ratio in this rear bending part.
59. according to the described eyeglass of claim 55, wherein alicyclic co-polymer is 55:45 with polyacrylic ratio in this rear bending part.
60. a production method that is coated with eyeglass, this method comprises:
(1) use the HMW coating composition that is coated with effective dose to be coated with the surface of at least one formation eyeglass of lens mold, wherein said lens mold contains alicyclic co-polymer and at least one forms the surface of eyeglass;
Wherein said alicyclic co-polymer polymerization is from least two kinds of alicyclic monomers with different chemical structures;
(2) uncured eyeglass preparaton is distributed on the surface of described at least one formation eyeglass; And
(3) under the condition that is suitable for forming the coating eyeglass, described eyeglass preparaton and described coating composition are solidified, it solidifies time of staying is below the 5min.
61. according to the described method of claim 60, described alicyclic co-polymer polymerization is from two kinds of alicyclic monomers, wherein these alicyclic monomers contain saturated carbon ring.
62. according to the described method of claim 60, wherein said alicyclic monomer is selected from following one group:
Figure C03823975C00131
Figure C03823975C00132
With
Figure C03823975C00133
R in the formula 1-6Be independently selected from hydrogen, C 1-10Alkyl, halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10The C of alkoxyl, cyano group, amide groups, imino group, silicyl and replacement 1-10One or more in the alkyl are wherein at the C of described replacement 1-10In the alkyl substituting group be selected from following one group: halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10Alkoxyl, cyano group, amide groups, imino group and silicyl.
63. according to the described method of claim 60, wherein said alicyclic monomer is selected from following one group:
With
Figure C03823975C00142
R in the formula 1-6Be independently selected from hydrogen, C 1-10Alkyl, halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10The C of alkoxyl, cyano group, amide groups, imino group, silicyl and replacement 1-10One or more in the alkyl are wherein at the C of described replacement 1-10In the alkyl substituting group be selected from following one group: halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10One or more in alkoxyl, cyano group, amide groups, imino group and the silicyl.
64. according to the described method of claim 62, wherein R 1-6Be C 1-10Alkyl, or the C that replaces 1-10Alkyl, wherein substituting group is selected from following one group: halogen, hydroxyl, C 1-10Alkoxy carbonyl group, C 1-10Alkoxyl, cyano group, amide groups, imino group and silicyl.
65. according to the described method of claim 60, wherein said alicyclic monomer is selected from following one group:
Figure C03823975C00143
R wherein 1-4Be independently selected from C 1-10Alkyl.
66. according to the described method of claim 60, wherein said HMW coating composition comprises polyvinyl alcohol, PEO, polymethylacrylic acid 2-hydroxy methacrylate, polymethyl methacrylate, polyacrylic acid, polymethylacrylic acid, poly, poly-itaconic acid, polyacrylamide, PMAm, polydimethylacrylamiin, the polymethyl acid glyceride, polystyrolsulfon acid, the polysulfonates polymer, PVP, the carboxy methylation polymer, polysaccharide, the Glucoamino glycan, the block of PLA or polyglycolic acid or above-mentioned polymer or random copolymer or its mixture.
67. according to the described method of claim 60, wherein said HMW coating composition comprises polymethylacrylic acid 2-hydroxy methacrylate, PVP, polyacrylic acid, polymethylacrylic acid, poly-(methyl) acrylamide or polyacrylamide or its mixture.
68. according to the described method of claim 60, wherein said HMW coating composition comprises polymethylacrylic acid 2-hydroxy methacrylate.
69. according to the described method of claim 60, wherein said HMW coating composition comprises polyvinyl alcohol, PEO, polymethylacrylic acid 2-hydroxy methacrylate, polymethyl methacrylate, polyacrylic acid, polymethylacrylic acid, poly, poly-itaconic acid, polyacrylamide, PMAm, polydimethylacrylamiin, the polymethyl acid glyceride, polystyrolsulfon acid, the polysulfonates polymer, PVP, the carboxy methylation polymer, polysaccharide, the Glucoamino glycan, the block of PLA or polyglycolic acid or above-mentioned polymer or random copolymer or its mixture.
70. according to the described method of claim 60, wherein said die surface comprises front curved part and rear bending part.
71. according to the described method of claim 70, wherein alicyclic co-polymer is contained in the front curved part, and polypropylene is contained in the rear bending part.
72. according to the described method of claim 70, wherein a kind of alicyclic co-polymer is contained in the front curved part, and a kind of alicyclic co-polymer and polypropylene are contained in the rear bending part.
73. according to the described method of claim 70, wherein a kind of alicyclic co-polymer is contained in the front curved part, the MFR of this alicyclic co-polymer is 11.0-18.0g/10min, and proportion is 1.01, and glass transition temperature is 105 ℃, and polypropylene is contained in the rear bending part.
74. according to the described method of claim 70, wherein a kind of alicyclic co-polymer is contained in the front curved part, the MFR of this alicyclic co-polymer is 11.0-18.0g/10min, proportion is 1.01, glass transition temperature is 105 ℃, and polypropylene and a kind of alicyclic co-polymer are contained in the rear bending part, and the MFR of this alicyclic co-polymer is 11.0-18.0g/10min, proportion is 1.01, and glass transition temperature is 105 ℃.
75. according to the described method of claim 74, wherein alicyclic co-polymer is 20:80 to 80:20 with polyacrylic ratio in the rear bending part.
76. according to the described method of claim 74, wherein alicyclic co-polymer is 55:45 with polyacrylic ratio in the rear bending part.
77. according to claim 66 or 69 described methods, wherein said carboxy methylation polymer is a carboxymethyl cellulose.
78. mould according to claim 5, wherein said carbocyclic ring are carbocyclic ring or the aromatic rings that contains one or more unsaturated bonds.
79. mould according to claim 23, wherein said carbocyclic ring are carbocyclic ring or the aromatic rings that contains one or more unsaturated bonds.
80. mould according to claim 35, wherein said carbocyclic ring are carbocyclic ring or the aromatic rings that contains one or more unsaturated bonds.
CNB038239752A 2002-08-16 2003-08-13 Molds for producing contact lenses Expired - Lifetime CN100519124C (en)

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