CN1064752A - Improved the soft gas permeable contact lens of clinical performance - Google Patents
Improved the soft gas permeable contact lens of clinical performance Download PDFInfo
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- CN1064752A CN1064752A CN91101622A CN91101622A CN1064752A CN 1064752 A CN1064752 A CN 1064752A CN 91101622 A CN91101622 A CN 91101622A CN 91101622 A CN91101622 A CN 91101622A CN 1064752 A CN1064752 A CN 1064752A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
- G02B1/043—Contact lenses
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Abstract
The hydrophilic ventilative soft contact lens that clinical performance has improved greatly is that the surface treatment of scioptics makes in the lens top layer and than the lens core ratio of sufficiently high hydroxyl propylene units to siloxane unit to be arranged.This surface treatment for example makes the lens surface reaction with polyvalent alcohol and alkali or acid, or by irradiation treatment, on lens surface, merge lens matrix, deposition or coating hydroxyl propylene units.
Description
The present invention relates to contact lens, more particularly, relate to the hydrophilic soft contact lens of the gas penetration potential of having improved clinical performance.
The most important performance of contact lens and be, oxygen permeability (the logical DK that is referred to as), good wettability and surface basically with anti-deposition to its requirement.
People extremely pay close attention to the plastic material that is used for contact lens and the exploitation and the use of composition for many years.
Exploitation the earliest is to use the so-called hard lenses of the rigid plastic of polymethylmethacrylate (PMMA).But the oxygen permeability of this material is not good, and its surface wettability is also very poor.After this technological development proceeds to the soft lens with polymethylacrylic acid 2-hydroxyl ethyl ester (poly-HEMA) again.This material oxygen permeability is better, and surface quality is also good than PMMA rigid plastic.But these performances are desirable not enough and can not satisfy the demand fully, and some serious problems usually appear in this lens: such as contamination, swelling, ulcer, muddiness and the infection etc. of cornea.
Not long ago, according to the further understanding of the good oxygen permeability of corneal needs, the present technique field proposes to use by a kind of plastic material in following two classes: so-called gas penetration potential hard (HGP) lens that polyacrylic acid siloxane or polyacrylic acid fluorosilicone are formed.For example referring to United States Patent (USP) 3,808,178.In general, the oxygen permeability of HGP lens can increase with the increase of siloxane in the composition and/or fluorosilicone content; But meanwhile, the surface wettability of lens is variation gradually thereupon also.For addressing this problem, knownly can in prescription, add quite a large amount of ionic material methacrylic acids (MAA), can make lens surface have to a certain degree negative charge.Although this expedient method can be improved surface wettability really, negative charged surface has very strong adsorbability, thereby causes serious deposition problems.Therefore, the HGP lens only obtain limited application.
Recently, developed hydrophilic soft gas permeable (SGP) lens, it is to use the composition that contains for example a kind of polymerisable ethene siloxanyl monomers and a kind of hydrophilic vinyl monomer.For example referring to United States Patent (USP) 4,136,250; 4,182,822; 4,261,875; 4,343,927; 4,426,389; 4,486,577; 4,605,712; 4,711,943 and 4,837,289.General moisture about 25%-75%(weight) this class SGP lens have good oxygen permeability and water wettability.But curiously, the clinical performance of SGP lens comprises: function wetting state (i.e. wetting state on eyes), anti-deposition properties, anti-dehydration performance and/or comfort are all very poor, so that this lens are unsuitable for long periods of wear.
Therefore, though made many effort up to now, still there is new demand in SGP class plastics contact lens, promptly it not only will have good oxygen permeability, and excellent clinical performance will be arranged: as function wetting state, anti-deposition properties and comfort.Like this, this lens just are suitable for long periods of wear.Fundamental purpose of the present invention that Here it is.
The present invention has realized above-mentioned and other purpose, and a kind of soft gas permeable contact lens of being made up of a kind of polymerizate of composition promptly is provided.Said composition contains a kind of polymerisable ethene siloxanyl monomers and a kind of hydrophilic vinyl monomer, in lens surface hydroxyl propylene monomer units siloxane unit there is certain ratio, this ratio is enough to make the SGP lens to have required high DK, flexibility and rebound resilience, make lens have clinical performance highly simultaneously, thereby these lens are suitable for the long periods of wear use highlightedly.
Be that by purpose the surface go up to increase the hydroxyl propylene monomer units and/or reduces the surface treatment of siloxane unit, can be implemented on the lens surface hydroxyl propylene monomer units necessary enough ratios of siloxane unit.In a preferred embodiment of the invention, can carry out surface treatment with one of two kinds of methods.A kind of method is to react at lens surface with polyvalent alcohol and/or alkali or acid.Other method is that lens are carried out irradiation treatment, merges, deposits at lens surface or coating hydroxyl propylene monomer units.
Should be pointed out that and provide or attempt to provide water-wetted surface on the hydrophobic lens relevant prior art and the present invention to have significantly different.Hydrophobic lens known in the art are to be made by silicon rubber (a kind of crosslinked polysiloxane), for example can be referring to United States Patent (USP) 3,228, and 741 explanation.The oxygen permeability of this hydrophobic lens is good, but its function wetting state, anti-deposition properties and comfort are all very poor, but also can cause mysterious airtight lens syndrome.Known in the artly can seek to improve the function wetting state of this lens by a kind of ultra-thin hydrophilic polymer coating is provided.For example referring to United States Patent (USP) 3,854,982; 3,916,033; 3,925,178 and 4,143,949.These effort all do not prove effective in general.A reason is that silicone lens is quite hard, thus ultra-thin (be dust
Level) hydrophilic coating just is easy to wipe in the cleaning operation of routine, the wetting state of these lens as a result, and anti-deposition properties, comfort degenerate very soon, the airtight syndrome of very fast again appearance.For the thickness that prevents to wipe erosion and increase hydrophilic polymer layer on the lens also is unpractiaca, because the oxygen permeability of lens will degenerate, and owing to the difference of the index of refraction between silicon rubber and the thick new aqueous polymer coating, the result makes this lens become very undesirable.
Lens of the present invention itself are to contain the big water gaging water of (for example generally containing 25%(weight at least)) hydrophilic SGP lens, thereby, different fully with silicone lens, its surface of lens of the present invention is very hydrophilic, there is no need provides one deck hydrophilic polymer surface coating according to about the instruction to hydrophobic lens material at all from the teeth outwards.Be surprisingly found out that in the present invention, even have very water-wetted surface SGP lens, its clinical performance is also still very poor, and this problem can solve by following method, the certain ratio of hydroxyl propylene units to siloxane unit promptly is provided on the SGP lens surface, and this ratio is enough to obviously improve clinical performance.
Contrasting with the processing of hydrophobic silicone lens, also find to improve by the hydrophilic monomer coating the employed standard of wetting state of these lens, is incoherent with the improvement to the clinical performance of hydrophilic SGP lens that obtains that the present invention endeavours.For example, for hydrophobic lens according to contact angle determination its acceptable wetting state (for example referring to United States Patent (USP) 4,143,949 the 7th hurdle 13-16 is capable), thereby find can to improve the wetting state embodiment 1-2 of above-mentioned patent (for example referring to) quite effectively with the coating of amide monomer (for example N-vinylpyridine alkane ketone).Under the situation of hydrophilic SGP lens of the present invention, under the situation of the lens that particularly preferred center thickness is 0.05-0.08mm, the monomer of this amide containing is invalid for the clinical performance that improves the SGP lens but in contrast.
Therefore, can not be guided out and give result of the present invention and the technology seen from known technology about the wetting state of improving hydrophobic silicone lens.
About basic skills, prescription and the technology of the manufacturing of siloxane SGP lens is known in the art, existing reflection in aforesaid patent, the disclosure of these patents is all clearly listed this paper in as a reference.The SGP lens are that the polymerizate by the composition that contains at least a polymerisable ethene siloxane (PVS) monomer and at least a hydrophilic vinyl monomer generates.Polymerisable ethene siloxanyl monomers contain at least a polymerisable thiazolinyl such as propylene, styrene or vinyl, at least a many siloxies with at least a with these two kinds of chains that group is connected;
Methacrylic acid three (trimethyl silica) silicon propyl group-glycerine-ethyl ester
Methacrylic acid-γ-three (trimethyl silica) silicon propyl ester (hereinafter also abbreviating TSM sometimes as)
The hydrophilic vinyl monomer that is applicable to SGP lens composition and PVS for example comprises: N,N-DMAA (NNDMA), methacrylic acid 2-hydroxyl ethyl ester (HEMA), glycerine methacrylate (GMA), N-vinyl pyrrolidone etc.
Lens itself with lathe cut, the casting molding, revolve the casting or other known technology make.
As previously mentioned, the SGP lens oxygen permeability of making by known formulations is good, but clinical performance is poor.Find among the present invention, improve lens surface hydroxyl propylene monomer (HAM) unit (preferably HEMA and/or GMA unit) and, just can improve clinical performance widely the ratio of siloxane unit.Be meant structure monomeric unit or silicon atom number as the unit therefor of mentioning herein, comprise those silicon atoms as a whole polymer architecture part.
Be applicable to that hydroxyl propylene monomer of the present invention (HAM) accords with following formula:
R is that hydrogen or one replace or unsubstituted alkyl in the formula, as methyl or CH
2COOH; With X be a group that is selected from the group group that hydroxyl alkoxy, hydroxyalkyl amine and hydroxyl form; And described replacement or unsubstituted alkyl are to be selected from C
1-C
10Alkyl, C preferably
2And C
3Alkyl; Hydroxyl on the described alkyl or monohydroxy (as the hydroxyl in 2-hydroxyethyl methacrylate) or polyhydroxy (as the hydroxyl in the glycerine acrylate).The example of preferred hydroxyl propylene monomer has:
1. acrylic acid 2-hydroxyl ethyl ester or methacrylic acid 2-hydroxyl ethyl ester;
2. the acrylate of glycerine or methacrylate;
3. the acrylate of a condensed ethandiol or methacrylate, promptly
CH
2＝CRCOO-CH
2-CH
2-O-CH
2-CH
2-OH;
4. an acrylate or a methacrylate that contracts glycerine, promptly
CH
2＝CRCOO-CH
2CH（OH）-CH
2-O-CH
2-CH（OH）-CH
2-OH;
5.N-methylol, the acrylamide of N-methyl or Methacrylamide;
6.N-2-hydroxyethyl, the acrylamide of N-methyl or Methacrylamide;
7.N-2,3-dihydroxypropyl, the acrylamide of N-methyl or Methacrylamide;
8. acrylic acid, methacrylic acid or itaconic acid.
As pointing out, SGP lens of the present invention are to be made by known SGP lens composition, making the back at lens handles it, make the ratio (for example increase HAM unit and/or reduce siloxane unit) of its surperficial HAM unit to siloxane unit, reach be enough to make lens clinical performance (as the function wetting state, anti-deposition properties, anti-dehydration and comfort) improve.
Making the HAM on surface and a kind of method that the amount of siloxane unit reaches required ratio is to be R with a kind of formula
1(OH)
nPolyvalent alcohol react at lens surface (being preferably in dewatering state).R in the following formula
1Be to replace or not substituted alkyl, preferably C
2-C
5Alkyl and n are at least 2 integer.Glycerine methacrylate for example, ethylene glycol, glycerine, the glycerine that contracts, polyglycerol etc.Reaction is preferably in alkali or acid or contains under the acid blend existence to be carried out.Described alkali is NaOH for example, and it is that the concentration of benchmark is preferably the 0.1-10%(mole with the polyvalent alcohol); Described acid or contain for example ethanol/sulfuric acid of acid blend.Above-mentioned reaction proceeds to such degree, and promptly the physical property (as intensity, oxygen permeability, flexibility, rebound resilience etc.) of lens matrix (base lens) is unaffected substantially.This reaction is to want to increase the HAM unit in the top layer and/or reduce siloxane unit by the cracking that is subjected to alkali or acid catalyzed silicon oxygen bond by transesterification.
Another kind method is, use HAM, preferably the acrylate of 2-hydroxyethyl or methacrylate are handled lens core body (core lens), by fusion, deposition or the coating at lens surface, make lens surface HAM unit reach enough numerical value to the ratio of siloxane unit.Can utilize known radiation-bring out reaction to merge, deposit and apply.Saidly bring out the electron beam irradiation that reaction comprises electromagnetic radiation such as ultraviolet, X-ray, gamma-radiation and other such as rf wave, microwave and comprises electron discharge etc.Wherein preferably ultraviolet, gamma-radiation or electron beam.It itself is known in the art can be used for treatment technology of the present invention, and for example by ultraviolet, the fusion of gamma-radiation or electron beam treatment, deposition or coating method be at United States Patent (USP) 3,916, existing explanation in 033 and 3,854,982; By the radiation treatment lens through revolve the casting or the casting molding coating; Or the Cement Composite Treated by Plasma technology, these treatment technologies are at United States Patent (USP) 3,925, and are disclosed in 178 and 4,143,949, all are that territory, present technique field is well-known.The present invention clearly lists the prior art of these patent disclosures in this paper as a reference.In a preferred embodiment of the invention, surface treatment makes lens surface produce the shallow layer of mainly being made up of poly-(acrylate of hydroxyalkyl and/or methacrylate), is more preferably the shallow layer of being made up of poly-(acrylate of 2-hydroxyethyl and/or methacrylate).
Providing the HAM unit that required enough ratios of siloxane unit are changed for producing required clinical performance at lens surface, mainly is to depend on the type of concrete PVS and quantity and employed hydrophilic monomer and decide.But no matter adopt which kind of ratio, in the ratio on top layer always than higher in the ratio of lens matrix or core.Be preferably in HAM unit, top layer the ratio of siloxane unit is at least 0.5.In general, ratio heal high lens clinical performance better, and the top layer of handling is thicker, the lens wetting state more can be durable.But processing layer can not be too thick, and too thick ideal performance to lens produces adverse influence.The surface-treated acceptable degree can be monitored with high-resolution electronic spectrograph (ESCA) or according to the clinical testing of being narrated among this instructions embodiment.Therefore, according to the present invention, those skilled in the art is easy to determine in lens surface HAM unit the enough ratios to siloxane unit.
Though do not want to be bound by any theory, but can suppose: improving to small part of lens clinical performance is owing to reach to compatible between the composition of the wetting mechanism of the sensitivity of eyes cornea and lens surface and the structure.Known SGP lens surface HAM unit is too high to the ratio of siloxane unit content not enough or siloxane unit, thereby too hydrophobic to cause mucus not disperse well and to adhere on the lens surface.Mucus is to be used for the best wetting agent of cornea and to contain the certain proportion of hydrophilic site to hydrophobic position.Along with the amount of lens surface HAM unit increase and increased with mucus on hydrophilic site generate the position of hydrogen bond, what siloxane unit was gone up on the surface simultaneously reduces just to provide still less hydrophobic position, thereby makes mucus be able to better dispersion at lens surface.In preferred version of the present invention, because lens surface HAM unit is enough high to the ratio of siloxane unit, thereby lens surface just is easier to accept tears mucus and closely contact with it.Mucus just can be disperseed better and be sticked to lens surface as a result, thereby clinical performance is improved, and like this, when the wetting angle of lens was controlled in the angle of no mucus anterior corneal surface, the present invention just obtained optimal results.
Further specify the present invention with reference to following embodiment.
Example 1
The SGP lens are by United States Patent (USP) 4 by a kind of, 182, the button base that 822 prescription and method obtain is made, consisting of of composition of raw materials: (trimethyl silica) the silicon propyl ester of methacrylic acid γ-three 36%(weight) (TSM), it is by example 1 preparation of above-mentioned patent, 59%(weight) N,N-DMAA (NNDMA) and 5%(weight) methyl methacrylate (MMA) (contain 0.3% t-butyl peroxy pivalate and make catalyzer).This formula mixture is placed teflon tube.After the logical nitrogen deoxygenation in 15 minutes,, in 40 ℃ of water-baths, made formula mixture generation polymerization in warm 6 hours, then handled again 6 hours at 100 ℃ with the seal of tube.Take out club and be cut into the button base, processing 6 hours is solidified in (0.5 holder) back under 100 ℃ of high vacuum.
Use machined into known in the art, can be made into lens.The lens of extraction hydration also soak the enough time in physiological saline, guarantee can not cause infection.
The lens DK value of making like this is high, approximately doubly than the conventional high 4-5 of the soft lens of poly-HEMA, and moisture about 50%(weight), thereby have flexibility, the lens surface of rebound resilience and highly-hydrophilic.Is zero in lens surface HAM unit to the ratio of siloxane unit.Clinically, its performance: all very poor as function wetting state, anti-deposition and comfort, thereby be not suitable for wearing for a long time.
If HEMA adding 6%(weight in prescription), like this, prescription just comprises 36%TSM, 58%NNDMA and 6%HEMA, can obtain high DK, flexibility, rebound resilience, high water-wetted surface and HAM unit is 0.15 lens to the ratio of siloxane unit, thereby with above-mentioned, the lens that are used to contrast are compared, these improved SGP lens, its clinical performance: function wetting state, anti-deposition and comfort all are improved.Clinically, tried patient wear, wear life reaches several hrs.
Use same quadrat method, but HEMA use 20%(weight), like this, prescription just contains: 36%TSM, 44%NNDMA and 20%HEMA, can obtain high DK, flexibility, rebound resilience, high water-wetted surface and HAM unit is 0.5 lens to the ratio of siloxane unit, and compare clinical performance with the above-mentioned lens that are used to contrast: function wetting state, anti-deposition and comfort are better improved.Clinically, worn continuously to trying the patient, wear life reaches several days, but wetting state has just arrived unacceptable degree in some cases.
If further improve the ratio of HAM to siloxane, just need to increase the amount of HEMA in the composition, like this, will sacrifice TSM, thereby reduce the oxygen permeability of lens and/or form opaque materials.And from following embodiment as can be seen, further improve HAM and can obtain by surface treatment the ratio of siloxane.
Example 2
The lens of making by example 1 that contain 20% HEMA are in physiological saline after the hydration, in isopropyl alcohol, extracted 24 hours, then under drying regime with containing the 1%(mole) glycerine (purity 96%Calgate Palmolive company products) of NaOH do not stop to stir ground processing 30 minutes at 70 ℃.After the processing, the intensity of lens is not subjected to tangible influence.The lens that obtain are reached at least in week to trying the patient wear wear life.The clinical testing of the long periods of wear that a patient is carried out shows, this lens can be worn for some patient at least really continuously, and wear life is for 3 months.Therefore surface treatment has improved clinical performance greatly.
Example 3
Found to form and comprised 47%(weight) TSM, 45%NNDMA and 8% HEMA, liquid water content are 38%, and to have high DK value, flexibility, high hydrophilic lens surface and HAM unit be that 0.15 SGP lens are unsuitable for long periods of wear to the ratio of siloxane unit.Through clinical testing, this lens wear that the visual field is unclear less than just producing in 4 hours, sense of discomfort and serious deposition problems.But with these same lens at dewatering state through containing the 10%(mole) the glycerine reagent (purity 96% of NaoH, Colgate Palmolive company produces) in stir 2 hours processing 70%, just change another lens into, these lens are still undertaken wearing test by week by the identical patient that tried, eyesight is stable always in three experimental periods in week, and not observing deposition and confirming all has liquid layer at whole lens surface.
Example 4
The independently surface of analyzing with electronic spectrograph (ESCA) by the lens of example 3 described processing (about 100
Superficial layer) research, the result proves: after the processing, siloxane reduced about 18% or siloxy reduced about 30%; Increased 62.5-65.0% with total carbon content, wherein the carbon that increased in 10.5-12.5% and the COOR base of the carbon in the CO base has increased 5.3-6.3%.The increase of CO and COOR content should show: the transesterification of glycerine takes place, has promptly generated the glycerine methacrylate.The minimizing of siloxane unit and/or the increase of glycerine methacrylate unit have just improved the ratio of HAM unit to siloxane unit, thereby the foregoing obvious improved clinical performance that has are provided after handling.(annotate: the ESCA data are 100
The mean value of the treatment surface of the degree of depth.Therefore the true value on the surface is the numerical value far above above-mentioned report).
Example 5
According to United States Patent (USP) 4,182,822 use the 36%(weight) the unhydrated lens button base of the optical polish made of TSM, 42%NNDMA and 22%HEMA uses the method that proposes by this paper example 3 to carry out the glycerine surface treatment.Make the abundant hydration of button base in physiological saline, carry out a series of simulation washing tests then, each test comprises: wipe 10 times with thumb in tap water, it is wetting to put into physiological saline again.Use visual inspection behind 60 washing tests, the surface wettability of handling by physiological saline is essentially identical, and this is equivalent to be approximately 1 year the serviceable life that lens wear by Zhou Lianxu.
And under same test condition, not carrying out surface-treated button base surface by the present invention basically can not be wetting by physiological saline institute.
Though the present invention is described in conjunction with concrete preferred embodiment, is not meant to limit the present invention within the concrete form that is proposed.Antithesis, for including among the present invention in spirit of the present invention that claims limited and some variations, modification and the equivalent within the protection domain.
Claims (17)
1, a kind of ventilative hydrophilic soft contact lens, these lens have high oxygen permeability, flexibility and rebound resilience, polymerizate by the composition that contains polymerisable ethene siloxanyl monomers and hydrophilic vinyl monomer is formed, contain the ratio of sufficiently high hydroxyl propylene monomer units on the lens top layer than lens matrix, thereby the clinical performance of described contact lens is improved significantly siloxane unit.
2, according to the contact lens of claim 1, wherein said sufficiently high ratio is because to the surface treatment of described lens, makes just that the hydroxyl propylene monomer units reaches enough ratio to siloxane unit in the top layer.
3, according to the contact lens of claim 2, wherein said hydroxyl propylene monomer is acrylic acid hydroxy alkyl ester and/or hydroxyalkyl methacrylate.
4, according to the contact lens of claim 3, wherein said processing comprises uses formula R
1(OH)
nPolyvalent alcohol react R in the formula at lens surface
1Be that a replacement or unsubstituted alkyl and n are one and are at least 2 integer.
5, according to the contact lens of claim 4, wherein said polyvalent alcohol is selected from ethylene glycol, glycerine and composition thereof.
6, according to the contact lens of claim 2, wherein said processing is included in described lens surface by radiation-bring out reaction, and the hydroxyl propylene monomer is reacted.
7, according to the contact lens of claim 6, wherein said hydroxyl propylene monomer is acrylic acid hydroxy alkyl ester and/or hydroxyalkyl methacrylate.
8, according to the contact lens of claim 7, wherein said radiation is electromagnetic radiation.
9, according to the contact lens of claim 7, wherein said radiation is gamma-radiation or ultraviolet ray.
10, according to the contact lens of claim 7, wherein said radiation is to be selected from electron beam, electron discharge and rf wave.
11, according to the contact lens of claim 7, wherein said polymerizable ethene siloxanyl monomers is that methyl-prop acrylic acid-γ-three (trimethyl silica) silicon propyl ester and wherein said hydrophilic vinyl monomer are N, N methacrylamide.
12, according to the contact lens of claim 3, wherein said acrylic acid hydroxy alkyl ester and/or hydroxyalkyl methacrylate are to be selected from methacrylic acid 2-hydroxyl ethyl ester and glycerine methacrylate.
13, according to the contact lens of claim 12, wherein said polymerisable ethene siloxanyl monomers is that methacrylic acid-γ-three (trimethyl silica) silicon propyl ester and wherein said hydrophilic vinyl monomer are N,N-DMAAs.
14, according to the contact lens of claim 7, wherein said outer reason produces the shallow layer of being made up of poly-(acrylic acid hydroxyalkyl acrylate and/or methacrylic acid hydroxyl Arrcostab) substantially at described lens surface.
15, according to the contact lens of claim 14, wherein said poly-(acrylic acid hydroxyalkyl acrylate and/or methacrylic acid hydroxyl Arrcostab) is poly-(acrylic acid 2-hydroxyl ethyl ester and/or methacrylic acid 2-hydroxyl ethyl ester).
16, according to the contact lens of claim 11, wherein said processing produces the shallow layer of being made up of poly-(acrylic acid hydroxyalkyl acrylate and/or methacrylic acid hydroxyl Arrcostab) substantially at described lens surface.
17, according to the contact lens of claim 16, wherein said poly-(acrylic acid hydroxyalkyl acrylate and/or methacrylic acid hydroxyl Arrcostab) is poly-(2-hydroxypropyl olefin(e) acid 2-hydroxyl ethyl ester and/or methacrylic acid 2-hydroxyl ethyl ester).
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2512563A JPH04501882A (en) | 1989-09-14 | 1990-09-07 | Flexible gas permeable contact lenses with improved clinical performance |
| PCT/US1990/005032 WO1991004283A1 (en) | 1989-09-14 | 1990-09-07 | Soft gas permeable contact lens having improved clinical performance |
| EP19900913584 EP0443005A4 (en) | 1989-09-14 | 1990-09-07 | Soft gas permeable contact lens having improved clinical performance |
| KR1019910700493A KR920701271A (en) | 1989-09-14 | 1990-09-07 | Gas Permeable Soft Contact Lenses with Improved Clinical Performance |
| CN91101622A CN1064752A (en) | 1989-09-14 | 1991-03-13 | Improved the soft gas permeable contact lens of clinical performance |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US40726189A | 1989-09-14 | 1989-09-14 | |
| US55115690A | 1990-07-11 | 1990-07-11 | |
| CN91101622A CN1064752A (en) | 1989-09-14 | 1991-03-13 | Improved the soft gas permeable contact lens of clinical performance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1064752A true CN1064752A (en) | 1992-09-23 |
Family
ID=67840865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91101622A Pending CN1064752A (en) | 1989-09-14 | 1991-03-13 | Improved the soft gas permeable contact lens of clinical performance |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0443005A4 (en) |
| JP (1) | JPH04501882A (en) |
| KR (1) | KR920701271A (en) |
| CN (1) | CN1064752A (en) |
| WO (1) | WO1991004283A1 (en) |
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| TW585882B (en) * | 1995-04-04 | 2004-05-01 | Novartis Ag | A method of using a contact lens as an extended wear lens and a method of screening an ophthalmic lens for utility as an extended-wear lens |
| US6329024B1 (en) | 1996-04-16 | 2001-12-11 | Board Of Regents, The University Of Texas System | Method for depositing a coating comprising pulsed plasma polymerization of a macrocycle |
| US6482531B1 (en) | 1996-04-16 | 2002-11-19 | Board Of Regents, The University Of Texas System | Non-fouling, wettable coated devices |
| US8039026B1 (en) | 1997-07-28 | 2011-10-18 | Johnson & Johnson Consumer Companies, Inc | Methods for treating skin pigmentation |
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| US6849671B2 (en) | 1998-03-02 | 2005-02-01 | Johnson & Johnson Vision Care, Inc. | Contact lenses |
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| US6822016B2 (en) | 2001-09-10 | 2004-11-23 | Johnson & Johnson Vision Care, Inc. | Biomedical devices containing internal wetting agents |
| US6087415A (en) | 1998-06-11 | 2000-07-11 | Johnson & Johnson Vision Care, Inc. | Biomedical devices with hydrophilic coatings |
| US6500481B1 (en) | 1998-06-11 | 2002-12-31 | Johnson & Johnson Vision Care, Inc. | Biomedical devices with amid-containing coatings |
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| CS154977B1 (en) * | 1971-10-08 | 1974-04-30 | ||
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| US4861840A (en) * | 1986-12-03 | 1989-08-29 | Barnes-Hind, Inc. | Novel siloxanyl acrylic monomer and gas-permeable contact lenses made therefrom |
| US4734475A (en) * | 1986-12-15 | 1988-03-29 | Ciba-Geigy Corporation | Wettable surface modified contact lens fabricated from an oxirane containing hydrophobic polymer |
-
1990
- 1990-09-07 KR KR1019910700493A patent/KR920701271A/en not_active Application Discontinuation
- 1990-09-07 EP EP19900913584 patent/EP0443005A4/en not_active Ceased
- 1990-09-07 WO PCT/US1990/005032 patent/WO1991004283A1/en not_active Application Discontinuation
- 1990-09-07 JP JP2512563A patent/JPH04501882A/en active Pending
-
1991
- 1991-03-13 CN CN91101622A patent/CN1064752A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| KR920701271A (en) | 1992-08-11 |
| JPH04501882A (en) | 1992-04-02 |
| EP0443005A4 (en) | 1992-02-19 |
| WO1991004283A1 (en) | 1991-04-04 |
| EP0443005A1 (en) | 1991-08-28 |
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