CN101688042A - Silicone-hydrogel compound for soft contact lens and soft contact lens produced using the compound - Google Patents
Silicone-hydrogel compound for soft contact lens and soft contact lens produced using the compound Download PDFInfo
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- CN101688042A CN101688042A CN200780053507A CN200780053507A CN101688042A CN 101688042 A CN101688042 A CN 101688042A CN 200780053507 A CN200780053507 A CN 200780053507A CN 200780053507 A CN200780053507 A CN 200780053507A CN 101688042 A CN101688042 A CN 101688042A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/14—Eye parts, e.g. lenses, corneal implants; Implanting instruments specially adapted therefor; Artificial eyes
- A61F2/16—Intraocular lenses
-
- 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
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
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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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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
Abstract
The present invention relates to a silicone hydrogel composition for a soft contact lens and a soft contact lens using the same which comprises silicone N,O-bis(trimethylsilyl)acrylamide monomer and 2-hydroxyethyl methacrylate added with water soluble N-vinyl-2-pyrrolidone or N,N-dimethylacrylamide monoer to improve hydrophilic property and a cross-linking agent such as ethylene glyx>l dimethacrylate or divinyl benzene to provide a hydrophilic property, high water content rate, high oxygen permeability, good elongation and optical transmission.
Description
Technical field
The present invention relates to a kind of silicone-hydrogel (silicone hydrogel) soft contact lens (soft contactlens), more specifically, the present invention relates to a kind of soft contact lens that is used for the silicone-hydrogel composition of soft contact lens and uses this silicone-hydrogel composition, wherein, described silicone-hydrogel composition contains monomeric 2-hydroxyethyl methacrylate and the N as silicone resin, two (trimethyl silyl) acrylamides of O-.
Background technology
Usually, contact lens divide for by methacrylic ester (MMA) as the rigid glasses of basic material with by the soft glasses of 2-hydroxyethyl methacrylate (HEMA) as basic material, wherein soft contact lens has obtained increasingly extensive application owing to have higher relatively oxygen permeability (oxygen permeability) and water ratio.Because HEMA has hydroxyl (typical hydrophilic molecule structure), and therefore different with MMA, HEMA has higher water ratio (Refojo et., J.appl.Poly.Sd., 9:2425 (1965)), this is possible in monomer.
Simultaneously, hydrogel is a kind of crosslinked polymer, it have high moisture equilibrium and widely physiology use, for example be used to make contact lens the medical science macromolecular material (reference: United States Patent (USP), No.4300820).
At present, the hydrogel that is used for contact lens comprises usually as monomeric 2-hydroxyethyl methacrylate, be mixed with a spot of linking agent in this monomer, and this monomer is heat polymerization (radical thermal polymerization) the preparation contact lens by free radical.Because the character of material, the contact lens made from above-mentioned materials have about 40% water ratio, and these contact lens are hydrophilic and flexible, can bring less foreign body sensation and lower to the pressure of cornea to the user during use.Yet the bad mechanical strength of this contact lens has limited about 10Dk[10
-11Cm
2/ sec] (ml O
2MmHg) oxygen permeability has protein attachment (Wilson et al., Encyclo.Of Chem.Tech., 7:192 (1976) on the glasses when user wears for a long time; And U.S. Patent No. 6096138).
Be well known that, contact lens wear comfort level and its water ratio is closely related, be to improve the water ratio of contact lens, the investigator has done a lot of trials, some is commercialization.Concrete, a kind of water ratio reaches 80%, oxygen permeability reaches 40Dk[10
-11Cm
2/ sec] (ml O
2MmHg) high-grade products are successfully developed, and this product adopts N-vinyl-2-Pyrrolidone (NVP) and N,N-DMAA (DMA) as water-soluble monomer.But this contact lens with high-moisture percentage are easy to become dry, and the optical correction ability of material, and it is inconvenient that the user can feel when wearing and extract.Therefore, the higher contact lens of this water ratio mainly can not be worn (Refojo.et al., Cont.﹠amp for a long time as day throwing type; Intracular Lens Med.J., 1:36 (1975)).
Be commonly used to make RGP (rigid gas permeable, rigidity and ventilation property) the methacrylic acid macromolecular material that contains siloxanes or fluorine of contact lens, can provide good wearing to feel and higher oxygen permeability, the influence of corneal is little, even the material of using is harder, its stability is also fine.In addition, compare with the polymethylmethacrylate that routine is used, the side effect that the methacrylic acid polymer causes is also less.Yet the macromolecular material that contains siloxanes or fluorine is typical hydrophobic material, when being used for making contact lens, can not bedewed by tears.Because the RGB contact lens have certain rigidity and the shape of self, thereby can be owing to cornea being deformed and making the mobile variation of tears cause some side effects or complication.Also have, the intensity difference of RGB contact lens is difficult to make, and this can cause the cost height, easily contaminated and damage when wearing.
For these problems that exist in the contact lens that solve widespread use, use silicone resin to make a kind of soft contact lens (softish silicone hydrogel contact lens) that contains hydrogel, wherein said hydrogel has higher oxygen permeability.1998, this contact lens were put on market first, and the share of market sharp increase reached about 1.5 hundred million sales volume (Optician 2005) to 2003.
The silicone-hydrogel of producing is hydrophilic monomer (as HEMA) and the polymer of monomers that contains silicone resin.Usually the monomeric hydrophobicity of silicone resin is very strong, and when with hydrophilic monomer (as HEMA) polymerization owing to phase separation is difficult to keep visibility.In order to overcome these problems, should develop a kind of expanding material (compatibilizer) to be used to improve the consistency between hydrophobic monomer and the hydrophilic monomer.PBVC (poly-[dimethyl-silicon alcoxyl base] two [silyl butanols] two [vinyl carbamates]) and silicone resin macromonomer (silicone macromer) can be used as expanding material, but its cost of development height, and, be difficult to be used for making contact lens because its molecular weight is big and the viscosity height.
Usually, silicone resin is hydrophobic, and the application in the gel-type contact lens is limited, because it can reduce water ratio.Because the surface of contact lens is hydrophobic, it is hydrophilic to become that oxygen plasma treatment should be carried out by last handling process in its surface, can avoid occurring when wearing contact lens the problems referred to above thus.But brought another problem thus, promptly protein attachment is on the surface of contact lens.
Because the character of the material of silicone-hydrogel own, so its poor ductility, when being used as contact lens, restorability is poor during distortion.Along with the hydrophobicity of contact lens surface strengthens because of silicone resin, the epithelium of cornea and contact lens fit (compatible), glasses are attached on the cornea.
Summary of the invention
Therefore, one aspect of the present invention is by making hydrophobicity silicone resin monomer and hydrophilic monomer polymerization, thereby makes silicone resin monomer possess hydrophilic property improve the oxygen permeability of contact lens.
Another aspect of the present invention provides silicone-hydrogel composition that is used for soft contact lens and the soft contact lens that uses this silicone-hydrogel composition, wherein, said composition is by adding N-vinyl-2-Pyrrolidone (NVP＞99%:Aldrich) or N in right amount, N-DMAA (DMA, Aldrich) contain water, good light transmission (opticaltransmission) is provided under the situation of not using expanding material, even do not pass through other surface treatment, when wearing, can not have problems yet.
By a kind of silicone-hydrogel composition that is used for soft contact lens is provided, aforementioned and/or other aspects of the present invention have been realized, the N that said composition contains methacrylic acid 2-hydroxyl ethyl ester and is shown below, the silicone resin monomer of two (trimethyl silyl) acrylamides of O-:
Chemical formula 1
According to a further aspect in the invention, N, the two content of (trimethyl silyl) acrylamide in composition of O-are below the 10 weight %.
According to a further aspect in the invention, described composition contains Ethylene glycol dimethacrylate.
According to a further aspect in the invention, in the described composition, N, the content of two (trimethyl silyl) acrylamides of O-is below the 10 weight %, the content of Ethylene glycol dimethacrylate is below the 0.5 weight %.
According to a further aspect in the invention, described composition contains Vinylstyrene.
According to a further aspect in the invention, in the described composition, N, the content of two (trimethyl silyl) acrylamides of O-is below the 10 weight %, the content of Vinylstyrene is below the 0.4 weight %.
According to a further aspect in the invention, described composition contains any one in N-vinyl-2-Pyrrolidone and the N,N-DMAA.
According to a further aspect in the invention, N, the content of two (trimethyl silyl) acrylamides of O-is below the 5 weight %, and the content of Ethylene glycol dimethacrylate is below the 0.4-0.7 weight %, and the content of N-vinyl-2-Pyrrolidone is below the 45 weight %.
According to a further aspect in the invention, described composition contains N-vinyl-2-Pyrrolidone.
According to a further aspect in the invention, in the described composition, N, the content of two (trimethyl silyl) acrylamides of O-is below the 5 weight %, the content of Vinylstyrene is below the 0.3-0.5 weight %, and the content of N-vinyl-2-Pyrrolidone is below the 35 weight % in the composition.
According to a further aspect in the invention, described composition contains N,N-DMAA.
According to a further aspect in the invention, in the described composition, N, the content of two (trimethyl silyl) acrylamides of O-is below the 5 weight %, the content of Ethylene glycol dimethacrylate is below the 0.4 weight %, and the content of N,N-DMAA is below the 40 weight %.
According to a further aspect in the invention, described composition contains N,N-DMAA.
According to a further aspect in the invention, in the described composition, N, the content of two (trimethyl silyl) acrylamides of O-is below the 5 weight %, and the content of Vinylstyrene is below the 0.4 weight %, and the content of N,N-DMAA is below the 30 weight %.
By a kind of soft contact lens of being made by described composition is provided, aforementioned and/or other aspects of the present invention have been realized.
As mentioned above, be used to make the silicone-hydrogel composition of soft contact lens and use the soft contact lens of making according to composition of the present invention, provide a kind of and can directly be worn on the eyes with myopia correction, long sight and contact lens astigmatic and that regulate eyesight.According to the present invention, this soft contact lens possess hydrophilic property made from silicone-hydrogel and water ratio are up to 40-70%; Oxygen permeability is up to 50-100DK; Ductility is 200-400%; And good light transmission; Make eye health; The pressure of foreign body sensation, dry sensation and corneal is reduced to minimum, so that the wearer feels comfortable.In addition, this contact lens can reduce corneal edema or other diseases odds.
In addition, according to the present invention, the soft contact lens made from silicone-hydrogel have that high oxygen flow hard contact lens (RGP contact lens) had high oxygen permeability and soft contact lens had wears comfort, can wear fortnight to month continuously, solve the shortcoming that existing contact lens need every day and wear and extract.
Other aspects and the advantage of thought of the present invention will be described hereinafter, and these contents can draw apparently from specification sheets of the present invention or can learn by implementing thought of the present invention.
Embodiment
The present invention relates to a kind of polymkeric substance, this polymkeric substance makes by following steps: following substances is mixed: as hydrophilic monomer 2-hydroxyethyl methacrylate (the BISOMER HEMAULTRA of main raw, Cognis makes), as the monomeric N of silicone resin, two (trimethyl silyl) acrylamides of O-(oneself is synthetic), they are used to increase oxygen permeability; The water-soluble monomer of N-vinyl-2-Pyrrolidone (NVP＞99%, Aldrich makes) or N,N-DMAA (DMA made by Aldrich), they are used to increase wetting ability; A small amount of Ethylene glycol dimethacrylate (EGDMA＞98%, Aldrich makes) or Vinylstyrene (DVB＞80%, Aldrich makes) as linking agent; Pass through then as 2 of radical initiator (radical initiator), 5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane carries out thermopolymerization.This polymkeric substance has long molecular structure, wherein, is called as monomeric junior unit and repeatedly connects mutually and have these monomeric chemical bonds (three-dimensional structure).
The contact lens that the present invention makes do not need through special surface treatment, because it has the water ratio of 40-70%, and possess hydrophilic property.The present invention does not use expanding material.Though have very high water ratio, these contact lens are not easy to wear, can wear fortnight.
Many clinical trials show that the oxygen permeability of silicone hydrogel contact lens of the present invention is up to 50-100Dk ([10
-11(cm
2/ sec) (ml O
2MmHg)], and be free from side effects, provide comfortable and worn sensation and wear without any problem for a long time.
The shortcoming of silicone hydrogel contact lens is improved, and the result is as follows.
The ductility of silicone hydrogel contact lens of the present invention is 200-400%, and Young's modulus (youngmodulus) is 50-65g/mm
2, tensile strength is 80-110g/mm
2, toughness is 120-145g/mm
2, for contact lens, these parameters are very outstanding.
Below by embodiments of the present invention and exemplary accompanying drawing, the present invention will be described in more detail, and reference number similar in the literary composition is represented identical implication.The embodiment that hereinafter provides is used for setting forth in conjunction with the drawings the present invention.
Embodiment 1
N, the polymerization of two (trimethyl silyl) acrylamides of O-and 2-hydroxyethyl methacrylate
N, the amount of two (trimethyl silyl) acrylamides of O-is increased to 90g from 10g, increases 10g at every turn, and the amount of 2-hydroxyethyl methacrylate reduces to 10g from 90g, reduces 10g at every turn, makes mixture thus.The initiator 2 of dissolving 0.1-1g, 5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane is to make polymerization of mixtures 30 minutes at 110 ℃.
The result shows, when initiator that uses 0.2g (0.2 weight %) and above-mentioned substance, no matter the content of initiator is what, polymerization takes place, but initiator has nothing to do with transparency (consistency) all.Use the above N of 10g (10 weight %), during O-pair of (trimethyl silyl) acrylamide, mixture solidifies, but consistency is relatively poor, and has become the color of opaque milk.N, the consumption of two (trimethyl silyl) acrylamides of O-is many more, solidifies difficult more generation.Like this, polymkeric substance becomes soft.
Preferably, the amount of the initiator that uses is 0.2g (0.2 weight %) during polymerization.Because N, two (trimethyl silyl) acrylamides of O-have higher degree of crosslinking, so do not need linking agent during mixture solidified.Use the N of 2-hydroxyethyl methacrylate and 10g (10 weight %), during O-pair of (trimethyl silyl) acrylamide monomer, consistency (transparency) is better.
Embodiment 2
N, the polymerization of two (trimethyl silyl) acrylamides of O-and N-vinyl-2-Pyrrolidone
N, the amount of two (trimethyl silyl) acrylamides of O-is increased to 90g from 10g, increases 10g at every turn, and the amount of N-vinyl-2-Pyrrolidone reduces to 10g from 90g, reduces 10g at every turn, makes mixture thus.The initiator 2 of dissolving 0.1-1g, 5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane is to make polymerization of mixtures 30 minutes at 110 ℃.
The result shows no matter use the content of initiator what are, mixture does not all solidify.N, the consumption of two (trimethyl silyl) acrylamides of O-is high more, solidifies difficult more generation.Like this, during promptly convenient polymerization, the mixture thickness must look like tackiness agent, and mixture can not solidify yet.
In the polymerization of present embodiment, though N, two (trimethyl silyl) acrylamides of O-and water-soluble monomer N-vinyl-2-Pyrrolidone generation polymerization, polymkeric substance can not solidify yet.Such mixture discomfort is fit to do contact lens, and needs linking agent that it is solidified.
Embodiment 3
N, the polymerization of two (trimethyl silyl) acrylamides of O-, 2-hydroxyethyl methacrylate and Ethylene glycol dimethacrylate
N, the amount of two (trimethyl silyl) acrylamides of O-is increased to 90g from 10g, increases 5g at every turn, and the amount of 2-hydroxyethyl methacrylate reduces to 50g from 90g, each 5g that reduces, the linking agent Ethylene glycol dimethacrylate of in mixture, adding 0.1-1g again.The initiator 2 of dissolving 0.2g, 5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane makes mixture 110 ℃ of polyase 13s 0 minute.
The result shows that along with the increase of Ethylene glycol dimethacrylate consumption, transparency of polymkeric substance (consistency) and ability to cure improve thereupon, but the ductility variation.For making polymkeric substance be suitable for making contact lens, the amount that needs the adding Ethylene glycol dimethacrylate is 0.5g (0.5 weight % is following).Work as N, the consumption of two (trimethyl silyl) acrylamides of O-is when 20 weight % are following, and polymkeric substance solidifies, and become transparent, but N, the consumption of two (trimethyl silyl) acrylamides of O-is when 10-20 weight % is following, after the polymer hydration effect, water-intake rate reduces.N, the consumption of two (trimethyl silyl) acrylamides of O-are 20 weight % when above, and obviously curing takes place polymkeric substance, but the opaque and easy fragmentation that becomes after the hydration.
In the polyreaction of present embodiment, use the linking agent Ethylene glycol dimethacrylate to improve the degree of crosslinking and the transparency (consistency) of polymkeric substance, increase ability to cure and intensity simultaneously.Known, when adding the Ethylene glycol dimethacrylate of 0.5 weight %, the polymkeric substance suitable for making contact lens that obtain.
If use the following N of 10 weight %, during the following linking agent Ethylene glycol dimethacrylate generation polymerization of 2-hydroxyethyl methacrylate that two (trimethyl silyl) acrylamides of O-, 90 weight % are above and 0.5 weight %, can improve the consistency of polymkeric substance, and obvious curing can take place in polymkeric substance, hydration can take place well, and this polymkeric substance is the flexible contact lens of suitable for making to a certain extent.
Embodiment 4
N, the polymerization of two (trimethyl silyl) acrylamides of O-, 2-hydroxyethyl methacrylate and Vinylstyrene
N, the consumption of two (trimethyl silyl) acrylamides of O-is increased to 90g gradually from 10g, increases 5g at every turn, and the consumption of 2-hydroxyethyl methacrylate reduces to 5g gradually from 90g, each 5g that reduces, the linking agent Vinylstyrene of interpolation 0.1-1g in mixture again.The initiator 2 of dissolving 0.2g, 5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane makes mixture 110 ℃ of polyase 13s 0 minute.
The result shows that along with the increase of Vinylstyrene consumption, transparency of polymkeric substance (consistency) and ability to cure improve thereupon, but the ductility variation.For making polymkeric substance be fit to make contact lens, needing the amount of adding Vinylstyrene is below the 0.4g (0.4 weight %).Work as N, the consumption of two (trimethyl silyl) acrylamides of O-is 20 weight % when following, and polymkeric substance solidifies, and become transparent, but N, the consumption of two (trimethyl silyl) acrylamides of O-is when 10-20 weight % is following, after the polymer hydration effect, water-intake rate reduces.N, the consumption of two (trimethyl silyl) acrylamides of O-are 20 weight % when above, and obviously curing takes place polymkeric substance, but the opaque and easy fragmentation that becomes after the hydration.
In the polyreaction of present embodiment, use the linking agent Vinylstyrene to improve the degree of crosslinking and the transparency (consistency) of polymkeric substance, increase ability to cure and intensity simultaneously.Known, the amount that adds Vinylstyrene when 0.4 weight % is following, the polymkeric substance suitable for making contact lens that obtain.
Compare with the Ethylene glycol dimethacrylate of using among the embodiment 3, present embodiment uses Vinylstyrene, and the consistency (transparency) that obtains polymkeric substance is better.
Embodiment 5
N, the polymerization of two (trimethyl silyl) acrylamides of O-, 2-hydroxyethyl methacrylate, N-vinyl-2-Pyrrolidone and Ethylene glycol dimethacrylate
Reference example 3, in the polymeric process, the water ratio of telomerized polymer is controlled the process of polymerizable raw material to improve its wetting ability by adding water-soluble monomer N-vinyl-2-Pyrrolidone.
N, the consumption of two (trimethyl silyl) acrylamides of O-is increased to 50 weight %90g gradually from 5 weight %, each 5 weight % that increase, the consumption of 2-hydroxyethyl methacrylate reduces gradually from 90 weight %, each 5 weight % that reduce, the consumption of N-vinyl-2-Pyrrolidone increases gradually from 5 weight %, increases by 5 weight % at every turn, adds the linking agent Ethylene glycol dimethacrylate of 0.1-1 weight % again in mixture.Dissolve the initiator 2 of 0.2 weight %, 5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane makes mixture 110 ℃ of polyase 13s 0 minute.
The result shows, when linking agent Ethylene glycol dimethacrylate consumption is 1 weight %, use the N of 5-10 weight %, two (trimethylsilyl) acrylamides of O-, following 2-hydroxyethyl methacrylate and the above N-vinyl-2-Pyrrolidone of 40 weight % of 50 weight %, polymkeric substance solidifies, wherein, their polymerizations are also solidified transparently.But hydration post polymerization thing becomes frangible, loses ductility and easy to wear.When the consumption of linking agent Ethylene glycol dimethacrylate is 0.4-0.9 weight %, use the following N of 5 weight %, during the following N-vinyl of 2-hydroxyethyl methacrylate that two (trimethylsilyl) acrylamides of O-, 5-90 weight % are following and 5-40 weight %-2-Pyrrolidone, polymkeric substance solidifies, wherein, their polymerizations are also solidified transparently.Especially, when the consumption of linking agent is 0.4-0.7 weight %, has good water-intake rate and ductility after the polymer hydration.
When the consumption of N-vinyl-2-Pyrrolidone increased, the water ratio of raw material and consistency improved, so transparency also improves.When the consumption of N-vinyl-2-Pyrrolidone is 45 weight % when following, consistency is better, can obtain transparent polymkeric substance.This moment, water ratio was 38%-55%.When the consumption of N-vinyl-2-Pyrrolidone is 45 weight % when above, can obtain water ratio up to the polymkeric substance more than 55%.
In the present embodiment, use N, the amount of two (trimethyl silyl) acrylamides of O-is 5 weight % when following, can make polymkeric substance have transparency, ductility and water ratio preferably, suitable for making contact lens.
Use Ethylene glycol dimethacrylate to be linking agent, can improve degree of crosslinking, increase transparency (consistency) and ability to cure, thereby make polymkeric substance become tough.After the hydration, the ductility of contact lens reduces, and uses the amount of Ethylene glycol dimethacrylate to be 0.4-0.7 weight %, and the polymkeric substance that obtains is fit to make contact lens.
Increase the consumption of N-vinyl-2-Pyrrolidone, can improve the consistency and the transparency of storeroom, but can increase water ratio, reduction ductility and the tensile strength of polymkeric substance like this.If the consumption of N-vinyl-2-Pyrrolidone is below the 45 weight %, can obtain water ratio is 38-55%, the polymkeric substance that is fit to make contact lens, because it has ductility and humidity preferably.
Embodiment 6
N, the polymerization of two (trimethyl silyl) acrylamides of O-, 2-hydroxyethyl methacrylate, N-vinyl-2-Pyrrolidone and Vinylstyrene
Reference example 4, in the polymeric process, the water ratio of telomerized polymer is controlled the process of polymerizable raw material to improve its wetting ability by adding water-soluble monomer N-vinyl-2-Pyrrolidone.Use Vinylstyrene to make linking agent, so that make comparisons with the linking agent Ethylene glycol dimethacrylate among the embodiment 5.
N, the consumption of two (trimethyl silyl) acrylamides of O-is increased to 50 weight % gradually from 5 weight %, each 5 weight % that increase, the consumption of 2-hydroxyethyl methacrylate reduces gradually from 90 weight %, each 5 weight % that reduce, the consumption of N-vinyl-2-Pyrrolidone increases gradually from 5 weight %, increases by 5 weight % at every turn, adds the linking agent Vinylstyrene of 0.1-1 weight % again in mixture.Dissolve the initiator 2 of 0.2 weight %, 5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane makes mixture 110 ℃ of polyase 13s 0 minute.
The result shows, when the amount of using the linking agent Vinylstyrene is 1 weight %, the N of 5-10 weight %, polymerization takes place and also solidifies transparently in two (trimethyl silyl) acrylamides of O-, following 2-hydroxyethyl methacrylate and the above N-vinyl-2-Pyrrolidone of 10 weight % of 50-90 weight %.But hydration post polymerization thing becomes frangible, loses ductility and easy to wear.When the amount of using linking agent during as 0.4-0.9 weight %, the N that 5 weight % are following, polymerization takes place and also solidifies transparently in 2-hydroxyethyl methacrylate two (trimethyl silyl) acrylamides of O-, that 5-90 weight % is following and the following N-vinyl-2-Pyrrolidone of 5-40 weight %.Especially, when the consumption that uses linking agent during, has good water-intake rate and ductility after the polymer hydration as 0.4-0.7 weight %.
When the consumption of N-vinyl-2-Pyrrolidone increased, the consistency of raw material and transparency improved.When the consumption of N-vinyl-2-Pyrrolidone is 35 weight % when following, consistency is better, can obtain transparent polymkeric substance.This moment, water ratio was 38%-55%.When the consumption of N-vinyl-2-Pyrrolidone is 35 weight % when above, can obtain water ratio up to the polymkeric substance more than 55%.
In the present embodiment, use N, the amount of two (trimethyl silyl) acrylamides of O-is 5 weight % when following, can make polymkeric substance have transparency, ductility and water ratio preferably, suitable for making contact lens.
Use Vinylstyrene to be linking agent, compare, can further improve transparency (consistency) and degree of crosslinking, thereby increase the ability to cure of polymkeric substance, become tough with the Ethylene glycol dimethacrylate of using among the embodiment 5.After the hydration, the ductility of contact lens reduces, and compares with using Ethylene glycol dimethacrylate, and polymer sizes diminishes.The amount of using Vinylstyrene is during as 0.3-0.5 weight %, and the transparency of the polymkeric substance that obtains and ductility increase, and are fit to make contact lens.
Increase the consumption of N-vinyl-2-Pyrrolidone, can improve the consistency and the transparency of storeroom, but, reduced ductility and tensile strength thus owing to increased the water ratio of polymkeric substance.If the consumption of N-vinyl-2-Pyrrolidone is below the 35 weight %, can to obtain water ratio be 38%-55%, have transparency and ductility preferably, be fit to make the polymkeric substance of contact lens.
Embodiment 7
N, the polymerization of two (trimethyl silyl) acrylamides of O-, 2-hydroxyethyl methacrylate, N,N-DMAA and Ethylene glycol dimethacrylate
Reference example 3, in the polymeric process, the water ratio of telomerized polymer is controlled the process of polymerizable raw material to improve its wetting ability by adding another water-soluble monomer N-vinyl-2-Pyrrolidone.
Result according to embodiment 5, N, the consumption of two (trimethyl silyl) acrylamides of O-is below the 5 weight %, the consumption of 2-hydroxyethyl methacrylate reduces gradually from 90 weight %, each 5 weight % that reduce, the consumption of N,N-DMAA increases gradually from 5 weight %, each 5 weight % that increase, the linking agent Ethylene glycol dimethacrylate of in mixture, adding 0.4 weight % again.Dissolve the initiator 2 of 0.2 weight %, 5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane makes mixture 110 ℃ of polyase 13s 0 minute.
The result shows, the N of the N,N-DMAA of 40 weight % and 5 weight %, and two (trimethyl silyl) acrylamides of O-are complementary, and curablely obtain transparent polymkeric substance.Its water ratio is more than the 55 weight %, and has very high rate of expansion.Along with the increase of N,N-DMAA content, water ratio and rate of expansion all increase, and the consistency of stock yard improves the transparency increase.
In the present embodiment, use N, the amount of two (trimethyl silyl) acrylamides of O-is 5 weight % when following, can make polymkeric substance have transparency, ductility and water ratio preferably, suitable for making contact lens.
When the consumption of N,N-DMAA increased, the consistency of stock yard improved, and transparency increases, but owing to increased the water ratio of polymkeric substance, caused very high rate of expansion thus, had reduced the ductility and the tensile strength of polymkeric substance simultaneously.When the amount of using N,N-DMAA more than 40 weight %, when 70 weight % are following, polymkeric substance has transparency, water ratio and ductility preferably, is fit to make contact lens.
Embodiment 8
N, the polymerization of two (trimethyl silyl) acrylamides of O-, 2-hydroxyethyl methacrylate, N,N-DMAA and Vinylstyrene
Reference example 4, in the polymeric process, the water ratio of telomerized polymer is to improve its wetting ability, the suitable polymerization ratio of control stock yard.Simultaneously with embodiment 7 in the linking agent Ethylene glycol dimethacrylate of use make comparisons.
Result according to embodiment 5, N, the content of two (trimethyl silyl) acrylamides of O-is below the 5 weight %, the content of 2-hydroxyethyl methacrylate reduces gradually from 90 weight %, each 5 weight % that reduce, the content of N,N-DMAA increases gradually from 5 weight %, each 5 weight % that increase, the linking agent Vinylstyrene of interpolation 0.4 weight % in mixture again.At the initiator 2 of 110 ℃ of dissolving 0.2 weight %, 5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane made polymerization of mixtures 30 minutes.
The result shows, when using the content of N,N-DMAA to be 30 weight %, can with N, the content of two (trimethyl silyl) acrylamide 5 weight % of O-is complementary, and solidifies to obtain transparent polymkeric substance.Its water ratio is more than the 55 weight %, and has very high rate of expansion.Along with the increase of N,N-DMAA content, water ratio and rate of expansion all increase, and the consistency of raw material improves the transparency increase.
In the present embodiment, use N, the content of two (trimethyl silyl) acrylamides of O-is 5 weight % when following, can make polymkeric substance have transparency, ductility and water ratio preferably, suitable for making contact lens.
When the consumption of N,N-DMAA increased, the consistency of raw material improved, and transparency increases, but owing to increased the water ratio of polymkeric substance, caused very high rate of expansion thus, had reduced the ductility and the tensile strength of polymkeric substance simultaneously.When the amount of using N,N-DMAA more than the 30 weight % to 70 weight % when following, polymkeric substance has transparency, water ratio and ductility preferably, is fit to make contact lens.
Compare with the linking agent Ethylene glycol dimethacrylate of using among the embodiment 7, present embodiment uses the linking agent Vinylstyrene, and the consistency (transparency) that obtains polymkeric substance is better, but the ductility reduction, diameter diminishes.
Embodiment 9
N, the polymerization of two (trimethyl silyl) acrylamides of O-, 2-hydroxyethyl methacrylate, N,N-DMAA, N-vinyl-2-Pyrrolidone and Ethylene glycol dimethacrylate
Reference example 4, in the polymeric process, the water ratio of telomerized polymer is controlled proper proportion between two kinds of water-soluble monomer N,N-DMAAs and the N-vinyl-2-Pyrrolidone to improve its wetting ability.
Result according to embodiment 7, N, the consumption of two (trimethyl silyl) acrylamides of O-is below the 5 weight %, the consumption of 2-hydroxyethyl methacrylate is 60 weight %, regulate N, content between N-DMAA and the N-vinyl-2-Pyrrolidone adds the linking agent Ethylene glycol dimethacrylate of 0.4 weight % again than in 40 weight % in mixture.Dissolve the initiator 2 of 0.2 weight %, 5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane makes mixture 110 ℃ of polyase 13s 0 minute.
The result shows, no matter how much content between N,N-DMAA and the N-vinyl-2-Pyrrolidone is than being, mixture all has consistency preferably, and generates transparent polymkeric substance when solidifying, but becomes the milk look after the polymkeric substance suction.
In the present embodiment polymerization process, mixture has consistency preferably, generates transparent polymkeric substance during curing, but no matter how many ratios between N,N-DMAA and the N-vinyl-2-Pyrrolidone is, all becomes the milk look after the polymkeric substance generation hydration.Such polymkeric substance is not suitable for making contact lens, should select in N,N-DMAA and the N-vinyl-2-Pyrrolidone any one to prepare polymkeric substance as contact lens.
Embodiment 10
N, the polymerization of two (trimethyl silyl) acrylamides of O-, 2-hydroxyethyl methacrylate, N-vinyl-2-Pyrrolidone, N,N-DMAA and Vinylstyrene
Reference example 5, in the polymeric process, the water ratio of telomerized polymer is controlled proper proportion between two kinds of water-soluble monomer N,N-DMAAs and the N-vinyl-2-Pyrrolidone to improve its wetting ability.
Result according to embodiment 8, N, the content of two (trimethyl silyl) acrylamides of O-is 5 weight %, the content of 2-hydroxyethyl methacrylate is 60 weight %, regulate N, content between N-DMAA and the N-vinyl-2-Pyrrolidone compares in 40 weight %, the middle 0.4 weight % linking agent Vinylstyrene that adds in mixture.Dissolve the initiator 2 of 0.2 weight %, 5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane makes mixture 110 ℃ of polyase 13s 0 minute.
The result shows, no matter how much content between N,N-DMAA and the N-vinyl-2-Pyrrolidone is than being, mixture all has better consistency, and generates transparent polymkeric substance when solidifying, but becomes the milk look after the polymkeric substance suction.
Polymerization process from present embodiment, the result of its result and embodiment 9 is consistent, mixture has consistency preferably, generate transparent polymkeric substance during curing, but N no matter, how many ratios between N-DMAA and the N-vinyl-2-Pyrrolidone is, all becomes the milk look after the polymkeric substance generation hydration.Such polymkeric substance is not suitable for making contact lens, should select in N,N-DMAA and the N-vinyl-2-Pyrrolidone any one to prepare polymkeric substance as contact lens.
In other words, the result of the polymerization result of present embodiment and embodiment 9 is consistent.
Embodiment 11-16 and Comparative Examples 1
Result based on embodiment, according to embodiment 11-16, by making 2-hydroxyethyl methacrylate, N, two (trimethyl silyl) acrylamides of O-, Vinylstyrene (or Ethylene glycol dimethacrylate) and N-vinyl-2-Pyrrolidone or N, the N-DMAA carries out polymerization, makes a kind of soft contact lens.According to Comparative Examples 1; by mixed methyl vinylformic acid 2-hydroxy methacrylate, linking agent Vinylstyrene and initiator 2; 5-dimethyl-2; 5-two (peroxidation-2-ethyl hexanoyl base) hexane is made a kind of soft contact lens, thereby contrast is such as these performance perameters of water ratio, ductility, tensile strength and oxygen permeability.
Oxygen permeability is meant that when unit pressure changed, oxygen saw through the speed of unit thickness unit surface contact lens.The method of measuring oxygen permeability is as follows.
A. sample to be tested and instrument is dry to greatest extent.
B. contact lens to be measured are placed on the instrument of bottom, the instrument of fixing this bottom by the O-ring also covers with top instrument, fixes with four screws, prevents gas leakage.
C. in telltale, be about 10% suds and make bubble with concentration.
D. use each circuit to connect gas tank, operation baroceptor (gas pressure sensor).
E. clear up each part that to measure, about 2 hours with gas.
F. when beginning bubble to occur in the telltale, writing time; Write down the environmental factors of this moment simultaneously; At regular intervals, check also recording status.
G. calculate with formula.Formula is as follows:
Wherein, P, V and T are meant the environmental aspect when experiment is carried out, and P ' and T ' are meant stp state, and V ' is meant the numerical value that calculates according to stp state.
Wherein, the 1st, the mean thickness of sample, force value obtains by the indication of pressure transmitter.With formula value generation 1. to formula 2. in, to calculate rate of permeation.
Water ratio calculates the percentage of expression moisture weight and sample dry weight by doing-weigh method usually; But also can calculate, represent contained moisture weight and the percentage that comprises the gross weight of moisture weight by wet-heavy method.Yet, also have a lot of definition to represent water ratio, such as " relative content in saturation water " or " with respect to the equilibrium moisture content of ambient moisture ".Recently, the volumetric water content of representing with the ratio of water content and sample gross weight in some cases.
The water content of contact lens records with wet-heavy method.
Measuring method is as follows.
A. contact lens are fully soaked (about 24 hours or longer);
B. remove surface-moisture with deerskin, and (the M that weighs
1);
C. contact lens are placed baking box more than at least 20 minutes (time point no longer change be as the criterion) with weight;
D. weight (the M of contact lens after the weighing drying
2);
E. with reference to the described method of A-D, measure the weight of 10 samples at least, obtain the mean value of water ratio.
Formula is as follows:
Embodiment 11: the making of contact lens 1
2-hydroxyethyl methacrylate, N, two (trimethyl silyl) acrylamides of O-, N-vinyl-2-Pyrrolidone and Vinylstyrene (or Ethylene glycol dimethacrylate)
Containing the 2-hydroxyethyl methacrylate more than the 64.3 weight %, the N-vinyl-2-Pyrrolidone below the 30 weight %, the N below the 5 weight %; in the mixture of two (trimethyl silyl) acrylamides of O-; add the above Vinylstyrene of 0.5 weight % (or the above Ethylene glycol dimethacrylate of 0.6 weight %) as linking agent; and dissolve 0.2 weight % above 2; 5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane is as initiator.Said mixture is injected in the mould (mold) of making contact lens, 110 ℃ of polyase 13s 0 minute, to be cured.Then, contact lens are taken out from mould, check consistency (transparency).Contact lens are transparent, measure water ratio and performance after the hydration.
Embodiment 12: the making of contact lens 2
2-hydroxyethyl methacrylate, N, two (trimethyl silyl) acrylamides of O-, N-vinyl-2-Pyrrolidone and Vinylstyrene (or Ethylene glycol dimethacrylate)
Containing the 2-hydroxyethyl methacrylate more than the 83.5 weight %, the N-vinyl-2-Pyrrolidone below the 15 weight %, the N below the 1 weight %; in the mixture of two (trimethyl silyl) acrylamides of O-; add the above Vinylstyrene of 0.3 weight % (or the above Ethylene glycol dimethacrylate of 0.4 weight %) as linking agent; and dissolve 0.2 weight % above 2; 5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane is as initiator.Make recessive glasse according to the method identical, with assess performance with embodiment 11.
Embodiment 13: the making of contact lens 3
2-hydroxyethyl methacrylate, N, two (trimethyl silyl) acrylamides of O-, N-vinyl-2-Pyrrolidone and Vinylstyrene (or Ethylene glycol dimethacrylate)
Containing the 2-hydroxyethyl methacrylate more than the 71.4 weight %, the N-vinyl-2-Pyrrolidone below the 25 weight %, the N below the 3 weight %; in the mixture of two (trimethyl silyl) acrylamides of O-; add the above Vinylstyrene of 0.4 weight % (or the above Ethylene glycol dimethacrylate of 0.5 weight %) as linking agent; and dissolve 0.2 weight % above 2; 5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane is as initiator.Make recessive glasse according to the method identical, with assess performance with embodiment 11.
Embodiment 14: the making of contact lens 4
2-hydroxyethyl methacrylate, N, two (trimethyl silyl) acrylamides of O-, N-vinyl-2-Pyrrolidone and Vinylstyrene (or Ethylene glycol dimethacrylate)
Containing the 2-hydroxyethyl methacrylate more than the 64.3 weight %, the N-vinyl-2-Pyrrolidone more than the 30 weight %, the N below the 5 weight %; two (trimethyl silyl) acrylamides of O-mix; to wherein adding Vinylstyrene (or the Ethylene glycol dimethacrylate more than the 0.6 weight %) more than the 0.5 weight % as linking agent; and 2 more than the dissolving content 0.2 weight %; 5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane is as initiator.Make recessive glasse according to the method identical, with assess performance with embodiment 11.
Embodiment 15: the making of contact lens 5
2-hydroxyethyl methacrylate, N, two (trimethyl silyl) acrylamides of O-, N-vinyl-2-Pyrrolidone and Vinylstyrene (or Ethylene glycol dimethacrylate)
Containing the 2-hydroxyethyl methacrylate more than the 65.4 weight %, the N-vinyl-2-Pyrrolidone more than the 30 weight %, the N below the 4 weight %; in the mixture of two (trimethyl silyl) acrylamides of O-; add the above Vinylstyrene of 0.4 weight % (or the above Ethylene glycol dimethacrylate of 0.5 weight %) as linking agent; and dissolve 0.2 weight % above 2; 5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane is as initiator.Make recessive glasse according to the method identical, with assess performance with embodiment 11.
Embodiment 16: the making of contact lens 6
2-hydroxyethyl methacrylate, N, two (trimethyl silyl) acrylamides of O-, N,N-DMAA and Vinylstyrene (or Ethylene glycol dimethacrylate)
Containing the 2-hydroxyethyl methacrylate more than the 66.4 weight %, the N more than the 30 weight %; the N of N-DMAA, 0.3g; in the mixture of two (trimethyl silyl) acrylamides of O-; add the above Vinylstyrene of 0.4 weight % (or the above Ethylene glycol dimethacrylate of content 0.5 weight %) as linking agent; and dissolve 0.2 weight % above 2; 5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane is as initiator.Make recessive glasse according to the method identical, with assess performance with embodiment 11.
Comparative Examples 1: the making of contact lens
With content is the 2-hydroxyethyl methacrylate of 9g and the linking agent Vinylstyrene mixing commonly used that content is 1g, 2 more than the dissolving 0.02g, and 5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane is as initiator.Said mixture is injected in the mould (mold) of making contact lens, at 0 minute after fixing of 110 ℃ of polyase 13s.Then, contact lens are taken out from mould, measure water ratio.According to measuring result, the contact lens water ratio is lower, is 38%, and oxygen permeability is 10-20Dk[10
-11(cm
2/ sec) (ml O
2MmHg)].
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative Examples | |
| Methacrylic acid 2-hydroxyethyl ester | More than 64.2% | More than 83.4% | More than 71.3% | More than 64.2% | More than 65.3% | More than 69% | ??99.4％ |
| N, two (trimethyl silyl) acrylamides of O- | Below 5% | Below 1% | Below 3% | Below 5% | Below 4% | Below 0.3% | ??- |
| N-vinyl-2-Pyrrolidone | Below 30% | Below 15% | Below 25% | Below 30% | Below 30% | ??- | ??- |
| N,N-DMAA | ??- | ??- | ??- | ??- | ??- | Below 30% | ??- |
| Vinylstyrene (or Ethylene glycol dimethacrylate) | More than 0.5% (or 0.6%) | More than 0.3% (or 0.4%) | More than 0.4% (or 0.5%) | More than 0.5% (or 0.6%) | More than 0.4% (or 0.5%) | More than 0.4% (or 0.5%) | ??10％ |
| 2,5-dimethyl-2,5-two (peroxidation-2-ethyl hexanoyl base) hexane | More than 0.2% | More than 0.2% | More than 0.2% | More than 0.2% | More than 0.2% | More than 0.2% | More than 0.2% |
The performance of the contact lens of being made by the described method of front embodiment and Comparative Examples is as follows.
Table 2
| Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 | Comparative Examples | |
| Water ratio (%) | ??40-50 | ??40-50 | ??40-50 | ??50-70 | ??50-70 | ??50-70 | ??38 |
| Ductility (%) | ??200-300 | ??250-300 | ??300-350 | ??250-350 | ??300-350 | ??300-400 | |
| Tensile strength (g/mm 3) | ??80-100 | ??90-110 | ??90-110 | ??80-100 | ??80-100 | ??90-100 | |
| Oxygen permeability (DK) | ??70-90 | ??50-70 | ??60-80 | ??80-100 | ??65-85 | ??70-90 | ??10-20 |
As shown in table 2, the contact lens of making according to the embodiment of the invention have up to the water ratio of 40-70% with up to 50-90Dk[10
-11(cm
2/ sec) (ml O
2MmHg)] oxygen permeability is compared with the contact lens of making according to Comparative Examples, and its performance will be got well a lot.
Although only provide and described several embodiments of the present invention, but will be understood that, some variations that those skilled in the art has done under the situation that does not break away from fundamental principle of the present invention and spirit should be considered as a part of the present invention, and its scope is embodied in additional claims.
Claims (7)
1, a kind of silicone-hydrogel composition that is used for soft contact lens, wherein, the N that said composition contains 2-hydroxyethyl methacrylate and is shown below, two (trimethyl silyl) acrylamide silicone resin monomers of O-:
2, composition according to claim 1, wherein, described N, the two content of (trimethyl silyl) acrylamide in said composition of O-are below the 10 weight %.
3, composition according to claim 1, wherein, said composition contains Ethylene glycol dimethacrylate.
4, composition according to claim 1, wherein, said composition contains Vinylstyrene.
5, composition according to claim 3, wherein, said composition contains any one in N-vinyl-2-Pyrrolidone and the N,N-DMAA.
6, composition according to claim 4, wherein, said composition contains any one in N-vinyl-2-Pyrrolidone and the N,N-DMAA.
7, a kind of soft contact lens, wherein, this soft contact lens is to be made by any described composition of claim among the claim 1-6.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020070061970 | 2007-06-25 | ||
| KR10-2007-0061970 | 2007-06-25 | ||
| KR1020070061970A KR101231181B1 (en) | 2007-06-25 | 2007-06-25 | Silicone-hydrogel compound for soft contact lens and soft contact lens produced using the compound |
| PCT/KR2007/005098 WO2009001987A1 (en) | 2007-06-25 | 2007-10-18 | Silicone-hydrogel compound for soft contact lens and soft contact lens produced using the compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101688042A true CN101688042A (en) | 2010-03-31 |
| CN101688042B CN101688042B (en) | 2012-01-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800535071A Active CN101688042B (en) | 2007-06-25 | 2007-10-18 | Silicone-hydrogel compound for soft contact lens and soft contact lens produced using the compound |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP2170992A4 (en) |
| JP (1) | JP5432133B2 (en) |
| KR (1) | KR101231181B1 (en) |
| CN (1) | CN101688042B (en) |
| AU (1) | AU2007355828B2 (en) |
| CA (1) | CA2686938C (en) |
| RU (1) | RU2434899C2 (en) |
| UA (1) | UA92126C2 (en) |
| WO (1) | WO2009001987A1 (en) |
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- 2007-10-18 JP JP2010514580A patent/JP5432133B2/en active Active
- 2007-10-18 RU RU2009146491/05A patent/RU2434899C2/en active
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- 2007-10-18 AU AU2007355828A patent/AU2007355828B2/en active Active
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| US11433628B2 (en) | 2013-11-15 | 2022-09-06 | Tangible Science, Inc. | Contact lens with a hydrophilic layer |
| US10330951B2 (en) | 2013-11-15 | 2019-06-25 | Tangible Science, Llc | Contact lens with a hydrophilic layer |
| CN106999295A (en) * | 2014-07-21 | 2017-08-01 | 实体科学有限责任公司 | Contact lenses and the method for preparing contact lenses |
| US10525170B2 (en) | 2014-12-09 | 2020-01-07 | Tangible Science, Llc | Medical device coating with a biocompatible layer |
| US11260150B2 (en) | 2014-12-09 | 2022-03-01 | Tangible Science, Inc. | Medical device coating with a biocompatible layer |
| US11256003B2 (en) | 2017-12-13 | 2022-02-22 | Alcon Inc. | Weekly and monthly disposable water gradient contact lenses |
| CN114176895A (en) * | 2021-11-23 | 2022-03-15 | 天津世纪康泰生物医学工程有限公司 | Cornea protective glasses for animals |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101688042B (en) | 2012-01-11 |
| WO2009001987A1 (en) | 2008-12-31 |
| CA2686938C (en) | 2013-04-02 |
| RU2009146491A (en) | 2011-07-27 |
| KR101231181B1 (en) | 2013-02-07 |
| RU2434899C2 (en) | 2011-11-27 |
| AU2007355828B2 (en) | 2011-03-03 |
| JP5432133B2 (en) | 2014-03-05 |
| AU2007355828A1 (en) | 2008-12-31 |
| EP2170992A1 (en) | 2010-04-07 |
| EP2170992A4 (en) | 2010-08-04 |
| JP2010531474A (en) | 2010-09-24 |
| UA92126C2 (en) | 2010-09-27 |
| CA2686938A1 (en) | 2008-12-31 |
| AU2007355828A8 (en) | 2010-03-18 |
| KR20080113467A (en) | 2008-12-31 |
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