Silicone hydrogels, ophthalmic and contact lenses

FIELD: medicine.

SUBSTANCE: invention refers to transparent silicone hydrogels. What is presented is silicone hydrogel prepared by polymerisation of mixture of monomers containing (a) 30-98 wt % of at least one silicone (meth)acrylamide monomer and (b) 1-50 wt % of at least one non-silicone (meth)acrylamide monomer containing two or more hydroxyl groups in its molecule; wherein weight percentage is calculated from a total amount of monomer and polymer components in the monomer mixture, and a total amount of monomers (a) and (b) makes 90 wt % or more in relation to the total amount of the monomer and polymer components in the monomer mixture. There are also presented a medical device, an ophthalmic lens and a contact lens made of the above silicone hydrogel.

EFFECT: presented silicone hydrogel has the high content of acrylamide monomer and the excellent balance of humidity, elasticity, wetting ability and transparency, and is applicable to produce lenses having the excellent characteristics.

19 cl, 4 tbl, 27 ex

 

RELATED APPLICATIONS

The present application claims the priority stated in the provisional application for U.S. patent No. 13/048252, filed March 15, 2011, and to provisional patent application of Japan No. JP2010-061991, filed on March 18, 2010.

Background of the INVENTION

The present invention relates to silicone-hydrogels. Silicone-hydrogel suitable for use in such medical devices such as ophthalmic lenses, endoscopes, catheters, tubes for blood transfusion, airline tubing, stents, wires for catheter, cuff, medical connector, ports for vascular access, drainage bags, the contours of the circulation of materials to cover wounds and various types of medical devices, but it is particularly suitable for contact lenses, ophthalmic lenses and artificial corneas.

Description of the materials used in the examination of the application

In recent years silicone hydrogels became known as materials for the manufacture of contact lenses used for extended wear. Silicone hydrogels are obtained by combining at least one silicone component, at least one hydrophilic component. For example, in U.S. patents No. 7396890 and No. 7214809 describes a silicone hydrogel obtained by polymerization of the polymerization mixture containing the monomer (meth)acrylamide silicone and hydrophilic components which may include hydrophilic acrylamide monomers such as N,N-dimethylacrylamide, hydrophilic ester of methacrylic acid, such as 2-hydroxyethylmethacrylate, and an internal wetting agent.

However, in the compositions have a relatively high content of methacrylic acid ester. If the acrylamide monomer has a higher rate constant of polymerization than the methacrylic acid ester during homopolymerization, then the rate of copolymerization of acrylamide and methacrylate significantly lower and, as a result, the polymerization rate in the entire system will be reduced.

On the other hand, in U.S. patent No. 4711943 and Japanese unexamined patent application No. H10-212355 describes silicone-hydrogels containing acrylamide monomer of silicone and a hydrophilic acrylamide monomer. The acrylamide monomers make up a large part of these compositions, which allows to expect a higher rate of polymerization in the whole system. However, acrylamide amide bond group is highly hydrophilic, and therefore, there are problems with the transparency of the lens from the point of view of achievement of both desired permeability for oxygen, and ensure sufficient moisture content necessary to make the lens elasticity. In particular, obtaining clear lens is especially difficult, if� to improve the wettability of its surface is added to an internal wetting agent.

On the other hand, Andre Laschewsky et al., Macromol. Chem. Phys. 2001, 202, 276 286, described polymer in which a hydrophilic acrylamide monomer with two or more hydroxyl groups in one molecule. However, it was not given information about its copolymerization with silicone monomer, about transparency and other physical properties of this copolymer.

The summary of the invention

The present invention relates to silicone-hydrogels with a high content of acrylamide monomer and an excellent balance between moisture, elasticity, wettability, and transparency. This silicone-hydrogel suitable for use in various types of medical devices, in particular for the manufacture of ophthalmic lenses such as contact lenses, intraocular lenses and artificial cornea, and is particularly suitable for contact lenses.

To achieve the above objectives, the present invention has the following composition. Namely,

(1) silicone-hydrogel obtained by polymerization polymerization mixture comprising a plurality of monomers containing from about 30 to 98% by weight of at least one silicone monomer; and about 1 to 50% by weight. at least one naselyonnogo (meth)acrylamide monomer, represented in the

[Formula 1]

where R1means hydrogen or methyl;

at least one of R14and R15substituted by at least one C1-C20 alkyl, substituted by at least one hydroxyl group, and

if

(i) one of R14and R15represented by hydrogen

ii) and the other of R14and R15substituted by at least two hydroxyl groups,

where mentioned mass percent based on a total content of monomer components and polymer components in the monomer mixture.

In addition, the present invention relates to medical devices made from the above-described silicone-hydrogels, which are contact lenses, artificial cornea, endoscopes, catheters, tubes for blood transfusion, airline tubing, stents, wires for catheter, cuff, medical connector, ports for vascular access, drainage bags, the contours of the circulation, materials for covering wounds and medical media.

In addition, the present invention relates to silicone-hydrogels with a high content of acrylamide monomer and an excellent balance between moisture, elasticity, wettability, and transparency. This silicone-hydrogel suitable for use in various types of medical devices, in particular for izgotovleniya ophthalmic lenses as contact lenses, intraocular lenses and artificial cornea, and is particularly suitable for contact lenses.

DETAILED description of the INVENTION

Used here, the term (meth) or (methyl) indicates an optional methyl Deputy. Thus, the term "(meth)acrylate" refers to both methacrylic and acrylic radicals.

The silicone hydrogel of the present invention is produced by polymerization of a mixture of monomers consisting of

(A) from 30 to 98% by weight., at least one silicone monomer relative to the total content of the monomer and polymer component.

(B) from 1 to 50% by weight. naselyonnogo (meth)acrylamide monomer having two or more hydroxyl groups in the molecule, relative to the total content of the monomer and polymer component.

In the present invention the silicone monomer refers to monomers containing the polymerizable group and siloxanic group. Filoxenia group refers to a group having at least one bond of Si-O-Si.

Examples of the silicone monomers used for obtaining the silicone hydrogels of the present invention are silicone monomers belonging to the following General formulas (a1)-(a4).

[Formula 6]

In formulas (a1)-(a4), R1discover about�means a hydrogen atom or a methyl group. In this case the hydrogen atoms are preferable from the viewpoint of further increasing the speed of polymerization.

R2means an alkyl group containing from 1 to 20 carbon atoms, in some embodiments of the present invention from 1 to 10 carbon atoms, and in other embodiments of the present invention from 1 to 6 carbon atoms, any of which may be substituted by at least one hydroxyl group. Examples include 2-hydroxyethylene group, 2-hydroxyproline group, 3-hydroxiproline group, 2,3-dihydroxypropyl group, 4-hydroxybutyl group, 2-hydroxy-1,1-bis(gidroximetil)ethyl group, 2-hydroxymethylene group, 3-hydroxymethylene group, 4-hydroxymethylene group and the like. In one embodiment of the present invention, R2is selected from 2-hydroxyethylene groups, 2-hydroxypropyl groups and 2,3-dihydroxypropyl groups, and in another embodiment of the present invention, R2denotes 2,3-dihydroxypropyl group.

R3denotes alkylenes group having from 1 to 20 carbon atoms, or Allenova group having from 6 to 20 carbon atoms which may be unsubstituted or independently to have such substituents as hydroxyl, acid, ester, PR�wait ether, thiol group, or combinations thereof. In one embodiment of the present invention, R3denotes a C1-10 alkylene, which may be unsubstituted or independently to have such substituents as hydroxyl, acid, ester, ether, thiol group, or combinations thereof. Their examples include methylene group, ethylene group, propylene group, butylene group, pentalenene group, octalene group, decenoic group and phenylene group and the like. These alkylene and Allenova group can be straight or branched. In another embodiment of the present invention, R2is selected from C1-5alkilinity groups which may be unsubstituted or substituted hydroxyl group, ether group or their combinations. In another embodiment of the present invention, R2is selected from C2-5alkilinity groups which may be unsubstituted or substituted with hydroxyl, ether groups or combinations, and in yet another embodiment of the present invention, R2represents C3alkylene group which may be unsubstituted or substituted with hydroxyl, ether groups or combinations.

R4denotes a hydrogen atom or an alkyl or aryl group which has from 1 to 20 carbon atoms, which may be substituted by a hydroxyl group, acid, ester, simple ester, thiol group or their combinations. Their examples include hydrogen atoms, methyl group, ethyl group, propyl group, n-propyl group, isopropylene group, n-butyl group, S-butyl group, tert-butyl group, n-pentingnya group, isopentyl group, S-pentingnya group, neopentylene group, hexylene group, heptylene group, aktiline group, monilinia group decile group, modelline group, akosile group, phenyl group, naftalina group and the like. These alkyl groups may be straight or branched. If the number of carbon atoms in R4is too high, the silicone content will be relatively low, the more preferable the presence of a hydrogen atom or an alkyl or aryl group containing from 1 to 10 carbon atoms, and most preferably the presence of a hydrogen atom or an alkyl group containing from 1 to 4 carbon atoms.

A stands for siloxanic group. Preferred examples of these groups include silicone group corresponding to the following General formula (f):

[Formula 7]

In the General formula (f), E1-E11independently represent a hydrogen atom, alkyl group containing from 1 to 20 carbon atoms, in some embodiments of the present invention contains from 1 to 10 carbon atoms, and in other embodiments of the present invention contains from 1 to 6 carbon atoms, any of which may be substituted with fluorine, hydroxyl group, acid, ester, simple ester, thiol group, and their combinations, or aryl group containing from 6 to 20 carbon atoms which may be substituted with fluorine, hydroxyl group, acid, ester, simple ester, thiol group and their combinations.

In the General formula (f), h denotes an integer from 0 to 200, and i, j and k independently represent integers from 0 to 20 (except when h=i=j=k=0). If the sum of h+i+j+k is too small, a sufficient oxygen permeability is not achieved, but if the amount is too large, it will decrease the compatibility with the hydrophilic monomer. Therefore, the preferred amount is from 2 to 100, more preferred from 2 to 10, and most preferred from 3 to 10. Moreover, i=j=k=0 preferred from the viewpoint of obtaining a polymer with shape memory obtained by polymerization of the silicone prepolymer.

In accordance with the foregoing, (meth)acrylamide monomer of silicone, indicated in General formula (a1) and (a2), preferable from the point of view of increasing the speed of polymerization throughout the system.

More to�ncrete examples of the structure of (meth)acrylamide monomers, silicone, indicated in the General formulas (a1) and (a2) represented by (meth)acrylamide monomers silicone indicated in the General formulas (b1) to(b4).

[Formula 8]

In chemical formulas (b1) to(b4), R1independently denotes a hydrogen atom or a methyl group. Of these, more preferred hydrogen atoms from the point of view of increasing the speed of polymerization.

R5-R13independently denote an alkyl group containing from 1 to 20 carbon atoms, or aryl group containing from 6 to 20 carbon atoms. If the number of carbon atoms in R5-R8will be too large, and the content of silicon is relatively low, it will lead to a reduction in the permeability of the silicone hydrogel oxygen. Therefore, a more preferable alkyl group containing from 1 to 10 carbon atoms, or aryl group containing from 6 to 10 carbon atoms, even more preferred alkyl group containing from 1 to 4 carbon atoms, and most preferred a methyl group, consisting of 1 atom of carbon. If the number of carbon atoms in R9is too small, the polysiloxane chain is easy to be hydrolyzed, if the quantity is too large, the silicone hydrogel will have a low permeability for �of ikorodu. Therefore, a more preferable alkyl group containing from 1 to 10 carbon atoms, or aryl group containing from 6 to 10 carbon atoms, even more preferred alkyl group containing from 1 to 6 carbon atoms, and most preferred alkyl group containing from 1 to 4 carbon atoms. If the number of carbon atoms in R9-R13is too large, the silicone hydrogel will have too low a permeability to oxygen, and therefore preferable alkyl group containing from 1 to 10 carbon atoms, or aryl group containing from 6 to 10 carbon atoms, even more preferred alkyl group containing from 1 to 4 carbon atoms, and most preferred methyl or ethyl group.

n is a natural number in the range from 1 to 50. If n is too small, there can be achieved a sufficient permeability for oxygen, but if you set it too high, it will reduce the compatibility with the hydrophilic monomer. Therefore, the preferred values are from 2 to 30, more preferred from 3 to 10, and most preferred from 3 to 10.

m means an integer from 0 to 2. To obtain sufficient permeability to oxygen the more preferred value of m is 0 or 1.

From monomers of (meth)acrylamide silicone matching Fort�Ulam (b1)-(b4), the monomers (meth)acrylamide silicone corresponding to General formulas (b1) and (b2) are preferable from the viewpoint of the shape memory obtained silicone hydrogel, which is a positive factor because Filoxenia the group has a linear chain monomers and (meth)acrylamide silicone corresponding to the General formula (b2), more preferred from the viewpoint of transparency of the obtained silicone hydrogel.

If the amount of silicone monomer used to obtain the silicone hydrogel of the present invention, it will be too small, the permeability of the silicone hydrogel oxygen will be insufficient, but if the quantity is too high, the hydrophilicity is insufficient, therefore, the monomer and polymer components in the mixture of monomers should be from about 30 to 98% by weight, preferably from 40 to 80% by weight, and most preferably from 50 to 70 mass%. Lower limit content is preferably 30% by mass, more preferably 40% by mass, and still more preferably 50% by mass. The upper limit content is preferably 98% by mass, more preferably 80% by mass, and still more preferably 70% by mass. Any of the preferred lower limits of the content may be combined with any preferred upper limit �of obsession.

In silicone-hydrogel of the present invention, the monomer and polymer component in the monomer mixture is from 1 to 50% by mass from naselyonnogo (meth)acrylamide monomer corresponding to the following formula (c0)

[Formula 9]

In the chemical formula (c0), R1denotes hydrogen or methyl. At least one of R14and R15substituted with at least C1-C20 alkyl, substituted by at least one hydroxyl group, and provided that, if (i) one of R14and R15is hydrogen, (ii) the other of R14and R15is C1-C20 alkyl group substituted with two or more hydroxyl groups, substituted by one hydroxyl group, the weight percent shown in the present application, based on the total content of the monomer and polymer component in the monomer mixture. In this case, in the present invention, resiliancy (meth)acrylamide monomer refers to a (meth)acrylamide to monomers that do not contain in its molecule siloxanic groups.

In one embodiment of the present invention resiliancy (meth)acrylamide monomer contains in the molecule two or more hydroxyl groups. In the chemical formula (c0) of the present invention, R1denotes hydrogen or a methyl group. In some embodiments, osushestvlenie� present invention, the hydrogen atoms are preferable from the viewpoint of increasing the speed of polymerization. In this embodiment of the present invention, at least one of R14and R15is selected from hydrogen, optionally substituted C1-C20 alkyl groups or optionally substituted C6-C20 aryl group, provided that the total number of hydroxyl groups in R14and R15is two or more. In one embodiment of the present invention, R14and R15independently selected from C1-C10 alkyl group which may be substituted by at least one hydroxyl group, and, in another embodiment of the present invention, C1-C6 alkyl group which may be substituted by at least one hydroxyl group, as long while resiliancy (meth)acrylamide meets the conditions described above. Examples R14and R15include hydrogen atoms, methyl group, ethyl group, propyl group, n-propyl group, isopropylene group, n-butyl group, S-butyl group, tert-butyl group, n-pentingnya group, isopentyl group, S-pentingnya group, neopentylene group, hexylene group, heptylene group, aktiline group, monilinia group decile group, modelline group, akosile group, phenyl group, naftalina group, 2-hydroxyethylene group, 2-hydroxyproline group, 3-hydroxyproline �the group, 2,3-dihydroxypropyl group, 4-hydroxybutyl group, 2-hydroxy-1,1-bis(gidroximetil)ethyl group, 2-hydroxymethylene group, 3-hydroxymethylene group, 4-hydroxymethylene group and the like. These alkyl and hydroxyalkyl groups can be straight and branched chain. Particularly preferred examples resiliancy (meth)acrylamide monomers containing two or more hydroxyl groups in the molecule include the monomers corresponding to the following General formulae (c1) to(c3).

[Formula 10]

In the chemical formula (c1)-(c3) R1independently denotes hydrogen or a methyl group. In some embodiments of the present invention the hydrogen atoms are preferable from the viewpoint of increasing the speed of polymerization. Moreover, of these monomers, the monomers corresponding to the formula (c1), used for the manufacture of contact lenses and increased transparency in the polymerization with other components that are used in these examples.

In another embodiment of the present invention resiliancy (meth)acrylamide monomer contains in its molecule, one hydroxyl group and contains no amide hydrogen. In the chemical formula (c0) of the present invention, R1denotes hydrogen or methyl �the Rupp. In some embodiments of the present invention the hydrogen atoms are preferable from the viewpoint of increasing the speed of polymerization. Preferably, R14and R15independently selected from optionally substituted C1-C20 alkyl groups or optionally substituted C6-C20 aryl group, provided that one of R14and R15substituted by at least one hydroxyl group. Examples R14and R15include methyl group, ethyl group, propyl group, n-propyl group, isopropylene group, n-butyl group, S-butyl group, tert-butyl group, n-pentingnya group, isopentyl group, S-pentingnya group, neopentylene group, hexylene group, heptylene group, aktiline group, monilinia group decile group, modelline group, akosile group, phenyl group, naftalina group, 2-hydroxyethylene group, 2-hydroxyproline group, 3-hydroxiproline group, 4-hydroxybutyl group, 2-hydroxymethylene group, 3-hydroxymethylene group, 4-hydroxymethylene group and the like. These alkyl groups can be straight and branched chain. Examples resiliancy (meth)acrylamide monomers with a hydroxyl group and no amide hydrogen in the molecule include the monomers correspond�s the following General formulas (c11) to(c13).

[Formula 11]

In the chemical formula (c11) to(c13) R1independently denotes hydrogen or a methyl group. In some embodiments of the present invention the hydrogen atoms are preferable from the viewpoint of increasing the speed of polymerization. Moreover, of these monomers, the monomers corresponding to the formula (c11), are more preferred from the viewpoint of transparency of the obtained silicone hydrogel.

Given the fact that the resulting silicone hydrogel is flowable, preferably the acrylamide monomer containing one hydroxyl group and one amide hydrogen in its molecule. Examples of acrylamide monomers containing in their molecule one hydroxyl group and one amide hydrogen, include N-(monohydroxyethyl C1-C20 alkyl)acrylamide and N-(monohydroxyethyl C6-C20 aryl)acrylamide. More specific examples include N-(2-hydroxyethyl)acrylamide, N-(2-hydroxypropyl)acrylamide, N-(3-hydroxypropyl)acrylamide, N-(2-hydroxybutyl)acrylamide, N-(3-hydroxybutyl)acrylamide, N-(4-hydroxybutyl)acrylamide, N-(2-hydroxymethylene)acrylamide, N-(3-hydroxymethylene)acrylamide, N-(4-hydroxymethylene)acrylamide and the like. These alkyl and aryl groups may have a direct and time�evennou chain. Given the fact that the resulting silicone hydrogel is flowable, more preferred N-(monohydroxyethyl C2-C4 alkyl)acrylamide, and most preferred N-(2-hydroxyethyl)acrylamide.

If the number naselyonnogo (meth)acrylamide monomer is too small, the silicone hydrogel will be or have low transparency or high modulus of elasticity, or both, but if the quantity is too large, the silicone hydrogel will have a low permeability for oxygen, and therefore, this quantity must be from 1 to 50% by weight., in some embodiments, the present invention is from 2 to 30% by weight., in other embodiments, the present invention is from 3 to 20% wt., and in yet other embodiments, from about 5 to about 15% by weight., based on the content of the monomer and polymer component in the monomer mixture. The appropriate values of the lower limit of content include about 1% by weight., about 2% wt., about 3% by weight. and about 5% by weight. A suitable value of the upper limit of the content include about 50% by weight., about 30% wt., about 20% of the weight. and about 15% by weight. Any of the values preferred lower limit of the content may be combined with any of the values the preferred upper limit of the content.

The monomer mixture to obtain a silicone-hydrogels of the present from�retenu may also contain reactive and directionsone a wetting agent.

Suitable wetting agents include hydrophilic polymers having a molecular weight of about 1000 or more. Hydrophilic polymers can be included in the monomer mixture in an amount of from about 1 to about 30% by weight. the total amount of the monomer and polymer components.

Examples of hydrophilic polymers that can be used to obtain the silicone hydrogel of the present invention include poly-N-vinylpyrrolidone, poly-N-vinyl-2-piperidone, poly-N-vinyl-2-caprolactam, poly-N-vinyl-3-methyl-2-caprolactam, poly-N-vinyl-3-methyl-2-piperidone, poly-N-vinyl-4-methyl-2-piperidone, poly-N-vinyl-4-methyl-2-caprolactam, poly-N-vinyl-3-ethyl-2-pyrrolidone, poly-N-vinyl-4,5-dimethyl-2-pyrrolidone, polyvinylimidazole, poly-N-vinylformamide, poly-N-vinyl(methyl)acetamide, poly-N-methyl-N-vinyl(methyl)acetamide, poly-N-vinyl-N-(methyl)propionamide, poly-N-vinyl-N-methyl-2-(methyl)propionamide, poly-N-vinyl-2-(methyl)propionamide, poly-N-vinyl-N,N'-dimethyloxetane, poly-N,N-dimethylacrylamide, poly-N,N-diethylacrylamide, poly-N-isopropylacrylamide, polyvinyl alcohol, polyacrylate, polyethylene oxide, poly-2-ethyloxazole, heparin, polysaccharide, polyacrylonitril and their mixtures and copolymers. Hydrophilic polymers selected from polyvinylpyrrolidone, poly-N,N-dimethylacrylamide, polyacrylic acid, polyvinyl alcohol, poly-N-methyl-N-vinyl(methyl)acetam�and their mixtures and copolymers, can be particularly effective to enhance the wettability of some silicone-hydrogels. Polyvinylpyrrolidone and poly-N,N-dimethylacrylamide provide a balance between the wettability of silicone hydrogel and compatibility with the monomer mixture in some formulations. Examples of suitable wetting agents are described in U.S. patents No. 2006-0072069A1, No. 6367929 and No. 2008-0045612A1.

If the amount of hydrophilic polymer used to obtain the silicone hydrogel of the present invention, it will be too little, it will not be achieved the desired wettability, however, if the quantity is too large, the hydrophilic polymer is not easily dissolved in the monomer mixture, and therefore, this amount should be from about 1 to about 30% by weight., in some embodiments, the present invention is from about 2 to about 25% by weight., other embodiments of the present invention is from about 3 to about 20% wt., and in yet another embodiments, the present invention is from about 6 to about 20% by weight. the monomer and polymer component in the monomer mixture. The lower bound of contents include about 1% by weight., about 2% wt., preferably about 3% by weight. and about 6% by weight. The value of the upper limit of the content include about 30% by weight., about 25% wt., about 20% of the weight. and about 9% by weight. Any of the values of the lower border of the content can b�you combined with any of the upper bound value of the content.

If the molecular weight of the hydrophilic polymer used to obtain the silicone hydrogel of the present invention, is too small, it will not be achieved the desired wettability, but if this mass is too large, it will decrease the solubility in the monomer mixture and increase its viscosity. In one embodiment of the present invention, the molecular weight is preferably from 1,000 daltons to 10 million daltons, in some embodiments of the present invention is from 100,000 dalconzo 1 million daltons, in other embodiments of the present invention is from 200000 to 800000. In embodiments of the present invention where the hydrophilic polymer contains at least one reactive group capable to form a covalent bond with the silicone hydrogel matrix, the molecular weight should be at least about 2000 daltons, at least about 5000 daltons; and in some embodiments of the present invention range from about 5,000 to about 180,000 daltons, or from about 5,000 to about 150,000 daltons. The lower bound of molecular weight include about 1,000 daltons, about 100,000 daltons and 200,000 daltons. The value of the upper limit of molecular weight include about 10 million daltons, about 1 million daltons and about 800,000 daltons. Liu�th of preferred values of the lower bounds can be combined with any of the preferred values the upper bound. The molecular weight of the hydrophilic polymer of the present invention is expressed as a weighted average molecular weight (Mw), measured using chromatography on a permeable gel (column: TSK gel GMPWXL, the production company Tosoh Corporation, mobile phase: water/methanol = 50/50 with the addition of 0.1 N lithium nitrate, flow rate: 0.5 ml/min, detector: differential refractive index detector, a standard sample molecular weight: polyethylene glycol).

In one embodiment of the present invention, the monomer mixture to obtain the silicone hydrogel of the present invention preferably also satisfies the following conditions (D).

(D) At least part of the silicone monomer is a silicone (meth)acrylamide monomers, and the total number of all (meth)acrylamide monomers (silicone and resiliancy (meth)acrylamide monomers) is about 90% or more by weight relative to the total content of monomer components in the monomer mixture.

For the monomer component used in the polymerization of the silicone hydrogel of the present invention, logically, that if the number Niacinamide monomers is too large, the overall rate of polymerization will decrease, so the total number of all (meth)acrylamide monomers (silicone and resiliancy (meth)acrylamide monomer�in) in one embodiment of the present invention is about 90% weight. or more, in another embodiment about 95% by weight. or more.

The silicone hydrogel of the present invention may also contain a second resiliancy the amide type monomer in addition to the acrylamide monomer naselyonnogo type, which contains in its molecule two or more hydroxyl groups. Their examples include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, (meth)acryloylmorpholine, N-methoxymethyl(meth)acrylamide, N-gidroximetil(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide and the like. Of these, N,N-dimethylacrylamide is preferred from the viewpoint of the balance between hydrophilicity, compatibility with silicone monomer and the rate of polymerization.

If the number of used second naselyonnogo (meth)acrylamide monomer is too large, it will reduce the permeability to oxygen, however, if it is too low, the silicone hydrogel will be too hard, and therefore the amount of the second naselyonnogo (meth)acrylamide monomer in this embodiment of the present invention is from about 1 to about 50% by weight., more preferably from about 10 to about 40% by weight., and most preferably from 15 to 35% wt., based on the content of the monomer and polymer component in the monomer mixture. The lower bound of soda�Jania is about 1% wt., about 10% of the weight. and about 15% by weight. Value of upper limit of the content is about 50% wt., about 40% of the weight. and about 35% by weight. Any of the values of the lower bounds can be combined with any of the upper bound value.

The silicone hydrogel of the present invention can also include a monomer having two or more polymerizing groups as copolymerization component. In this case, the silicone hydrogel of the present invention creates a stable to solvents. Preferred examples of monomers with two or more polymerization groups include bifunctional and polyfunctional acrylates such as ethylene glycol(meth)acrylate, diethyleneglycol(meth)acrylate, triethyleneglycol(meth)acrylate, neopentylglycol(meth)acrylate, tetraethyleneglycol(meth)acrylate, glycerite(meth)acrylate, pentaerythritol(meth)acrylate, trimethylolpropane(meth)acrylate and bisacrylamide, such as N,N'-methylenebisacrylamide, N,N'-ethylenebisacrylamide , N,N'-propyleneamine and the like. Of them bisacrylamide are preferred from the viewpoint of increasing the speed of polymerization, and of these, preferred are N,N'-methylenebisacrylamide and N,N'-ethylenebisacrylamide. The amount used of the monomer containing two or more polymerization is from about 0.1 to about 10% in�S., in some embodiments, the present invention is from about 0.5 to about 8% by weight., in other embodiments, the present invention is from about 0.8 to about 5% by weight. The lower bound of contents are about 0.1% wt., about 0.5% by weight. and about 0.8% by weight. The value of the upper limit of the content of up to about 10% by weight., about 8% of the weight. and about 5% by weight. Any of the preferred values of the lower bounds can be combined with any of the preferred upper bound value.

When receiving the silicone hydrogel of the present invention by polymerization can also be added to the polymerization initiator for its acceleration. Suitable initiators include thermal polymerization initiators, such as peroxide compounds or azo compounds, photo-polymerization initiators (which may be made under the action of ultraviolet rays, light in the visible spectrum, or combinations thereof), or mixtures thereof. When applying thermal polymerization is selected and used in such a thermal polymerization initiator, which has optimal parameters of decomposition at the desired reaction temperature. Typically, the initiators presented azosoedineniem or peroxide compound, preferably, the temperature of the half-life of 10 hours was approx�tive from 40°C to 120°C . Examples of photo-polymerization initiators include carbonyl compounds, peroxide compounds, azo compounds, sulfur compounds, halogenated compounds, metal salts and the like. More specific examples of photoinitiators include aromatic alphahydroxy, alkoxycarbonyl, acetophenone, acylphosphatase, besatisfied and trerice amines with a diketone, mixtures thereof and the like. Illustrative examples of photoinitiators are 1-hydroxycyclohexyl, 2-hydroxy-2-methyl-1-phenylpropan-1-he, bis(2,6-dimethoxybenzoyl)-2,4-4- trimethylphosphine oxide (DMBAPO), bis(2,4,6-trimethylbenzoyl)-phenylphosphine (Irgacure 819), 2,4,6-trimethylbenzenesulfonyl oxide and 2,4,6-trimethylbenzenesulfonyl oxide, methyl ether of benzoin, and the combination of camphoroquinone and ethyl 4-(N,N-dimethylamino)benzoate. On sale are initiation system that is activated by light in the visible region of the spectrum, they include systems of Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 819, Irgacure 1850 (all produced by BASF) and the initiator Lucirin TPO (marketed by BASF). Commercially available UV photoinitiators include Darocur 1173 and Darocur 2959 (BASF). These and other photoinitiators, which could be used for this purpose are described in Volume III: Photoinitiators for Free Radical Cationic &Anionic Photopolymerization", 2ndEdition by J. V. Crivello &K. Dietliker; edited by G. radley; John Wiley and Sons; New York; 1998, which is incorporated herein by reference. These polymerization initiators can be used separately from each other, and in the mixture, and the amount used is approximately 1% by weight. from 100% weight. the monomer component.

Other components that may be present in the reaction mixture used to produce contact lenses of the present invention include compounds that absorb ultraviolet light, medicinal compounds, nutraceuticals, anti-microbial compounds, copolymerisate and non-polymerizing dyes, including dyes and compounds that are able to reversibly change color or reflect light when exposed to light with different wavelengths, release agents, reactive dyes, pigments, combinations thereof and the like.

When receiving the silicone hydrogel of the present invention by polymerization may be used a solvent. The solvent may be organic or inorganic solvent of any kind. Examples of solvents used include water, methanol, ethanol, propanol, 2-propanol, butanol, tert-butanol, tert-amyl alcohol, 3,7-dimethyl-3-octanol, tetrahydropyranol and other alcohol solvents; benzene, toluene, xylene and other aromatic hydrocarbon solvents; hexane, �eptan, octane, decane, petroleum ether, kerosene, naphtha, paraffin and other aliphatic hydrocarbon solvents; acetone, methyl ethyl ketone, methyl isobutyl ketone and other ketone solvents; ethyl acetate, butyl acetate, methylbenzoate, dioctyl phthalate, etilenglikolevye and other ester solvents; diethyl ether, tetrahydrofuran, dioxane, valkiry ether of ethylene glycol, valkiry ether of diethylene glycol, valkiry ether triethyleneglycol, valkiry ether tetraethyleneglycol, valkiry ether of polyethylene glycol, block copolymer of polyethylene glycol/polypropylene glycol, a non-statistical copolymer of polyethylene glycol/polypropylene glycol and other solvents glycol ethers. Solvents can be used individually or in combination. Of these, alcoholic solvents and solvent-based glycol ethers are preferred from the viewpoint that the solvent can be easily removed from the obtained silicone hydrogel by washing with water. The solvents used for the preparation of the devices of this invention include ethers, esters, alkanes, halide alkali, silanes and alcohols. Examples of ethers used in the present invention, suitable diluents include tetrahydrofuran. Examples of the ester�in, used in the present invention, suitable diluents include ethyl acetate. Examples of alkylhalides used in the present invention, suitable diluents include the methylene chloride. Examples of silanes used in the present invention, suitable diluents include octamethylcyclotetrasiloxane. Examples of alcohols used in the present invention, suitable diluents include hexanol, heptanol, octanol, nonanol, decanol, tert-butyl alcohol, 3-methyl-3-pentanol, isopropanol and 3,7-dimethyl-3-octanol. Additional diluents used in this invention are described in U.S. patent No. 6020445, which is incorporated herein by reference.

The silicone hydrogel of the present invention can be used independently by molding to desired shape, but it can also be mixed with other substances and then molded. Moreover, the surface of molded parts can be coated.

The field of application of the silicone hydrogels of the present invention include the manufacture of ophthalmic lenses, endoscopes, catheters, tubes for blood transfusion, airway tubes, stents, guidewires for catheter, cuff, medical connector, ports for vascular access, drainage bags, contours circulation, materials for pok�of itia wounds and various types of medical media but it is particularly suitable for contact lenses, intraocular lenses, artificial corneas, inlays and onlays for corneas, and is best suited for the manufacture of contact lenses.

When the silicone hydrogel of the present invention is subjected to molding and is used for the manufacture of ophthalmic lenses, the method of polymerization and the method of molding can be represented by the following standard methods. Examples include methods primary molding silicone hydrogel into a round billet or plate and methods of further processing to give the desired shape by cutting or lathing, etc., the method of polymerization of the molding material, the method of centrifugal casting in rubber mould and the like.

As an example, the following method, applicable in the case of ophthalmic lenses made from silicone hydrogel of the present invention, the method of polymerization of the molding material.

The monomer composition is introduced into the space between the two molds that are shaped like lenses. After that to obtain the shape of the lens is carried out photopolymerization or thermal polymerization. Forms can be made of plastic, glass, ceramic, metal, etc., however, for light curing materials are used, which are�Xia transparent to photopolimerization light with a specific wavelength, and this is usually done by glass or plastic. In the manufacture of silicone hydrogel space is formed by two facing each other of the molds, and the monomer composition is introduced into this space. After that, the casting with the space filled with the monomer composition, are exposed to activating light, such as ultraviolet rays, visible light spectrum, or a combination of, or is placed in an oven or in a bath and heated for polymerization of the monomer. You can also use both methods: first, photopolymerization is carried out, after light curing is carried out by thermal polymerization or Vice versa, when after thermal polymerization, photopolymerization is carried out. Usually in the case of photo-polymerization occurs intense irradiation by light from a source such as a mercury or fluorescent lamp, in a short period of time (usually 1 hour or less. Conducting thermal polymerization under conditions when the temperature is gradually increased from about ambient to high temperatures from about 60°C to about 200°C for several hours or several tens of hours, is preferred from the viewpoint of ensuring the optical density, the quality of the polymer and improve the reproducibility.

The silicone hydrogel of the present �of subramania may be modified in various ways. If it will be used for creating ophthalmic lenses, and a hydrophilic polymer was used as an internal additive, there must be a modification process to improve the wetting properties of a lens.

Special modification methods include electromagnetic (including light) irradiation, plasma irradiation, vacuum deposition, chemical treatment by vacuum deposition, such as plating plating, heat treatment, direct coating, form download with coating, processing bases, processing acids and processing of other substances which are suitable for surface treatment, can also be used combination thereof.

Examples of treatment with bases or acids include methods of treatment of the moulded product solutions of bases and acids or methods of processing of molded products of gaseous bases and acids. More specific methods include, for example, a method of dip molded products in the basic or acidic solution, a method of spraying a basic or acidic solution or a basic or acidic gas to the molded product, method of application of the basic or acidic solution on the molded product by means of paddle stirrers, brushes, etc., the method of coating the molded product a method�m centrifugation with a basic or acidic solution, the method of applying the coating layer by dipping, and the like. The most simple method, having a large modifying effect, is the method of dip molded products in the basic or acidic solution.

The temperature at which the silicone-hydrogel is immersed in a basic or acidic solution, usually not standardized, but usually the temperature is in the range from about -50°C to approximately 300°C. From the viewpoint of the convenience of a more preferred temperature range from about -10°C to 150°C, and most preferred temperature range from about -5°C to about 60°C.

The optimal time during which the silicone-hydrogel remains immersed in a basic or acidic solution varies with temperature, but usually it is preferably 100 hours or less, more preferably 24 hours or less, and most preferably 12 hours or less. If this contact will last for too long, you will suffer not only the convenience of work or reduced productivity, but also can result in such negative effects, such as reduced permeability to oxygen and the deterioration of mechanical properties.

Examples of bases that may be used include hydroxides of alkali metals, hydroxides of alkaline earth metals, various kinds of Carbo�of ATA, different types of borates, different types of phosphates, ammonia, various ammonium salts of various amines and polymeric bases, such as polyethyleneimine, polyvinyliden and the like. Of these the most preferred are the hydroxides of alkali metals, because they are cheap and have a strong impact.

Examples of acids that may be used include various types of inorganic acid, such as sulfuric acid, phosphoric acid, hydrochloric acid and nitric acid; various kinds of organic acids such as acetic acid, formic acid, benzoic acid and phenol; and various types of polymeric acids such as polyacrylic acid, polystyrene acid and the like. Of these the most preferred are polymeric acids, because they have a strong impact and a negative impact on physical properties is minimal.

Solvents in basic or acidic solutions can be inorganic or organic solvents of any kind. Examples include water, methanol, ethanol, propanol, 2-propanol, butanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerol and other alcohols, benzene, toluene, xylene and other aromatic hydrocarbons, hexane, heptane, octane, Dean, petrolei�th ether, kerosene, naphtha, paraffin, and other aliphatic hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone and other ketones, ethyl acetate, butyl acetate, methylbenzoate, dioctyl phthalate and other ester solvents, diethyl ether, tetrahydrofuran, dioxane, valkiry ether of ethylene glycol, valkiry ether of diethylene glycol, valkiry ether triethyleneglycol, valkiry ether tetraethyleneglycol, valkiry ether of polyethylene glycol, and other ethers; dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylimidazolidine, hexamethylphosphoric triamid, dimethylsulfoxide and other aprotic polar solvents, methylene chloride, chloroform, dichloroethane, trichloroethane, trichloroethylene and other halogenated solvents and solvent-freon type. Of these, water is most preferred from the standpoint of economy, ease of use, chemical stability and the like. The solvent may also be a mixture of two or more kinds of solvents.

In the present invention used basic or alkaline solvent may contain components that may vary from basic or acidic substances in the solvent.

Basic or acidic compounds can be removed from silicone hydrogel by washing after handling this base� or acid.

The solvent for washing can be inorganic or organic solvent of any kind. Examples include water, methanol, ethanol, propanol, 2-propanol, butanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerol and other alcohols, benzene, toluene, xylene and other aromatic hydrocarbons, hexane, heptane, octane, decane, petroleum ether, kerosene, naphtha, paraffin, and other aliphatic hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone and other ketones, ethyl acetate, butyl acetate, methylbenzoate, dioctyl phthalate and other ester solvents, diethyl ether, tetrahydrofuran, dioxane, valkiry ether of ethylene glycol, valkiry ether of diethylene glycol, valkiry ether triethyleneglycol, valkiry ether tetraethyleneglycol, valkiry ether of polyethylene glycol, and other ethers; dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylimidazolidine, hexamethylphosphoric triamid, dimethylsulfoxide and other aprotic polar solvents, methylene chloride, chloroform, dichloroethane, trichloroethane, trichloroethylene and other halogenated solvents and solvent-freon type.

The solvent for washing can be a mixture of two or more kinds of solvents. The solvent for washing can sod�neigh components which may differ from the solvent, such as inorganic salts, surfactants and cleansers.

The above-described modification can affect all silicone hydrogel and can only be performed on his part, such as the surface of a silicone hydrogel. If the modification was carried out only on the surface, the wettability of its surface may be increased without significantly changing the physical properties of the silicone hydrogel.

If the water content silicone hydrogel of the present invention is too low, the silicone hydrogel will be too hard, however, if the water content is too large, the water can evaporate from the surface of silicone hydrogel, which while wearing the lenses, the user can feel the dryness, so it is desirable that the water content ranged from about 20 to about 50% by weight., more preferably from about 25 to about 45% by weight., and most preferably from about 30 to about 40% by weight. The lower bound values is about 20% wt., about 25% of the weight. and about 30% by weight. The upper bound values is about 50% wt., about 45% of the weight. and about 40% by weight. Any of the preferred values of the lower bounds can be combined with any of the preferred upper bound value.

The elastic modulus of the silicone hydrogel of the present Fig�plants preferably is about 1379,0 kPa (200 psi) or less, in some embodiments, the present invention is about 689,58 kPa (100 psig) or less, from the point of view of achieving a sense of comfort when wearing ophthalmic lenses, especially when wearing soft contact lenses. The modulus of elasticity and elongation of the polymer are measured by circumcision of the molded mass of the sample as long, while its width at the thinnest parts will not be 5 mm, after which it is stretched at a speed of 100 mm / min using the apparatus for testing a tensile at break of the polymer. Measured initial standard length of the sample (Lo) and sample length at break (Lf). Produced by twelve measurements for each composition, and presents the average value. Module stretching is measured at the initial linear portion of a curve load/tension. Percentage elongation = [(Lf-Lo)/Lo]×100,

The elongation of the silicone hydrogel of the present invention preferably is about 100% or more, in some embodiments of the present invention is about 150% or more, and in the most preferred embodiments of the present invention is about 200% or more. Higher values indicate that silicone-hydrogel has a tensile strength.

If this material is used for the manufacture of ophthalmic lenses, the contact angle with Nate�spec silicone hydrogel of the present invention preferably is about 70° or less, about 60° or less, in some embodiments of the present invention is approximately 50° or less.

For oxygen permeability silicone hydrogel of the present invention it is desirable that the oxygen permeability coefficient was about 50×10-11(cm2/h)ml O2/(ml·hPa) or more, and in some embodiments of the present invention it is 50×10-11(cm2/h)ml O2/(ml·hPa) or more. The oxygen permeability coefficient of the polymer of the present invention is the value measured by the polarographic method.

If this material is used for the manufacture of ophthalmic lenses, for the transparency of the silicone hydrogel of the present invention, it is preferable that the total light transmittance in the visible region of the spectrum was about 85% or more, more preferably about 90% or more, and most preferably about 95% or more.

The silicone hydrogel of the present invention is suitable for use in such medical devices such as ophthalmic lenses, endoscopes, catheters, tubes for blood transfusion, airline tubing, stents, wires for catheter, cuff, medical connector, ports for vascular access, drainage bags, contours circulation, material�in to cover wounds and various types of medical media but it is particularly suitable for contact lenses, ophthalmic lenses and artificial corneas.

Further, the present invention is described in detail below using working examples, but the present invention is not limited to these working examples.

Methods of measurement for examples 1 to 17

(1) the Total light transmittance

The total light transmittance was measured using an SM color computer (model SM-7-CH, manufactured by Suga Test Instruments Co. Ltd.). Water on the surface of the sample lens was a bit dried, after which the sample was mounted under the stream of light was measured. The thickness was measured using ABC Digimatic Indicator (ID-C112, manufactured by Mitsutoyo Corporation), and samples with a thickness of 0.14-0.15 mm were measured.

(2) the Modulus of elasticity and elongation

From the sample lens was cut molded mass with the width at the thinnest part of 5 mm, the thickness was measured using ABC Digimatic Indicator (ID-C112, manufactured by Mitsutoyo Corp.), then the elastic modulus and elongation were measured using Tensilon (RTM-100, manufactured by Toyo Baldwin Co. Ltd., the speed of the cross head 100 mm/min).

(3) the water Content

We measured the weight of water containing a silicone-hydrogel (W1) and the weight in dry (W2), and the water content was calculated by the following formula.

Water content (%)=(W1-W2)/W1×10

However, in accordance with the present invention, in a state where the silicone-hydrogel contains water, corresponds to the condition where the silicone hydrogel is immersed in a physiological solution at 25°C for 6 hours or more. Moreover, the dry conditions silicone hydrogel corresponds to the state when the drying is carried out for 16 hours or more in a vacuum oven for drying at 40°C.

(4) Dynamic contact angle

From the sample lens was cut short strip with a width of 5 mm, and the dynamic contact angle was measured using the device for measuring dynamic contact angle WET-6000, manufactured by Rhesca Corporation (the sinking velocity of 7 mm/min).

(5) Mechanical stress in the initial moment of time

A long strip of the sample width of 5 mm and a length of 1.5 cm was cut from the Central part of the lens, and the measurement was conducted with the help of plastometer CR-500DX, manufactured by Sun Scientific Co. Ltd. The sample was mounted in a clamp with a width of 5 mm, and after stretching for 5 mm at a speed of 100 mm/min the sample was the same speed returned to its original length (5 mm), and this cycle was repeated three times. The moment of time when the voltage is absent, the length of time for which the sample a second time returns to its original length, the length of time before it was applied n�to the unit (when the voltage is not zero) after the beginning of the third cycle of stretching has been defined as the mechanical stress of the initial moment of time. Shorter mechanical stress in the initial time that the silicone-hydrogel has a good ability to recover form, and a value of 2 seconds or less is preferable, more preferable is equal to 1.5 seconds or less, and most preferred is equal to 1.2 seconds or less.

Working example 1

Silicone monomer corresponding to the following formula (s1)

[Formula 13]

(0,925 g, 56,06% wt.), N,N-dimethylacrylamide (0,510 g, 31,27% wt.), and resiliancy the acrylamide monomer corresponding to the following formula (h1)

[Formula 14]

(0,017 g, 1% wt.), polyvinylpyrrolidone (PVP K90, 0,132 g, 8% wt.), N,N'-methylenebisacrylamide (IBA, 0,018 g, 1.1% wt.), the absorber of ultraviolet rays 2-(2'-hydroxy-5'-methacryloyloxyethyl)-2H-benzotriazole (0.036 g, 2,22% wt.), 3-methyl-3-pentanol (3M3P, 1,350 g), and photoinitiator Irgacure 819 (0.004 g, 0.25% wt.) were mixed together and stirred. The obtained monomer mixture was degassed in argon. The monomer mixture was introduced into the cavity in a transparent plastic (the front surface shape: Zeonor, the base shape: polypropylene) form for casting in the form of lenses in the protective chamber with gloves in a nitrogen atmosphere, and the lens was obtained by irradiation with light (Philips TL03, 1.6 mW/cm2

Received total light transmittance, water content, elastic modulus and elongation of the sample lenses are shown in Table 1, and thus obtained lens was transparent and had a balance of desired physical properties.

[Table 1]
Silicone monomerResiliancy acrylamideDimethyl-acetamide
(% wt.)
%TWater content (%)The modulus of elasticity (kPa (lb per square inch))Extension explained (%)Mechanical� voltage at the initial moment of time (from) Dynamic contact angle (degrees)
monomerweight % monomerweight %
Working example 1(s1)56,06(h1)131,2792,040,7656,4 (95,2)2540,8136,5
Working example 2(s1)56,06(h1)230,2792,037,0592,9 (86,0)2930,9743,8
Working example 3(s1)56,06(h1)329,2791,738,0743,9 (107,9)306 0,9945,2
Working example 4(s1)56,06(h1)527,2791,6The 36.1657,8 (95,4)3640,9347,5
Working example 5(s1)56,06(h1)725,2791,537,3806,0 (116,9)3700,85A 50.1
Working example 6(s1)56,06(h1)1220,27About 91.834,7934,2 (135,5)2950,9150,2
Working example 7(s1)56,06(h2) 131,2791,240,0710.2 million (103,0)2321,0135,2
Working example 8(s1)56,06(h2)230,27To 91.137,7675,0 (97,9)2761,0135,9

309
Working example 9(s1)56,06(h2)329,2791,637,6663,3 (96,2)2820,9528,5
Working example 10(s1)56,06(h2)527,27To 91.137,0782,6 (113,5)0,9733,9
Working example 11(s1)56,06(h2)725,2791,636,3988,0 (143,3)2921,0934,5
Comparative example 1(s1)56,06HEAA131,2782,041,0589,5 (85,5)3691,0530,2
Comparative example 2(s1)56,06HEAA230,2743,842,0561,2 (81,4)3060,9333,9
Comparative example 3(s1) 56,06HEAA329,2718,743,6611,6 (88,7)3240,9336,6
Comparative example 4(s1)56,06HEAA527,2717,742,2599,8 (87,0)3020,9127,8
Comparative example 5(s1)56,06HEAA725,2711,841,1614,3 (89,1)2920,8132,4
Comparative example 6(s1)56,06HEAA1220,278,641,1 706,7 (102,5)1860,85The 38.6

Working examples 2-6

Sample lenses were obtained by polymerization similarly to the working example 1 except that the composition was changed as shown in Table 1. Appearance, total light transmittance ratio, water content, modulus, and elongation of the obtained sample are shown in Table 1.

Working example 7

The sample lens was manufactured similarly to the working sample 1 except that the monomer fits the following formula (h2)

[Formula 15]

was used instead of the monomer corresponding to the formula (h1), as naselyonnogo acrylamide monomer. Appearance, total light transmittance ratio, water content, modulus, and elongation of the obtained sample are shown in Table 1.

Working examples 8-11

The sample lens was obtained by polymerization similarly to the working example 7 except that the composition was changed as shown in Table 1. Appearance, total light transmittance ratio, water content, modulus, and elongation of the obtained sample are shown in Table 1.

Comparative examples 1-6

Sample lenses were obtained by polymerization Ana�ogino working example 1 except that 2-hydroxyethylacrylate (HEAA), corresponding to the following formula (h0)

[Formula 16]

was used instead of the monomer corresponding to the formula (h1), as naselyonnogo acrylamide monomer, and the composition was given in Table 1. Appearance, total light transmittance ratio, water content, modulus, and elongation of the obtained sample are shown in Table 1. According to the data of Table 1 one can see that the total light transmittance ratio lens was undesirably low. So asilicone the acrylamide monomers having hydrogen at the nitrogen atom and one hydroxyl group, can not provide the desired level of compatibility of components in the composition. Comparative examples 1-5 showed the desired values of the modulus of elasticity.

Working examples 12-16

Sample lenses were obtained similarly to the working example 1 using a monomer corresponding to the following formula (s2),

[Formula 17]

as the silicone acrylamide monomer, and the monomer corresponding to the formula (h1) or (h2), as naselyonnogo acrylamide monomer in the composition, which was shown in Table 2. Appearance, total light transmittance ratio, water content, elastic modulus and elongation of the sample obtained� shown in Table 2.

[Table 2]
Silicone monomerResiliancy
acrylamide
Dimethyl-acetamide
(% wt.)
%TThe substance of water
(%)
The modulus of elasticity (kPa (lb per square inch))Extension explained (%)Mechanical stress at the initial moment of time (from)Dynamic contact angle (degrees)
monomerweight % monomerweight %
Working example 12(s2)56,06(h1)527,2788,940,9648,1 (94,0)2720,9447,4
Working example 13 (s2)56,06(h1)725,2788,940,1601,2 (87,2)2201,0053,5
Working example 14(s2)56,06(h1)1220,27Of 89.439,5573,0 (83,1)232Of 0.8747,5
Working example 15(s2)56,06(h1)2012,2787,1Of 40.3550,2 (79,8)2170,83Of 55.4
Working example 16(s2)56,06(h2)725,2787,339,9 613,6 (89,0)2970,8844,8
Comparative example 7(s2)56,06HEAA527,273,244.1 kHz472,3 (68,5)2531,1553,5
Comparative example 8(s2)56,06HEAA725,273,344,0469,5 (68,1)2131,0254,4
Comparative example 9(s2)56,06HEAA1220,273,943,6450,2 (65,3)2561,0161,7

Comparative primary-9

Sample lenses were obtained similarly to the working example 1 using a monomer corresponding to the formula (s2), as naselyonnogo acrylamide monomer, and HEAA corresponding to the formula (h0), as the silicone acrylamide monomer in the composition shown in Table 2. Appearance, total light transmittance ratio, water content, modulus, and elongation of the obtained sample are shown in Table 2. Comparing the results of comparative examples 6-9 examples 12-16 can see that HEAA not have significant effect in these systems as compatibilizer. Surprisingly, the connection methacrylate, 2-hydroxyethylmethacrylate, plays in silicone hydrogels the role of a substance that improves the compatibility of the components. Despite this, the compositions of comparative examples 6-9, which used HEAA, showed the desired low modulus of elasticity.

Working example 17

The components shown in Table 3, were mixed with N,N'-methylenebisacrylamide (IBA, 1.1% wt.), 2-(2'-hydroxy-5'-methacryloyloxyethyl)-2H-benzotriazole (Norbloc, 2.2% wt.), the photoinitiator Irgacure 819 (0.25% wt.) and tertiary amyl alcohol (TAS) as a solvent in a ratio of 45% by weight. thinners to 55% by weight. components, and stirred. The following acronyms are used in Table 3.

(s1) denotes the m silicone�formula number:

[Formula 18]

(h1) denotes resiliancy the acrylamide monomer (HCA in Table 3), corresponding to the following formula:

[Formula 19]

DMAP,N-dimethylacrylamide

Pupilvandergraht (PVP K90).

The obtained monomer mixture was degassed in vacuum. The monomer mixture was introduced into the cavity in a transparent plastic (the front surface shape: Zeonor, the base shape: polypropylene) form for casting in the form of lenses in the protective chamber with gloves in a nitrogen atmosphere, and the lens was obtained by irradiation with light (Philips TL03, 1.5 mW/cm215 minutes) before curing. This lens was separated from the casting, and impurities such as residual monomer were extracted by immersing the lenses in a 70/30 (volume/volume) mixture of isopropyl alcohol (IPA) and deionized water for ~90 minutes at room temperature. After extraction, the lenses were immersed in deionized water for ~90 minutes to remove the IRS, and then stored in a standard storage solution for bringing in the equilibrium state. Individual lenses were placed in vials with a volume of ~5 ml of the storage solution and autoclavability at ~120°C for 30 minutes. The measured values of turbidity, water content, dynamic contact angle and elastic modulus re�Isley in Table 3. Thus, the obtained lens was transparent enough and had a balance of desired physical properties.

The contact angle in the case in examples 17-19 and examples 31-36 were measured as follows. For each set were prepared four samples, cutting out a strip width of approximately 5 mm from the Central part of the lens and keeping it in the storage solution before reaching the equilibrium state. Then, using the microbalance Wilhelmi, at 23°C measured wetting force between the surface of the contact lens material and borate buffer solution immersion of the sample into the solution and when removing the sample from the solution. To be processed using the following equation:

where F denotes the wetting ability, γ denotes the surface tension of the sample liquid, p denotes the perimeter of the convex-concave of the sample, and d θ denotes the contact angle. The contact angle in the case is determined from the portion of the wetting experiment where the sample is immersed in the storage solution. Each sample had four measurement cycle and the results averaged, obtaining the wetting angles in the case analyzed lenses.

Turbidity in examples 17-19 and examples 31-36 were measured by placing a hydrated test lens in borate buffer �actor in a clean glass cell size of 20×40×10 mm at ambient temperature above a flat black background, after that was done the irradiation of the cell with a lens optic lamp (Titna Tool Supply Co. fiber optic lamp with a set of optical fibers with a diameter of 0.5” and a capacity of 4-5. 4) at an angle of 66° to the normal of the image capturing lens from above, normal to the plane of the cell with a lens, using the camera (RGB camera DVC 1300C:19130 with a lens with a variable focal length Navitar TV Zoom 7000) placed at a distance of 14 mm above the platform with the lens. Background scattering was removed from the dispersion of the lens by subtracting the image of an empty cell using software EPIX XCAP V 1.0. The image is subtracted scattered light is subjected to quantitative analysis by integrating the Central 10 mm of the lens, and then comparing with -1,00 E lenses CSI Thin Lens®, for an arbitrary set opacity takes the value 100, and in their absence is 0. An analysis was conducted of five lenses, and the results were normalized to average values for percentage values of turbidity for standard lenses CSI.

The modulus of elasticity in examples 17-19 and examples 31-36 were measured using a testing machine tensile transverse head with a constant rate of displacement, which is equipped with a voltage sensor, which is reduced to the initial height of water level measurements. Suitable test machine Instron is, fashion�ü 1122. The sample in the form of a "dog bone" with a length of 1.33 cm (0,522 inches), width at the level of the clamp 0,701 cm (0,276 inch) and a width at the narrowest point 0,541 cm (0,213 in) was placed in a clamp and elongated at a constant speed and voltage of 2 inches per minute until failure. Measured initial standard length of the sample (Lo) and sample length at break (Lf). Produced by twelve measurements for each composition, and presents the average value. Module stretching is measured at the initial linear portion of a curve load/tension. Percentage elongation = [(Lf-Lo)/Lo]×100.

Working examples 18 and 19

Sample lenses were obtained by polymerization similarly to the working example 17 except that the composition was changed as shown in Table 3. The measured values of turbidity, water content, dynamic contact angle and elastic modulus are listed in Table 3.

Working examples 20-24

Sample lenses were obtained similarly to the working example 17 except that the composition was changed as shown in Table 3. The measured values of turbidity, water content, dynamic contact angle and elastic modulus are listed in Table 3. Comparing examples 20-22 with example 17, one can see that the PVP content decreased, and the obtained lenses have become more transparent, but less wettable. Comparing examples 23-25 with the example�m 17, you can see that the content of PVP was increased or resiliancy monomer was replaced by (h2), which made wettable lenses, but less transparent.

Working example 25

The sample lens was obtained similarly to the working example 17 except that was used resiliancy (meth)acrylamide monomer of formula (h2).

[Formula 20]

The measured values of turbidity, water content, dynamic contact angle and elastic modulus are listed in Table 3.

Table 3
No. example[s1] % weight.[NSA]
% weight.
[DMA] % weight.[PVP] % weight.Blurred
% CSI
% H2OThe modulus of elasticity
kPa (pounds per square inch)
Dynamic contact angle
1756330821±245827,4±68,9 (120±10)51±5
18453,440818±153779,1±62,1 (113±9)48±16
19483,439733±151827,4±68,9 (120±10)54±13
2055336217±1391130,7±110,3 (164±16)MS*
2140351216±155896,3±48,3 (130±7)MS*
2251338523±144841,2±75,8 (122±11)/td> MS*
23553261275±148910,1±41,4 (132±6)75±14
24453401042+255710,1±48,3 (103±7)50±8
2556330883±3345806,7±48,3 (117±7)57±4
MS= a lower wettability

The synthesis of monomer 1

2-(N-methylamino)ethanol (of 7.88 g, 0,105 mol) and tetrahydrofuran (100 ml) were placed in a flask with three necks, with a volume of 300 ml, and then in an ice bath (-10 to -5°C) dropwise using a dropping funnel for about 20 minutes add the chloride of acrylic acid (4,1 ml, 0.05 mol).

2 hours after the start of adding dropwise, the reaction Sol�R was filtered, and the precipitate was washed with hexane, which was chilled in the fridge. The solution for washing was mixed with the filtrate and then concentrated through evaporation apparatus. The crude substance was purified using column chromatography with silica gel (eluent is tetrahydrofuran). Was obtained a monomer corresponding to the following formula (h3)

[Formula 21]

The synthesis of monomer 2

The monomer was synthesized similarly to the synthesis of monomer 1 except that instead of 2-(N-methylamino)of ethanol was used 1-(N-methylamino)-2,3-dihydroxypropane. Was obtained a monomer corresponding to the following formula (h4)

[Formula 22]

The working sample 26-27

The sample lens was obtained similarly to the working example 1 except that the monomer corresponding to the formula (h3) and (h4), was used instead of the monomer corresponding to the formula (h1), as naselyonnogo acrylamide monomer, and except that the composition was changed as shown in Table 4. Appearance, total light transmittance ratio, the soda content, the modulus of elasticity and elongation of the obtained sample are shown in Table 4.

25,27
Table 4
silicone acrylamideresiliancy acrylamideN,N-dimethylacrylamide
(% wt.)
The transmittance of light (%)Water content (%)The modulus of elasticity
(kPa (pounds per square inch))
Elongation(%)Mechanical stress in the initial moment of time
Time(s)
The contact angle in the case of
(C)
Formula(% wt.)Formula(% wt.)
Working example 26(s1)56,06(h3)725,2790,3N/aN/aN/aN/aN/a
The working sample 27(s1)56,06(h4)791,937,41041,1 (151)1510,8058,5
N/a = no data

Thus, the present invention relates to silicone-hydrogel and silicone-hydrogel suitable for use in medical devices and is particularly suitable for use in contact lenses, intraocular lenses, artificial corneas, etc.

1. Silicone-hydrogel obtained by polymerization polymerization mixture comprising a plurality of monomers containing
(a) from about 30 to about 98% by weight. at least one silicone monomer represented by the formula (b1), (b2):
[Formula 3]

where in the chemical formula (b1) or (b2) R1independently denotes a hydrogen atom or a methyl group; R5-R9independently denotes an alkyl group that contains from 1 to 20 carbon atoms, or aryl group that contains from 6 to 20 carbon atoms; and n denotes a natural number in the range from 1 to 50;
(b) from about 1 to about 50% by weight. at least one naselyonnogo (meth)acrylamide monomer, the corresponding
[Formula 1]

where R denotes hydrogen or methyl;
at least one of R14and R15represents C1-20alkyl group substituted by at least one hydroxyl group, and
provided that if
(i) one of R14and R15denotes hydrogen,
(ii) the other of R14and R15substituted by at least two hydroxyl groups,
where the said percentages by weight are calculated on the basis of the total amount of the monomer and polymer component in the monomer mixture, and
where silicone (meth)acrylamide monomer and resiliancy (meth)acrylamide monomer are in the monomer mixture in an amount of about 90% or more by weight relative to the total content of the monomer and polymer component in the monomer mixture.

2. Silicone-hydrogel according to claim 1 where the above-mentioned resiliancy (meth)acrylamide monomer contains two or more hydroxyl groups.

3. Silicone-hydrogel according to claim 1 where the above-mentioned resiliancy (meth)acrylamide monomer contains one hydroxyl group and contains no amide hydrogen.

4. Silicone-hydrogel according to any one of claims. 1-3, where the polymerization mixture further comprises from about 1 to about 30% by weight. at least one hydrophilic polymer with a molecular weight of about 1000 or more; where mentioned weight percent based on the total content of the monomer and polymer to�of mponents in the monomer mixture.

5. Silicone-hydrogel according to any one of claims. 1-3, where the silicone monomers contain at least one hydroxyl group.

6. Silicone-hydrogel according to claim 4, wherein the silicone (meth)acrylamide monomer corresponds to the following General formula (a1) or (a2):
[Formula 2]

where in chemical formulas (a1) and (a2) R1independently denotes a hydrogen atom or a methyl group; R2denotes an alkyl group that contains from 1 to 20 carbon atoms and at least one hydroxyl group; R3independently denotes alkylenes group that contains from 1 to 20 carbon atoms, or Allenova group that contains from 6 to 20 carbon atoms which may have substituents; R4represents H, aryl or alkyl group that contains from 1 to 20 carbon atoms which may have substituents; and A denotes siloxanic group.

7. Silicone-hydrogel according to claim 1, wherein the silicone (meth)acrylamide monomer further includes at least one additional silicone (meth)acrylamide corresponding to the General formula (b3) or (b4):
[Formula 4]
(b3)
(b4),
where in the chemical formula (b3) or (b4) R1independently denotes a hydrogen atom or a methyl group; R10-R13independently denotes�t alkyl group, which contains from 1 to 20 carbon atoms, or aryl group that contains from 6 to 20 carbon atoms; and m denotes a natural number in the range from 0 to 2.

8. Silicone-hydrogel according to any one of claims. 1-3, 6 or 7, where resiliancy (meth)acrylamide monomer corresponds to any of the following General formulas (c1) to(c3):
[Formula 5]


where in chemical formulas (c1) to(c3) R1independently denotes a hydrogen atom or a methyl group.

9. Silicone-hydrogel according to claim 4, wherein the at least one hydrophilic polymer may be selected from the group comprising poly-N-vinylpyrrolidone, poly-N-vinyl-2-piperidone, poly-N-vinyl-2-caprolactam, poly-N-vinyl-3-methyl-2-caprolactam, poly-N-vinyl-3-methyl-2-piperidone, poly-N-vinyl-4-methyl-2-piperidone, poly-N-vinyl-4-methyl-2-caprolactam, poly-N-vinyl-3-ethyl-2-pyrrolidone, poly-N-vinyl-4,5-dimethyl-2-pyrrolidone, polyvinylimidazole, poly-N-vinylformamide, poly-N-vinyl(methyl)acetamide, poly-N-methyl-N-vinyl(methyl)acetamide, poly-N-vinyl-N-(methyl)propionamide, poly-N-vinyl-N-methyl-2-(methyl)propionamide, poly-N-vinyl-2-(methyl)propionamide, poly-N-vinyl-N,N'-dimethyloxetane, poly-N,N-dimethylacrylamide, poly-N,N-diethylacrylamide, poly-N-isopropylacrylamide, polyvinyl alcohol, polyacrylate, polyethylene oxide, poly-2-ethyloxazole, heparin, polysaccharide, polyacrilonitrile� and their mixtures and copolymers.

10. Silicone-hydrogel according to claim 4, wherein the at least one hydrophilic polymer may be selected from the group comprising polyvinylpyrrolidone, poly(N,N-dimethylacrylamide), poly-N-vinyl(methyl)acetamide, polyacrylate, polyvinyl alcohol and their copolymers.

11. Silicone-hydrogel according to claim 1, in which the number of (meth)acrylamide monomer relative to the total content of monomer components in the monomer mixture comprises by weight 95% or more.

12. Silicone-hydrogel according to any one of claims. 1-3, 6-7 9-11 or where the Monomeric mixture further comprises from about 1 to about 50% by weight. at least one naselyonnogo (meth)acrylamide monomer, which has no hydroxyl groups.

13. Silicone-hydrogel according to claim 12, wherein resiliancy (meth)acrylamide monomer which does not contain hydroxyl groups, selected from the group including (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, (meth)acryloylmorpholine and N-methoxymethyl(meth)acrylamide.

14. Medical devices made from silicone hydrogel described in any one of claims. 1-13.

15. A medical device according to claim 14, where the medical device is a contact lens, artificial cornea, endoscopes, catheters, tubes for blood transfusion, airline tubing, stents, wires for catheter site, cuffs�, medical connectors, ports for vascular access, drainage bags, the contours of the circulation, materials for covering wounds and medical media.

16. Ophthalmic lenses made from silicone hydrogel described in any one of claims. 1-13.

17. Contact lens made of silicone hydrogel described in any one of claims. 1-13.

18. Silicone-hydrogel according to claim 1, where R14and R15independently selected from the group including C1-10alkyl group substituted by at least one hydroxyl group.

19. Silicone-hydrogel according to claim 1, where R14and R15independently selected from the group including C1-6alkyl group substituted by at least one hydroxyl group.



 

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21 cl, 20 tbl, 28 ex

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