Ionic silicone hydrogels having improved hydrolytic stability

FIELD: chemistry.

SUBSTANCE: invention relates to polymers for producing ionic silicone hydrogels suitable for making ophthalmic devices. Disclosed are polymers obtained from reactive components comprising at least one silicone-containing component which includes at least one trimethylsilyl group and at least one ionic component comprising at least one anionic group, which is a carboxylic acid-containing component. Also disclosed is a contact lens made from the disclosed polymers.

EFFECT: disclosed polymers demonstrate improved thermal stability and desirable protein uptake.

24 cl, 5 dwg, 10 tbl, 18 ex

 

Related applications

This application will require priority on provisional application for U.S. patent No. 61101455, filed September 30, 2008, and the application for U.S. patent No. 12567352, filed September 25, 2009, the content of which is based the present application and which are incorporated into it by reference.

The scope of the invention

The present invention relates to ion silicone hydrogels and made of them, ophthalmic devices, which show a preferred profile of the absorption of proteins and improved hydrolytic stability.

Background of invention

It is well known that contact lenses can be used for vision correction. For many years in the sale there are different types of contact lenses. Today is a very popular hydrogel contact lenses. Such lenses are made of hydrophilic polymers and copolymers containing hydroxyethylmethacrylate (HEMA) units of repetition. One of the most comfortable and has the lowest level of development of the negative side effects are contact lenses made from HEMA copolymers and methacrylic acid (MAA). Made from copolymers of HEMA and MAA contact lenses, such as lenses ACUVUE demonstrate significant absorption of lysozyme (>500 g) and retain much of absorbitol the frame of the protein in its native form. However, as a rule, hydrogel contact lenses have a value of permeability to oxygen of no higher than about 30.

Previously described contact lenses made from silicone hydrogel. Such lenses made from silicone hydrogel have a permeability to oxygen of more than about 60, and many of them provide lower levels of hypoxia compared with contact lenses of conventional hydrogel. However, lenses made of silicone hydrogel have higher levels of negative side effects compared with lenses of conventional hydrogel, and it would be desirable to retain their silicone hydrogel permeability to oxygen, but to achieve low levels of negative side effects which are the best lenses of conventional hydrogel. Unfortunately, past attempts to introduce anionic components in silicone hydrogels resulted in the creation of contact lenses, which did not differ hydrolytic stability and modulus of elasticity are increased when exposed to water and heat. For example, the modulus of elasticity of the lens Purevision (Bausch&Lomb) increases with 1069 kPa (155 psi) to 3971 kPa (576 psi) as a result of aging at a temperature of 95°C for weeks. The reason for this increase in modulus is considered to be the hydrolysis of terminal snare is anovich groups followed by reaction of condensation, which leads to the formation of new siloxane groups and the formation of new cross-links in the polymer. Even though the lenses Purevision contained approximately 1 wt%. ion component, they are characterized by relatively low levels of absorption of lysozyme (less than approximately 50 μg), while the major part of the absorbed protein denaturised.

To reduce instability ion silicone hydrogels was proposed to use as the silicone monomer, silicone components with bulky alkyl or aryl groups, such as 3-methacryloxypropyl(trimethylsiloxy)silane (TRIS) or 2-methyl-,2-hyroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propoxy]propyl ester (SiGMA). However, such bulk siloxane monomers available for purchase and can be quite expensive to produce.

Brief description of the invention

The present invention relates to polymers to obtain ion silicone hydrogels which exhibit improved thermal stability and the desired level of absorption of proteins. More specifically, the present invention relates to polymers to obtain silicone hydrogels and contact lenses made of reactive components, which include at least one silicone component and at least one anionic component in an amount of from about 0.1 to 0.9 wt%.

The present invention relates to polymers to obtain ion silicone hydrogels which exhibit improved thermal stability and the desired level of absorption of proteins. More specifically, the present invention relates to polymers to obtain silicone hydrogels and contact lenses made of reactive components, which include at least one silicone component and at least one anionic component, which includes at least one carboxylic acid group in an amount of from about 0.1 to about 10 mmol/g

Description of the drawings

Figure 1 presents a graph of the elastic modulus at a temperature of 55°C for lenses of Examples 1-4 and Comparative example 1 depending on the time.

Figure 2-4 shows graphs of the variation of modulus of elasticity, tensile strength and relative elongation at a temperature of 55°C of the lenses of Examples 6-7 depending on time.

Figure 5 shows a graph of the concentrations of polyquaternium-1 (dimethyl-bis[(E)-4-[Tris(2-hydroxyethyl)azuni-yl]-but-2-enyl]Azania chloride) (PQ1) and lysozyme in the polymers produced in accordance with Examples 10-18 and Comparative example 2.

Detailed description

Was unexpectedly discovered the ability of polymers to create ionic strength is Kanovich hydrogels and manufactured from these products, having acceptable thermal stability and the desirable characteristics of absorption of proteins.

Used herein, the term "biomedical device" means any article intended for use inside and / or on the surface of a tissue or body fluids of mammals. Examples of such devices include without limitation catheters, implants, stents and ophthalmic devices such as intraocular lenses and contact lenses.

Used herein, the term "ophthalmic device" means any device, located inside or on the eye or of the eye, including the cornea, eyelids, and lacrimal gland. Such devices may be used for optical correction, for cosmetic purposes, to improve vision, therapeutic purposes (e.g. as a bandage) or to deliver active ingredients such as pharmaceutical and nutraceutical components, or any combination of these functions. Examples of ophthalmic devices include lenses and optical and ophthalmic inserts, including, without limitation, the tube for the lacrimal canals, etc.

Used herein, the term "lens" refers to ophthalmic devices located in or on the eye. The term "lens" without limitation includes soft the e contact lenses, hard contact lenses, intraocular lenses, overlay lenses.

These medical devices, ophthalmic devices and lenses constituting the present invention, made from silicone elastomers or hydrogels, which without limitation includes silicone hydrogels and silicone forhydrogen. Such hydrogels contain hydrophobic and hydrophilic monomers which are polymerized lens covalently linked to each other.

Used herein, the term "absorption" refers to substances associated inside, or on the surface of the lens, or delayed, inside or on the surface of the lens.

Used herein the term "reaction mixture" refers to the mixture of components (both reactive and preaction-able), which are mixed with each other and are placed in terms of course of polymerization with the formation of ionic silicone hydrogels that are the subject of the present invention. The composition of this reaction mixture comprises reactive components, such as monomers, macromer, prepolymers, cross-linking agents, initiators, solvents and additives, such as wetting agents, release agents, dyes, light absorbing compounds, such as UV blockers and photochromic connect the tion, each of them can be reactive or preaction-able, but is able to stay inside the finished medical device, and pharmaceutical and nutraceutical compounds. It is obvious that the composition of the reaction mixture can include a wide range of additives depending on the type manufactured medical device and its destination. The concentration of the components of the reaction mixture are given in weight percent (wt%) from the total content of all components of the reaction mixture except for the diluent. When using diluents their concentrations are given in wt%. from the total content of all components in the reaction mixture, including the diluent.

Anionic components are components comprising at least one anionic group and at least one reactive group. Anionic groups are groups that carry a negative charge. Examples of anionic groups include carboxylate groups, phosphates, sulfates, sulfonates, phosphonates, borates, and mixtures thereof, etc. In one embodiment, these anionic groups are composed of from three to ten carbon atoms, in another embodiment, from one to eight carbon atoms. In one embodiment, these anionic groups are groups carb is new acids.

Reactive groups include groups capable of free radical and (or) a cationic polymerization in the conditions of the polymerization reaction. Non-limiting examples of free radical reactive groups include (meth)acrylates, sterile, vinyls, vinyl ethers, C1-6the alkyl(meth)acrylates, (meth)acrylamide, C1-6the alkyl(meth)acrylamide, N-vinylacetate, N-vinylamide, C2-12alkenyl, C2-12alkenylphenol, C2-12alkenylacyl, C2-6alkenylphenol-C1-6alkali, O-vinylcarbazole and O-vinylcarbazole. Non-limiting examples of cationic reactive groups include vinyl ester or epoxy groups, and mixtures thereof. In one embodiment, reactive groups include (meth)acrylate, aryloxy, (meth)acrylamide, and mixtures thereof.

Any chemical name prefix (met), for example, (meth)acrylate includes both unsubstituted and appropriate methylsiloxane connection.

Examples of relevant anionic components include reactive carboxylic acids, including alkylacrylate acids such as (meth)acrylic acid, acrylic acid, taconova acid, crotonic acid, cinnamic acid, vinylbenzoic acid, fumaric acid, maleic acid, monetary fumaric acid, maleic acid and Iacono the Oh of the acid, N-vinyloxycarbonyloxy (VINAL), reactive sulphonate salts, including 2-(acrylamide)-2-methylpropanesulfonate sodium 3-sulfopropyl(meth)acrylate potassium, 3-sulfopropyl(meth)acrylate sodium bis-3-sulfobromophthalein disodium, bis-3-sulfobromophthalein of dicale, vinylsulfonate sodium, vinylsulfonate potassium, styrelseledamot, sulfoaildenafil, and mixtures thereof, etc. In one embodiment, the specified anionic component is selected from a reactive carboxylic acids, in another embodiment from methacrylic acid and N-vinyloxycarbonyloxy. In one embodiment, the specified ionic component is a methacrylic acid.

In one embodiment, the anionic component is introduced into the reaction mixture in an amount of from about 0.05 to about 0.8 wt%, in some other embodiments in an amount of from about 0.1 to about 0.8 wt%.

In another embodiment, the anionic component comprises at least one carboxyl group and is present in the reaction mixture in an amount of from about 0.1 mmol/100 g to about 10 mmol/g maintaining the concentration of the anionic component within the specified limits can improve the stability of the resulting polymer. Unexpectedly it was found that the polymers, operasie in its composition specified amount of anionic component, in addition to increased stability also demonstrate the desired profile of the absorption of proteins.

In another embodiment, the amount introduced into the mixture of the anionic component may vary depending on the structure and concentration used silicone components and structure of the anionic component, provided that the molar composition of anionic groups and Si trimethylsilyl groups (-OSiMe3TMS) does not exceed the following values.

The polymers to obtain a silicone hydrogel forming the subject of the present invention, also have a stable modulus of elasticity. Used in this application, the term "stable modulus of elasticity" means that the elastic modulus increases less than about 30%, and in some embodiments less than about 20% in the process of aging for eight weeks at a temperature of 55°C. In some embodiments the polymers to obtain a silicone hydrogel forming the subject of the present invention have a modulus of elasticity that increases less than approximately 20% in the process of aging for 20 weeks at a temperature of 55°C.

Silicone components are reactive and preaction-capable components, which include at least one group-Si-O-Si-. Silicon and C is directly associated with oxygen is preferably approximately 10% weight. the specified silicone component, more preferably up to about 20% weight. the specified silicone component.

Previous attempts at introducing anionic component in silicone hydrogels, as a rule, led to the formation of polymers, the modulus of elasticity which increases with time or exposure to elevated temperatures. The reason for this increase in modulus is considered to be the hydrolysis of terminal siloxane groups and subsequent reaction of the condensation, which leads to the formation of new siloxane groups and the formation of new cross-links in the polymer. It is considered that the hydrolytic stability of the silicone groups (more specifically, due to a silicon-oxygen) is determined by the substituents at the silicon atom. Larger substituents provide greater hydrolytic stability due to the increase of steric hindrance for hydrolysis. The role of such substituents can play alkyl groups (methyl, ethyl, propyl, butyl, etc.), aryl group (e.g. benzyl) or other silicon-containing group. On the basis of the new Deputy steric silicone materials containing trimethylsilyl (-OSiMe3TMS) groups (such as SiMAA or TRIS), generally have a lower hydrolytic stability in the presence of ion the x components in comparison with connections, containing polydimethylsiloxane [(-OSiMe2)n] chain, such as mPDMS. Thus, in the present embodiment, the stability of the polymer is further enhanced by selecting siliconsamurai component in combination with the control of the content of the anionic component.

In one embodiment, used silicone component contains at least one polydimethylsiloxane chain, and in another embodiment, all used silicone components do not contain TMS groups.

In one embodiment, the present invention works percentage molar content of silicon (Si) in trimethylsilyl (TMS) group used a silicone component and the percentage molar content of anionic groups in the used anionic component is less than approximately 0,002, in some embodiments less than approximately 0,001, and in other embodiments, the implementation is less than approximately 0,0006. The work is calculated as follows:

1) When calculating the molar fractions in accordance with the present invention, the reactive components of the initial mixture of the monomer (i.e. excluding diluent(s) and auxiliary additives, which do not remain in the finished lens) are represented as weight fractions, the total is 100,

2) the Molar content of anionic groups=(weight in grams of the anionic component/molecular weight anionic component)·the number of anionic groups in the anionic component. For Example 1, in which the mixture contains 1% methacrylic acid, such a calculation gives (1 g/86 g/mol)·1=0.012 mol carboxylate groups.

3) the Molar content TMS=(weight in grams of the silicone component/molecular weight of the silicone component)·number of TMS groups in the silicone component. For example, in Example 1, in which the mixture contains 30 g SiMAA, this calculation gives (30 g/422,7 g/mol)·2=0,142 mol TMS. In the compositions, including several containing group TMS silicone components, the molar content of TMS is calculated separately for each component, then the results are summed up.

4) the product of the resistance is calculated by multiplying the obtained values for the molar content of carboxylate groups and the molar content of TMS groups. So, for Example 1 piece of resistance is 0,012·0,142=0,0017.

Thus, in the present embodiment, silicone components, ionic components and their quantities used to obtain hydrogels in accordance with the present invention, are selected so that the product of the resistance does not exceed the specified values. In another embodiment, used si is Economie components do not contain groups TMS, thereby ensuring product stability, equal to zero. No groups TMS siliconsamurai components include compounds disclosed in international patent # WO 2008/0412158 and reactive components PDMS formula I:

where b is in the range from 2 to 20, 3 to 15, or, in some embodiments, from 3 to 10; at least one end group, R1represents a monovalent reactive group, and the other end group, R1represents a monovalent reactive group, or a monovalent alkyl group containing from 1 to 16 carbon atoms, and the remaining groups R1are selected from monovalent alkyl groups containing from 1 to 16 carbon atoms, and in another embodiment from monovalent alkyl groups containing from 1 to 6 carbon atoms.

In another embodiment, b is in the range from 3 to 15, one end group, R1represents a monovalent reactive group, such as (meth)aryloxy-C1-6alkyl which can be substituted by at least one hydrophilic group such as hydroxyl, ester, or combination thereof, the other end group, R1represents a monovalent alkyl group containing from 1 to 6 and the Ohm carbon, and the rest of the group R1represents a monovalent alkyl group containing from 1 to 3 carbon atoms.

In one embodiment, one end group, R1represents a (meth)aryloxy-C1-6alkyl, which may optionally be substituted ester or a hydroxyl group, the other end group, R1represents a C1-4alkyl, and the remaining groups R1represent a methyl or ethyl group.

Non-limiting examples of PDMS components of this implementation include (polydimethylsiloxane (400-1000 MV) with terminal mono-(2-hydroxy-3-methacryloxypropyl)-propyl ester group) (OH-mPDMS) and polydimethylsiloxane with integral monomethacrylate and integral mono-n-C1-4alkyl groups, including polydimethylsiloxane (MW 800-1000) with integral mono-n-utilname and end monomethacrylate groups (mPDMS) and polydimethylsiloxane (MW 800-1000) with integral methyl and end monomethacrylate groups (mPDMS).

In one embodiment, all of the silicone components in the reaction mixture are components of PDMS.

In another embodiment, b is in the range from 5 to 400, or from 10 to 300; and both end groups R1represent a monovalent reactive group, and the steel group, R 1independently selected from monovalent alkyl groups containing from 1 to 18 carbon atoms which may have ether bridging group between carbon atoms and can also contain halogen atoms.

In another embodiment, from one to four groups R1are vinylcarbene or vinylcarbene with the following formula:

Formula II

where Y represents an O-, S - or-NH-;

R represents hydrogen or methyl; q is 1, 2, 3 or 4; and b is in the range from 1 to 50. In these embodiments, the implementation should pay special attention to that used vinylcarbenes or vinylcarbenes silicone component did not contain groups TMS, otherwise difficulties in providing the necessary values above molar works.

More specifically, the objectives of the present invention siliconsamurai vinylcarbene or vinylcarbene monomers include 1,3-bis[4-(vinyloxycarbonyloxy)buta-1-yl]tetramethyldisiloxane;

Formula III

where the group R1is selected in accordance with the above description of end groups.

In some embodiments can be used small amounts of the group containing TMS vinylcarbene and wine is carbamate compounds. Such groups include 3-(vinyloxycarbonyl)propyl-[Tris(trimethylsiloxy)silane]; 3-[Tris(trimethylsiloxy)silyl]propylaniline; 3-[Tris(trimethylsiloxy)silyl]propylenecarbonate; trimethylsilylcyanation; trimethylsilylmethylamine, combinations thereof, etc.

In some embodiments it may be desirable to enter into a mixture of small amounts siliconsamurai components, including at least one TMS group. Such groups include the above-described containing groups of the TMS vinylcarbazole and vinylcarbazole and siliconsamurai components of the formula I where the group R1independently selected from monovalent reactive groups, monovalent alkyl groups, or monovalent aryl groups, any of the above groups, which optionally carry a functional group selected from the following groups: hydroxy, amino, oxa, carboxy, alkylcarboxylic, alkoxy, amido, carbamate, carbonate, halogenide a combination thereof, monovalent trimethylsiloxy groups,

where b=0;

moreover, at least one group R1represents a monovalent reactive group, and in some embodiments, the implementation of one to three groups R1represent a monovalent reactive group.

The goals of this is bretania monovalent alkyl and aryl groups include unsubstituted monovalent C 1-C16alkyl group, a C6-C14aryl group such as substituted and unsubstituted methyl, ethyl, propyl, butyl, 2-hydroxypropyl, propoxyphen, polyethylenoxide, as well as their various combinations, etc.

In one embodiment, b is zero, one group R1represents a monovalent reactive group, and at least three groups of R1selected from monovalent alkyl groups containing from 1 to 16 carbon atoms, and in another embodiment from monovalent alkyl groups containing from 1 to 6 carbon atoms.

Non-limiting examples siliconsamurai components of this implementation include 2-methyl-,2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propoxy]propyl ester (SiGMA),

2-hydroxy-3-methacryloxypropyl-Tris(trimethylsiloxy)silane,

3-methacryloxypropyl(trimethylsiloxy)silane (TRIS),

3-methacryloxypropyl(trimethylsiloxy)methylsilane and

3-methacryloxypropyltrimethoxysilane.

When included in the composition of the reaction mixture containing group TMS siliconsamurai components are present in amounts less than about 20 wt%, less than about 10 wt%, and in some embodiments less than about 5% weight.

If necessary, p. the receipt of biomedical devices with modulus less than approximately 200 only one of the groups R 1must be a monovalent reactive group.

In one embodiment, directed to obtain silicone-hydrogel lenses, lens in accordance with the present invention is made from a reaction mixture containing at least about 20 wt%, and in some embodiments from about 20 to 70 wt%. siliconsamurai components in terms of the total weight of reactive monomer components made from polymer.

Another class siliconsamurai components includes polyurethane macromer with the following formula:

Formula IV-VI

(*D*A*D*G)a*D*D*E1;

E(*D*G*D*A)a*D*G*D*E1or;

E(*D*A*D*G)a*D*A*D*E1

where

D represents an alkyl biradical, alkylcyclohexanes biradical, cycloalkenyl biradical, the aryl biradical or alcylaryl biradical containing from 6 to 30 carbon atoms;

G represents an alkyl biradical, cycloalkenyl biradical, alkylcyclohexanes biradical, the aryl biradical or alcylaryl biradical containing from 1 to 40 carbon atoms which may have in a main chain ether, thioester or amine bridge group;

* means of urethane or ureidosuccinate group;

aequal to at least 1;

Oznachaet divalently polymer moiety with the following formula:

Formula VII

R11independently represents an alkyl or fluoro-substituted alkyl group containing from 1 to 10 carbon atoms which may contain ether linkages between carbon atoms; y is at least 1; p is the mass of the molecule from 400 to 10,000; each of the groups E and E1independently represents a capable polymerization of unsaturated organic radical represented by the formula:

Formula VIII

where R12represents hydrogen or methyl; R13represents hydrogen, an alkyl radical containing from 1 to 6 carbon atoms, or the radical-CO-Y-R15where Y represents-O-,Y is-S - or-NH-; R14represents divalently radical containing from 1 to 12 carbon atoms; X represents-CO - or-OCO-; Z represents-O - or-NH-; Ar represents an aromatic radical containing from 6 to 30 carbon atoms; w is in the range from 0 to 6; x is 0 or 1; y is 0 or 1; and z is 0 or 1.

In one embodiment, siliconsamurai component is a polyurethane macromer, represented by the following formula:

Formula IX

where R16is biradical of a diisocyanate after removal of Isola atoi group, for example biradical isophorondiisocyanate. Other relevant purposes of the present invention siliconsamurai micromera is a compound of the formula X (where x+y is a number in the range from 10 to 30), obtained by reaction of Ftorafur, polydimethylsiloxane with terminal hydroxyl group, isophorondiisocyanate and isocyanatoacetate.

Formula X

Other relevant objectives of the present invention siliconsamurai components include the components described in the patent application no WO 96/31792, such as macromer containing polysiloxane, polyalkylene, diisocyanate, policeregistered, poliferation and polysaccharide groups. Another class are consistent with the objectives of the present invention siliconsamurai components includes siliconsamurai macromer obtained by polymerization with the transfer of the group (GTP), for example macromer described in U.S. patent No. 5314960, 5331067, 5244981, 5371147 and 6367929. In U.S. patent No. 5321108, 5387662 and 5539016 described polysiloxane with polar fluorinated graft or side group having a hydrogen atom attached to the end defensemastery the carbon atom. In the application for U.S. patent No. 2002/0016383 described hydrophilic siloksanchlorides containing essential and diloxanide bridge group, and the act is one to cross-linking of monomers, containing polyester and polysiloxane group. Any of the above polysiloxanes can also be used as siliconsamurai component for the purposes of the present invention.

In one embodiment of the present invention, when it is required to obtain the modulus of elasticity of the material of the lens is less than approximately 827 kPa (120 psi), a large part of the mass fraction is used in the reaction mixture siliconsamurai components must contain only one capable of polymerization functional group (monofunctional siliconsamurai component). In the present embodiment, to ensure the necessary balance between the ability to pass oxygen and modulus of elasticity of the material of the lens preferably, all components that have more than one capable of polymerization functional group (multi-component) amounted to no more than 10 mmol/100 g of reactive component and preferably not more than 7 mmol/100 g of reactive component.

Siliconsamurai components may be present in the reaction mixture in amounts up to about 95 wt%, in some embodiments in an amount of from about 10 to about 80 wt%. in other embodiments, the implementation - in the amount from about 20 d is approximately 70% weight. the total weight of reactive components.

In addition to the specified ion component of the reaction mixture may also contain at least one hydrophilic component. The role of the hydrophilic monomers can play any hydrophilic monomers used for the manufacture of hydrogels.

One of the classes relevant to the objectives of the present invention hydrophilic monomers include acrylic and vinylstyrene monomers. Such hydrophilic monomers can be used as cross-linking agents, however, when using hydrophilic monomers having more than one is capable of polymerization functional groups, their concentration should be limited as described above, to obtain a contact lens with the desired modulus of elasticity. The term "monomers of the vinyl type or vinylstyrene monomers" refers to monomers containing the vinyl group (-CH=CH2) and are generally highly reactive. It is known that such hydrophilic vinylstyrene monomers relatively easily polymerized.

The term "monomers acrylic-type" or "allstargame monomers" refers to monomers containing the acrylic group (CH2=CRCOX), where R represents H or CH3and X represents O or N, which are known to also easily polymerized, for example the er N,N-dimethylacrylamide (DMA), 2-hydroxyethylmethacrylate (HEMA), glycerinated, 2-hydroxyethylmethacrylate, polietilenglikolmonostearat, mixtures thereof, etc.

Hydrophilic vinylstyrene monomers that can be entered in the silicone hydrogels of the present invention, include such monomers as N-vinylamide, N-vinylacetate (for example, N-vinyl pyrrolidone (NVP)), N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformate, N-vinylformamide, while it is preferable to NVP.

Other hydrophilic monomers that can be used in the present invention include polyoxyethylene polyols, in which one or more terminal hydroxyl groups replaced with a functional group, capable of containing polymerization of the double bond. Examples of such monomers include polyethylene glycol, an ethoxylated Alkylglucoside and ethoxylated bisphenol A reacted with one or more molar equivalents closing groups, such as isocyanatoacetate (IEM), methacrylic anhydride, methacryloylamido, vinylbenzoate and similar compounds, with the formation of poliatilenglikola having one or more end-curable olefinic groups associated with poliatilenglikola through a connecting group, such as urethane or ester group.

Other example is of such monomers include hydrophilic vinylcarbene or vinylcarbene monomers, disclosed in U.S. patent No. 5070215, and hydrophilic oksazolonovye monomers disclosed in U.S. patent No. 4910277. The person skilled in the art may also offer other appropriate purposes of the present invention hydrophilic monomers.

In one embodiment, these hydrophilic monomers include at least one of the following hydrophilic monomers: DMA, HEMA, glycerinated, 2-hydroxyethylmethacrylate, NVP, N-vinyl-N-methylacrylamide, polietilenglikolmonostearat, and mixtures thereof. In another embodiment, the above hydrophilic monomers include at least one of the following monomers: DMA, HEMA, NVP and N-vinyl-N-methylacrylamide, and mixtures thereof. In another embodiment, the hydrophilic monomer is a DMA.

Concentration introduced into the reaction mixture of hydrophilic monomers can vary widely depending on the specific combination of the required properties of the finished polymer. Is acceptable concentration of hydrophilic monomers up to about 50, preferably from about 5 to about 50 wt%. in terms of all reactive components. For example, in one embodiment, the lenses constituting the present invention have a water content of at least about 25%,and in another embodiment, - from approximately 30 to approximately 70%. For these embodiments, the amount of hydrophilic monomer may be from about 20 to about 50 wt%.

Other components that may be present in the reaction mixture used to form contact lenses for the purposes of the present invention, include wetting agents, for example, described in U.S. patent No. 6367929, international patent number WO 03/22321, WO 03/22322, components, improves the compatibility, for example, described in patents No. U.S. 2003/162862 and 2003/2003/125498, compounds that absorb ultraviolet radiation, drugs, antimicrobial compounds, capable of copolymerization and depolymerizes dyes, release agents, reactive tinting compound, pigments, combinations thereof, etc. the Total number of additional components may approximately 20% of the weight. In one embodiment, the composition used in the reaction mixture includes up to about 18 wt%. the wetting agent, and in another embodiment from about 5 to about 18 wt%. the wetting agent.

In the reaction mixture may be added to the polymerization catalyst. The polymerization initiators include compounds such as laurelbrooke, benzoyl peroxide, isopropyl carbonate, azobisisobutyronitrile etc. that are sources of free radicals at moderately elevated temperatures, and fotosensibiliziruyuschimi systems, such as aromatic alpha hydroxyketone, alkoxycarbonyl, acetophenone, arylphosphonate, besatisfied, and Quaternary amine plus a diketone, mixtures thereof, etc. are Typical examples of photoinitiators are 1-hydroxycyclohexane,2-hydroxy-2-methyl-1-phenylpropane-1-he, bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylphosphine (DMBAPO), bis(2,4,6-trimethylbenzoyl)-phenylphosphine (Irgacure 819), 2,4,6-trimethylbenzenesulfonamide and 2,4,6-trimethylbenzenesulfonamide, benzoylmethylene ether and a combination of camphoroquinone and ethyl 4-(N,N-dimethylamino)benzoate. To a commercially available visible light initiators include Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 819, Irgacure 1850 (all production Ciba Specialty Chemicals) and the initiator Lucirin TPO (manufactured by BASF). To a commercially available UV photoinitiators include Darocur 1173 and Darocur 2959 (Ciba Specialty Chemicals). These and other photoinitiator that can be used for the purposes of the present invention, described in reference Photoinitiators for Free Radical Cationic &Anionic Photopolymerization, Volume III, 2-ndEdition, by J.V. Crivello&K. Dietliker; edited by G. Bradley; John Wiley and Sons; New York; 1998. The initiator used in the reaction mixture in an effective amount to initiate the photopolymerization is actionnow mixture, for example, in amounts of from about 0.1 to about 2 weight parts per 100 parts reacts monomer. The polymerization reaction mixture can be initiated by proper selection of heating or visible or UV light, or in other ways depending on the initiator of polymerization. Alternatively, the initiation can be done without photoinitiator, using, for example, e-beam. However, if you use photoinitiator, the preferred initiators are besatisfied, such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine (Irgacure 819®) or a combination of 1-hydroxycyclohexanone and bis(2,6-dimethoxybenzoyl)-2,4-4-tributyltinoxide (DMBAPO), in another implementation of the preferred method of initiating polymerization is the activation of visible light. The preferred initiator is bis(2,4,6-trimethylbenzoyl)-phenylphosphine (Irgacure 819®).

Reactive components (siliconsamurai component, hydrophilic monomers, wetting agents and other components, which react in the formation of the lens) are mixed together with a diluent or without it, with the formation of the reaction mixture.

In one embodiment, a diluent is used with a sufficiently low polarity to solubilize non-polar to the components in the reaction mixture in the reaction conditions. One of the ways of describing the polarity of the solvents for the purposes of the present invention is the solubility parameter Hansen, dp. In some embodiments, the implementation of the value dp is less than 10 and preferably less than 6. The objectives of the present invention thinners further disclosed in U.S. patent No. 60/452898 and 6020445.

Classes are consistent with the objectives of the present invention thinners inter alia include alcohols containing from 2 to 20 carbon atoms, amides containing from 10 to 20 carbon atoms and are derived from primary amines, ethers, polyethers, ketones containing from 3 to 10 carbon atoms, and carboxylic acids containing from 8 to 20 carbon atoms. For all solvents with increasing number of carbon atoms in the molecule, the number of polar functional groups can also be increased to provide the necessary Miscibility with water. In some embodiments, the preferred implementation are the primary and tertiary alcohols. Preferred classes of solvents include alcohols containing from 4 to 20 carbon atoms, and carboxylic acids containing from 10 to 20 carbon atoms.

In one embodiment, these diluents are selected from the following compounds: 1,2-octandiol, t-amyl alcohol, 3-methyl-3-pentanol, cekanova acid, 3,7-dimethyl-3-ctanol, tripropyleneglycol ether (TPME), butoxylated, mixtures thereof, etc.

In one embodiment, the diluents are selected from diluents, which are to some extent soluble in water. In some embodiments, the implementation of the Miscibility of the solvent with water is at least about 3%. Examples of the water-soluble diluents are: 1-octanol, 1-pentanol, 1-hexanol, 2-hexanol, 2-octanol, 3-methyl-3-pentanol, 2-pentanol, tert-amyl alcohol,tert-butanol, 2-butanol, 1-butanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, ethanol, 3,3-dimethyl-2-butanol, cekanova acid, octanoic acid, dodekanisa acid, 1-ethoxy-2 - propanol, 1-tert-butoxy-2-propanol, EH-5 (provider - Ethox Chemicals), 2,3,6,7-tetrahydroxy-2,3,6,7-tetramethylpentane, 9-(1-methylethyl)-2,5,8,10,13,16-hexoctahedron, 3,5,7,9,11,13-hexamethoxy-1-tetradecanol, mixtures thereof, etc.

The reaction mixture for the purposes of the present invention may be polymerized by any known molding process of the reaction mixture in the production of contact lenses, including centrifugal casting and static casting. Methods of centrifugal casting are disclosed in U.S. patent No. 3408429 and 3660545, and static methods of casting are disclosed in U.S. patent No. 4113224 and 4197266. In one embodiment, a contact lens for the purposes of the present invention is made by pramaggiore silicone-hydrogels, what is an economical way and allows you to precisely control the final shape of the hydrated lens. When using this method, the reaction mixture is placed in a mold for casting with a geometric shape that you want to give the finished silicone hydrogel, i.e. swollen from the water to the polymer, and the reaction mixture create conditions for polymerization of monomers, resulting in the polymer with the approximate shape of the final product.

After polymerization, the lens is extracted to remove unreacted components and removed from the molds. The specified extraction can be carried out using conventional extracting liquids such as organic solvents, such as alcohols, or may be carried out using aqueous solutions.

Aqueous solutions are solutions that contain water. In one embodiment, aqueous solutions for the purpose of this invention contain at least about 30% water, in some embodiments, the implementation of at least about 50% water, in some embodiments, the implementation of at least about 70% water, and in other embodiments, the implementation of at least approximately 90 wt%. water. The composition of the aqueous solutions can also include additional soluble in water to mponent, such as release agents, wetting agents which reduce friction additive, pharmaceutical and nutraceutical components, combinations thereof, etc. of release agents are compounds or mixtures of compounds which, in combination with water to reduce the time required to separate the contact lenses from the molds, compared to the time required to remove the lens from the mold using an aqueous solution that does not contain a separating agent. In one embodiment, aqueous solutions containing less than about 10 wt%, in other embodiments, the implementation is less than about 5% weight. organic solvents such as isopropyl alcohol, and in another embodiment not contain organic solvents. In these embodiments, the implementation of the aqueous solutions do not require special processing, such as purification, recycling or special disposal procedures.

In various embodiments, the implementation of the extraction can be performed, for example, by immersing the lens in an aqueous solution or by exposure to the lens of the flow of an aqueous solution. In a different implementation, the extraction may also include, for example, one or more of the following operations: heating an aqueous solution; mixing an aqueous solution; increasing the possession of the separating agent in aqueous solution to a level sufficient to remove the lens from the mold; mechanical or ultrasonic effect on the lens; and adding an aqueous solution of at least one leaching funds sufficient to ensure adequate removal of unreacted components from the lens. The above procedure can be carried out on batches of products, or in continuous processes with or without the use of heat and (or) mechanical or ultrasonic treatment.

Some embodiments of also may include the use of physical action to promote leaching and extraction of the lens. For example, a part form for casting lenses, depending on where you want to separate the lens may vibrate or move back and forth in aqueous solution. Other options for implementation may include the use of ultrasonic waves in water solution.

These and other similar processes may be acceptable methods of separating the lens from the mold.

Used herein, the term "lens, extracted from the mold for molding" means that the lens is either completely separated from the molds, or only weakly associated with it and can be separated light shaking or shifted by means of a tampon. Provided by the processes of the present invention technological services is via include use of a temperature less than 99°C for less than about 1 hour.

The lens can be sterilized by known methods including, inter alia by autoclaving.

In addition to the desired stability are the subject of the present invention, the lens also demonstrate compatibility with the components of the tear fluid of humans.

Tears man has a complex structure and contains a mixture of proteins, lipids and other components that help keep your eyes moistened condition. Examples of classes of lipids include wax esters, cholesterol esters and cholesterol. The examples present in the tear fluid of human proteins include lactoferrin, lysozyme, lipocalin, serum albumin, secretory immunoglobulin A. Lipocalin is a bind with lipids protein. A negative correlation between the level of absorption of lipocalin material contact lenses with the wettability of the lens (measured by the contact angle, for example, by the method of stationary droplets), the tendency of the lens to the absorption of lipids of the tear film and, as a consequence, to the formation of deposits on the anterior lens surface. Therefore, the desired lens with a low level of absorption of lipocalin. In one embodiment of the present invention obtained lenses absorb less than about 3 μg of lipocalin from a solution of lipocalin with a concentration of 2 mg/ml is and the time of incubation for 72 hours at 35°C.

Lysozyme is generally present in the tear fluid of humans in large quantities. Lysozyme has bacteriolytic properties and are believed to protect the eyes from bacterial infection. The amount of lysozyme that is associated with a commercially available contact lenses varies in a very wide range from a few micrograms to about 800 micrograms for contact lenses of the material etafilcon A (supplied by Johnson&Johnson Vision Care, Inc. under the brands ACUVUE and ACUVUE2). Contact lenses made from material etafilcon And commercially available for many years and have some of the lowest levels of development of the negative side effects of all soft contact lenses. Therefore, desirable contact lenses with a significant level of absorption of lysozyme. Lenses constituting the present invention absorb at least about 50 μg, 100 μg, 200 μg and 500 μg of lysozyme, and in some embodiments, the implementation of at least about 800 μg of lysozyme solution concentration of 2 mg/ml during incubation for 72 hours at 35°C.

In addition to lysozyme another important cationic protein lacrimal fluid is lactoferrin, mainly because of its antibacterial and anti-inflammatory properties. When wearing contact lenses absorb different to what icesta lactoferrin depending on the composition of the polymer material of the lenses (lenses without surface modification) and the composition and integrity of the coating of the lens surface (surface modified contact lenses). In one of the embodiments of the present invention obtained lenses absorb at least about 5 μg, and in some embodiments at least about 10 μg lactoferrin while keeping them overnight in 2 ml of lactoferrin concentration of 2 mg/ml Used solution contains lactoferrin lactoferrin from milk man (Sigma L-0520), the solubilized at a concentration of 2 mg/ml in phosphate buffer solution. Lenses were incubated in 2 ml of the indicated solution of lactoferrin on the lens for 72 hours at 35°C, following the procedure described below for lipocalin and lysozyme.

In addition, an important form in which the protein is present inside, on the surface of or associated with the lens. It is considered that denatured proteins play a role in inflammatory processes in the cornea and creating discomfort when wearing lenses. It is believed that the degree of protein denaturation depends on factors such as pH, temperature of the surface of the eyeball, the duration of wearing the lenses and the residence time of the lens on the closed eye. However, lenses of different composition can have very different profiles of absorption and protein denaturation. In one of the embodiments of the present invention a large part of the proteins which are absorbed by the lenses constituting the subject of the infusion is his invention, are in the process of wear left in its native form. In other embodiments, the implementation of at least about 50%, at least about 70% and at least about 80% of the absorbed proteins are and remain in their native form within 24 hours within 3 days and for the recommended period of wearing.

In one embodiment, the implementation of the ophthalmic device forming the subject of the present invention, also absorb less than about 20%, in some embodiments less than about 10%, and in other embodiments, the implementation is less than approximately 5% of polyquaternium-1 (dimethyl-bis[(E)-4-[Tris(2-hydroxyethyl)azuni-yl]-but-2-enyl]Azania chloride) (PQ1) of the ophthalmic solution containing about 0.001% weight. PQ1).

Lenses constituting the present invention, in addition to the above characteristics, the absorption of protein and also have a number of other desirable properties. In one of the embodiments of the lens have a permeability to oxygen of more than about 50, in another embodiment, more than about 60, in some embodiments, the implementation of more than about 80, and in other embodiments, the implementation of at least 100. In some embodiments of the lens module of elasticity when is asthenia less than about 689 kPa (100 psi).

It should be understood that all operations described in this document tests have some degree of inaccuracy inherent to the method. Accordingly, the results should not be considered as absolute values, but as the field of numerical values determined by the accuracy of a particular test method.

The modulus of elasticity (modulus of tensile elasticity) is measured using a traverse head bursting of the testing machine with a constant speed, equipped with a sensor voltage is lowered to the original standard height of the sample. Examples relevant to the objectives of the present invention of testing machines include Instron machine, model 1122. The sample in the form of a dog bone from lenses with optical power -1,00, having a length of 1,326 cm (0,522 inches), the width of the "loops" 0,701 cm (0,276 inches) and the width of the "neck" 0,541 cm (0,213 inch) is mounted in the clamps and stretched at a constant speed tension of 5.1 cm/min (2 inches/min) before breaking. Measured original standard sample length (Lo) and the sample length at break (Lf). For each of the studied compositions is measured at least five samples, as results are averages of those dimensions. The modulus of tensile elasticity is measured at initial linear fragment curve load/extension.

Percentage elongation Rasch is entangled as [(Lf-Lo)/Lo]×100.

The diameter of the lens can be measured using a modulated image obtained on the interferometer of the Mach-Zehnder with lens immersed in a buffer solution and installed in a ditch concave surface down, as described in detail in U.S. patent No. US2008/0151236. Before measuring lenses for 15 minutes, allowed to come to equilibrium at a temperature of approximately 20°C.

The water content is measured as follows. The test lenses incubated in the solution for storage within 24 hours. Then each of the three test lens is removed from the storage solution using ended sponge swab and placed on paper towels moistened with a solution for storage. Napkins touch the sides of the lens. Test the lens forceps is placed in a weighing boat and weighed. In the manner described above is prepared and weighed two sets of test specimens. Each boat and the lens is weighed three times, and as the weight of the wet lenses take the average of the results of the three measurements.

To determine dry weight boat with the sample is placed in a vacuum oven, pre-within 30 minutes heated to a temperature of 60°C. Include pumping and bring the vacuum in the furnace up to a level of at least about 1.35 kPa (6 mm RT. Art.). Then coming close to the pump vacuum valve and dried lenses within the amireh hours. After that open the faucet leak and wait until the recovery furnace atmospheric pressure. Then the boat out of the oven and weighed again. The water content is calculated as follows:

Inewith ainlandWnaboutylandnCs=with aymmandpnsyinewith ainlandWnaboutylandnCsandlaboutdabouthKand-inewith alaboutdabouthKand

Inewith awith ayxaboutylandnCs=with aymmandpnsyinewith awith ayxaboutylandnCsandlaboutdabouthKand-inewith alaboutdabouthKand

PpaboutCentwith aaboutdepWandnandIinaboutds=(inewith ainlandWnaboutylandnCs-inewith awith ayxaboutylandnCs)Inewith ainlandWnaboutylandnCs×100

For the samples is calculated and gives the mean water content and their standard deviations.

The levels of absorption of lysozyme and lipocalin was measured using the following method and solutions.

Used the solution of lysozyme contained lysozyme from chicken protein eggs (Sigma, L7651), the solubilized at a concentration of 2 mg/ml in phosphate buffer solution with the addition of 1.37 g/l sodium bicarbonate and 0.1 g/l D-glucose.

Used solution lipocalin contained B lactoglobulin (lipocalin) from bovine milk (Sigma, L3908), the solubilized at a concentration of 2 mg/ml in phosphate buffer solution with the addition of the 1,37 g/l sodium bicarbonate and 0.1 g/l D-glucose.

For each Example was tested on three lenses with each of the protein solutions. In addition, as a control were tested three lenses in buffered solution. The test lenses probatively sterile gauze to remove the storage solution and sterile tweezers aseptically transferred into a sterile 24-hole culture plates (one lens in the well)containing 2 ml solution of lysozyme in the hole. Each lens is completely immersed in the solution. As a control in one hole was placed 2 ml of lysozyme and did not put it in the lens.

Tablets with lenses, as well as control tablets only with the protein solution and lenses in buffered solution was sealed by parafilm to protect from evaporation and dehydration, were placed on an orbital shaker and incubated at 35°C and the intensity of shaking at 100 rpm for 72 hours. After 72 hours incubation, the lenses were washed 3-5 times by immersing the lenses in 3 (three) separate vial containing approximately 200 ml of buffer solution. Then the lens got wet paper towel to remove excess buffer solution and transferred into a sterile conical tubes (one lens in the tube, with each tube was buffered solution in quantities defined on the basis of estimates of the number of absorbed lysozyme expected the th for each lens on the basis of its composition. The concentration of lysozyme in each test tube with the test lens must be within the range of albumen standards in accordance with the description of the manufacturer (from 0.05 to 30 µg). Samples with a known level of absorption of lysozyme was less than 100 µg lens was diluted 5 times. Samples with a known level of absorption of lysozyme was more than 500 mcg per lens (such as lens made of material etafilcon A)was diluted 20 times.

For the samples from Example 9, Comparative example 2 and the lens material balafilcon took aliquots of buffer solution in a volume of 1 ml, for a lens of material etafilcon And took aliquots of 20 ml Each control lens was treated in the same way with the difference that the wells contained a buffer solution instead of the solution of lysozyme or lipocalin.

The levels of absorption of lysozyme and lipocalin was determined by the method "on the lens using bicinchoninic acid using a reagent kit QP-BCA (Sigma, QP-BCA) and follow prescribed by the manufacturer procedure (preparation of the standards described in the instructions to the set), and was calculated by subtracting the optical density measured for the present in a buffer solution of lenses (background), from the optical density measured for the lenses that were in the solution of lysozyme.

Optical density was measured on a spectrophotometer, the vertical scanning SynergyII Micro-plate reader, capable of measuring the optical density at a wavelength of 562 nm.

Lysozyme activity was measured using a mortar and procedures incubation described above for level measurement of absorbed lysozyme.

At the end of the period of incubation, the lenses were washed 3-5 times by immersing the lenses in 3 (three) separate vial containing approximately 200 ml of buffer solution. Then the lens got wet paper towel to remove excess buffer solution and transferred into a sterile 24-hole culture plates (one lens in the hole), and in each well was 2 ml extracting solution consisting of a mixture of 50:50 solution of 0.2% triperoxonane acid and acetonitrile (TFA/ACN). Lenses were incubated in extracting the solution for 16 hours at room temperature.

In parallel diluted control solution of lysozyme buffer for extraction to the range of concentrations covering the expected level of absorption of lysozyme in the analyzed lenses. For examples of this application of the expected concentration of lysozyme was 10, 50, 100, 800, and the control solution was diluted to these concentrations, and incubated for 16 hours at room temperature. Extracts of lysozyme from the test lens and the control samples were tested for lysozyme activity using a set of reagents EnzChek® Lysozyme Assay Kit (invirogen) and following the manufacturer's recommendations set.

The EnzChek kit allows fluorescence analysis activity of lysozyme in its levels in the solution up to 20 IU/ml During the analysis of the measured activity of lysozyme on the cell wall of the bacteria Micrococcus Lysodeikticus that state to such a degree that the fluorescence is suppressed. The effect of lysozyme removes this inhibition and leads to an increase in fluorescence that is proportional to the activity of lysozyme. The increase of fluorescence intensity is measured using a fluorescent scanner, which is able to detect fluorescein using wavelength excitation/emission 494/518 nm. In the examples of this application used the scanner Synergy HT Microplate Reader.

The analysis is based on the preparation of standard curve for lysozyme using the same lysozyme, which is in preproduction or incubated with lenses. Lysozyme activity is expressed in units of fluorescence intensity and delayed depending on the concentration of lysozyme expressed in IU/ml Measured the activity extracted from lenses of lysozyme and control samples of lysozyme and using the standard curve, counted its activity in units per ml.

The percentage of active or native lysozyme was determined by comparing the activity of lysozyme samples with lenses and activity of lysozyme pin is Aulnay samples and was calculated using the following expression:

% active (native) of lysozyme in the lens=extracted from lenses lysozyme (U/ml)×100/lysozyme (U/ml) from control sample.

The absorbance PQ1 was measured as follows. Using a set of standard solutions PQ1 with concentrations of 2, 4, 6, 8,12 and 15 μg/ml, have calibrated HPLC chromatograph. Lenses were placed in a polypropylene container for contact lenses containing 3 ml Opti-free Replenish (which contains about 0.001% weight. PQ1 and delivered by the company Alcon Also prepared a control container containing 3 ml of the indicated solution, but not containing contact lenses. Lenses and control solutions has stood at room temperature for 72 hours. From each sample and the control sample was taken and 1 ml of solution and mixed aliquots taken with triperoxonane acid (10 μl). Chromatographic analysis was performed by HPLC with evaporative light scattering detector (HPLC/ELSD) for column Phenomenex Luna C4 (4,6×5 mm; particle size 5 μm) under the following conditions.

Analyzer: Agilent 1200 HPLC or similar detector Sedere Sedex ELSD 85

Sedex ELSD 85: T=60°C, the amplification (Gain)=10, the pressure (Pressure)=3,4 bar, the time constant (Filter)=1 with

The mobile phase A (Mobile Phase A): H2About (0.1% of TFA)

The mobile phase B (Mobile Phase B: Acetonitrile (with 0.1% TFA)

The temperature of the column (Column Temperature): 40°C

The volume of the sample (Injection Volume: 100 ál

Table I
Conditions for HPLC analysis
Time (min)%A%BFlow rate (ml/min)
0,0010001,2
1,0010001,2
5,0051001,2
8,5051001,2
8,6010001,2
11,0010001,2

For each analysis took three lenses and averaged the results.

Permeability to oxygen (Dk) was measured by a polarographic method in accordance with the General description in the ISO 9913-1:1996(E), but with the following differences. The measurements are performed in an environment containing 2.1% of oxygen. This environment is created by the installation of a test cell inlet nozzle is La nitrogen and air and setting them on the appropriate cost of gas, for example 1800 ml/min of nitrogen and 200 ml/min of air. The value of t/Dk is calculated using the corrected oxygen concentrations. Used borate buffered saline solution. The dark current is measured using the environment clean humidified nitrogen instead of installing the lens of MMA. Lenses before measurement is not promahivaetsya. Instead of using lenses of different thickness is measured package of four stacked on top of each the lenses. Instead of the flat sensor is used curvilinear sensor. The measured values Dk are given Barrera.

The following examples do not limit the present invention. They are intended only to describe the practical use of the invention. Experts in the field of contact lenses and related fields will be able to find other ways of practical use of the invention. However, these methods will be considered as falling within the scope of the present invention.

Examples

In the examples below, the following abbreviations are used:

Macromer Macromer prepared in accordance with the procedure outlined in section "Preparing macromer" in Example 1 of patent # US-2003-0052424-A1

acPDMS bis-3-aryloxy-2-hydroxypropylmethylcellulose (MW 2000, acrylamides the polydimethylsiloxane) production company Degussa.

Goal the fight HEMA - the reaction product is Reactive blue 4 and HEMA, as described in Example 4 of U.S. patent No. 5944853

CGI 819 bis(2,4,6-trimethylbenzoyl)-phenylphosphine

CGI 1850 1:1 (weight) mixture of 1-hydroxycyclohexanone and bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylindolenine

D3O 3,7-dimethyl-3-octanol

DMA N,N-dimethylacrylamide

EGDMA etilenglikolevykh

HEMA 2-hydroxyethylmethacrylate

MAA methacrylic acid

mPDMS a polydimethylsiloxane with terminal mono-n-butilkoi and manometrically groups, the production company Gelest, molecular weights are indicated in the specific examples

Norbloc 2-(2'-hydroxy-5-methacryloyloxyethyl)-2H-benzotriazol

mPDMS-OH (polydimethylsiloxane with terminal mono-(3-methacrylate-2-hydroxypropoxy)-through and mono-butilkoi groups, produced in accordance with Example 8, a molecular weight of 612

PBS phosphate buffered saline containing calcium and magnesium (Sigma, D8662).

PQ-1 polyquaternium-1 (dimethyl-bis[(E)-4-[Tris(2-hydroxyethyl)azuni-yl]-but-2-enyl]Azania chloride)

PVP poly(N-vinyl pyrrolidone) (with specified values of K)

SiGMA (3-methacrylate-hydroxypropoxy)propylbis(trimethylsiloxy)silane

TEGDMA tetraethylethylenediamine

TPME tripropyleneglycol ether

Examples 1-3

Lenses are listed in table 1, compositions were made as follows.

As a diluent for Examples 1-3 used a mixture 18,33 g PVP 2500/48,34 g of t-amyl alcohol. As a diluent for Example 4 used a mixture of 16.2 g of PVP 2500/64,8 g of t-amyl alcohol. The mixture of monomers was placed in a mold for casting made from materials Zeonor front and mixtures Zeonor:polypropylene (55:45) forming the rear lens surfaces. The mixture of monomers was polymerizable under visible light (Philips TL-03) in nitrogen atmosphere (approximately 3% O2) using the following profile of polymerization: 1 mW/cm2for approximately 20 seconds at room temperature, and 1.8±0.5 mW/cm2for about 270 seconds at a temperature of 75±5°C, and 6.0±0.5 mW/cm2for about 270 seconds at a temperature of 75±5°C.

After polymerization, the molds were opened and removed the lens using 70% isopropyl alcohol solution in deionized water. Approximately 40-50 minutes obtained lens was moved to (i) 70% solution of isopropyl alcohol in deionized water for approximately 40-50 minutes; (ii) 70% solution of isopropyl alcohol in deionized water for approximately 40-50 minutes; (iii) deionized water of at least about 30 minutes.

Then, using polypropylene cups and foil lens was placed in 950+/-50 ál buffered borate solution Sul the ATA sodium with the addition of 50 parts per million of methyl cellulose (SSPS) and once autoclaved (124°C, 18 minutes).

Table 1
Component
Example 1Example 2Example 3Example 4Comparative example 1
Macromer0006,930
HO-mPDMS 100000045,540
SiGMA303030028
acPDMS 200055500
mPDMS 100028282803
DMA19191919,824
HEMAof 7.758,257,1512,416
MAA10,51,610
Norbloc2222,182
PVP 36000077711,887
Blue HEMA0,020,020,020,020,02
CGI 8190,230,230,230,250,25*
Just monomers100100100100100
Diluent:40404044,7523**
*CGI 1850
**D3O

Example 4

Manufactured lenses specified in table 1 of Example 4, the composition described in Example 1 with the following change in the profile of polymerization: 1 mW/cm2(10-30 seconds, room temperature), and 1.5±0.2 mW/cm2(approximately 160 seconds, the temperature of 80±5°C), 6,0±0,2 mW/cm2(approximately 320 seconds, a temperature of 80±5°C).

After polymerization, the molds were opened and removed the lens using 70% isopropyl alcohol solution in deionized water. After 60 minutes the obtained lens was moved to (i) 70% solution of isopropyl alcohol and deionized water for 60 minutes; (ii) 70% solution of isopropyl alcohol and deionized water for 60 minutes; (iii) deionized water for 30 minutes; (iv) deionized water for 30 minutes; (v) deionized water for 30 minutes.

Then the lens was treated with silver using the first aqueous potassium iodide solution and then an aqueous solution of NITR is the silver. The lens was placed in 10 ml SSPS in glass bottles with silicone stoppers and three times with autoclaved (121°C, 30 minutes).

Evaluation of stability

The lenses of Examples 1-4 and Comparative example 1 was placed in a chamber with controlled temperature of 55°C. After a certain period of time the lens was taken out from the chamber and tested them for the modulus of elasticity, maximum elongation and diameter (in Examples 1-3 to perform each measurement lenses were extracted in the following amount: 8-10 lenses for diameter measurement, 9 lenses for the measurement of the H2O and 8-10 lenses for testing mechanical properties; in Examples 4, 5 to perform each measurement lenses were extracted in the following quantity: 5 lenses for diameter measurement, 9 lenses for the measurement of the H2O and 5 lenses for testing mechanical properties). The stability data of the lenses of Examples 1-4 is shown in figure 1. In addition, the figure also shows the stability data of lenses fabricated as described below for Comparative example 1 not containing ionic components as nonionic control sample.

In tables 2 and 3 shows the results of measurement of the modulus of elasticity of manufactured lenses after a certain period of time.

0,0008
Table 2
Example No.Product sustainability[MAA]
% the weight.
MAATime (weeks)The modulus of elasticity (kPa (psi))Elongation (%)Diameter (mm)
10,001710,120558+48 (81+7)252+4713,66+0,06
10,001710,122552+41 (80+6)243+2013,59+0,06
10,001710,125607+41 (88+6)163+2813,59+0,14
10,001510,1210634+55 (92+8)175+34 13.56MHz+0,05
10,001710,1218807+76 (117+11)112+3413,54+0,1
20,00080,50,060558+55 (81+8)294+4213,53+0,04
20,00080,50,062558+34 (81+5)284+4113,59+0,05
20,00080,50,065586+34 (85+5)216+1513,49+0,08
20,00080,50,0610not MEAs.not MEAs.not MEAs.
20,50,0618814+55 (118+8)144+2013,49+0,12
30,00261,60,190796+34 (72+5)210+6714,00+0,07
30,00261,60,192558+41 (81+6)169+3713,94+0,05
30,00241,60,195669+28 (97+4)104+2613,89+0,04
30,00261,60,1910903+48 (131+7)81+1513,72+0,06
30,00261,6 0,19181200+76 (174+11)48+1113,62+0,07
* Mol/100 grams of reactive components

Table 3

Example No.Product sustainability[MAA]
% the weight.
MAA*Time (weeks)The modulus of elasticity (kPa (psi))Elongation (%)Diameter (mm)
40,0001910,120324+55 (47+8)73+5113,89+0,04
40,0001910,121386+76 (56+11)169+9713,94+0,09
40,0001910,124 407+103 (59+15)106+5613,92+0,05
40,0001910,126not MEAs.not MEAs.not MEAs.
40,0001910,128365+7 (53+1)140+7313,91+0,1
Comparative example 10000689+34 (100+5)247+4514,05+0,02
Comparative example 10001752+76 (109+11)234+5214,07+0,01
Comparative example 10004 772+21 (112+3)220+5214,05+0,02
Comparative example 10006717+62 (104+9)249+3814,08+0,02
Comparative example 10008731+110 (106+16)202+6114,05+0,01
*Mol/100 grams of reactive components

Figure 1 shows a graph of the modulus of elasticity depending on time according to the data presented in tables 2 and 3 above. Line for Comparative example 1 and Example 4 is almost horizontal, due to the small changes in the elastic modulus in the intervals of measurement. With increasing concentration of methacrylic acid and molar compositions of the slope of the lines also increases, and then increases significantly in the transition from Example 1 (concentration of methacrylic acid 1 wt%. and product stability 0,0017) for Example 3 with the concentration of methacrylic acid and 1.6% of the weight. and work ustoichivosti,0024. Change the diameter of the lens and the maximum tensile additionally confirm the trends observed for the change in the elastic modulus.

Figure 1 clearly shows the relationship between the hydrolytic stability of the lenses and the product of the molar concentrations of anionic (carboxylate) groups and silicon-containing groups TMS. In the calculation are listed in tables 2 and 3 molar products were taken into account only the molar content of silicon (Si) monomers containing trimethylsilyl group (TRIS or SIMAA2). The results of these experiments, it was unexpectedly discovered that the stability of the lenses made of silicone hydrogel, which include at least siliconsamurai component containing at least one TMS group and at least one anionic component, such as methacrylic acid, sharply decreases when exceeding a certain threshold concentration of the anionic component. So, the lenses of Examples 1 and 2 are mostly the same stability, even though the lenses of Example 1 contain twice as much of methacrylic acid (1%)than the lens of Example 2 (0.5 percent). However, the stability of the lenses produced in Example 3 was significantly lower than that of the lenses in Examples 1 and 2. This result is unexpected and provides a relatively narrow window of concentration of the anionic component having at least one group TMS siliconsamurai whom is onenow, introduced into the reaction mixture composition for the manufacture of such lenses. The inclusion in the composition of the reaction mixture with a group TMS siliconsamurai components in quantities to satisfy the works of sustainability, allows you to adjust the balance between stability and other properties, such as the required modulus of elasticity, elongation or loss tangent. Work stability, the concentration of methacrylic acid and the percentage change in the elastic modulus are shown in table 8 below.

Comparative example 1

The reaction mixture of monomer composition specified in table 1 for Comparative example 1, was placed in a mold for casting forming the front surface of the lens part of the material Zeonor and closed form forming the rear surface of the lens part of the material Zeonor. Lens has polymerizable under visible light in a nitrogen atmosphere. Profile of polymerization: 1) preliminary polymerization (lamp TLDK-30W/03, 30-120 seconds, 60-80°C); 2) polymerization (lamp TLD-30W/03, 320-800 seconds, 70-80°C). Then the molds were opened, removed the lenses were extracted and hydrational in mixtures of isopropyl alcohol/water. The finished lens was placed in storage in borate buffered saline solution.

Example 5

Prepared a mixture of monomers of the components and the quantities indicated in the table is 4. The mixture of monomers was placed into the mold forming the front surface of the lens part of the material Zeonor and forming the rear surface of the lens part of the material Zeonor:polypropylene (55:45). The form was closed and held in closed condition at a temperature of 65°C without exposure. The reaction mixture was polymerizable under visible light (Philips TL-03) at a temperature of 65ºC in a nitrogen atmosphere (approximately 3% O2)using the following profile polymerization: 1.5 mW/cm2for approximately 330 seconds, 7±0.1 mW/cm2for about 440 seconds.

After polymerization, the molds were opened and removed the lens in 70% isopropyl alcohol solution in deionized water. Approximately 60-70 minutes of the obtained lens was moved to (i) 70% solution of isopropyl alcohol in deionized water for approximately 30-40 minutes; (ii) 70% solution of isopropyl alcohol in deionized water for approximately 30-40 minutes; (iii) deionized water of at least about 30 minutes.

Then, using polypropylene cups and foil lens was placed in 950+/-50 ál of borate buffered solution of sodium sulfate with the addition of 50 parts per million of methyl cellulose (SSPS) and once autoclaved (124°C, 18 minutes).

Table 4
Component% the weight.
HO-mPDMS 100055
DMA13,53
HEMA12,5
TEGDMA3
MAA1,5
Norbloc2,2
PVP 36000012
Blue HEMA0,02
CGI 8190,25
Just monomers100
The diluent (TPME):45

Then the lens was placed in a chamber with controlled temperature of 55°C. After 5 and 10 weeks of the lens was taken out from the chamber and tested them for the modulus of elasticity, maximum elongation, diameter, and percentage of water. The results are shown in table 5.

Table 5
Example 5, 100% TPME
PropertiesInitial state 5 weeks10 weeks
The modulus of elasticity (kPa (psi))641±69 (93±10)724±55 (105±8)703±90 (102±13)
Elongation (%)231±61206±43196±39
The content of H2O (% wt.)52,2±0,252,2±0,152,5±0

Examples 6 and 7

He repeated the procedure described in Example 5, with the replacement of diluent specified in tables 6-7 below. Lenses were placed in a chamber with controlled temperature of 55°C. in 5, 10, 15 and 20 weeks of the lens was taken out from the chamber and tested them for the modulus of elasticity, maximum elongation, diameter, and percentage of water. The stability data of the lenses of Examples 6-7 are presented in figure 3 and 4.

Table 6
Example 6, 100% 3-methyl-3-pentanol
Initial state5 weeks10 weeks15 weeks20 weeks
Odul of elasticity (kPa (psi)) 676
(98)
856 (85)593 (86)600 (87)648 (94)
Elongation (%)179182174163147
The content of H2O (% wt.)53,154,653,553,954,0
Diameter (mm)
(lens -6,00 diopters)
br12.62to 12.4412,4212,4512,50

Table 7
Example 7, 75% of batxillerat/25% 3-methyl-3-pentanol
PropertiesInitial state5 weeks10 weeks15 weeks20 weeks
The modulus of elasticity (kPa (psi))579 (84)572 (83) 490 (71)517 (75)572 (83)
Elongation (%)232184209169178
The content of H2O (% wt.)53,354,253,753,854,1
Diameter (mm)
(lens -1,00 diopters)
14,4314, 48mm14,5014, 48mmof 14.46

Work stability, % weight. methacrylic acid and the percentage change in the elastic modulus for lenses all of the Examples are shown in table 8 below.

0,012
Table 8
Example No.Product sustainability[MAA]
(wt%)
[MAA]*Δ module @ ned (%)Δ module @ ned (%)
10,001711444
20,00080,50,006not MEAs.46
30,00261,60,01935141
40,0001910,00613*not MEAs.
Comparative example 100012*not MEAs.
501,50,017the 9.7not MEAs.
601,50,017-12-4**
701,5 0,017-15-1**
* measured on a 8 week
** measured at 20 week

The change in the elastic modulus for lenses of Comparative example 1 shows that the modulus of elasticity can vary up to 10% without the introduction into the composition of the lens material anionic component. This is also indicated and are shown in tables 2 and 3 standard deviations. Changes in the elastic modulus in Examples 6 and 7 are given as negative values, since the modulus of elasticity for these lenses decreased slightly to 10 and 20 weeks. However, these changes are within the standard deviation used for validating the modulus of elasticity and should be treated as corresponding to no change. In table 8 the data also show that the best results were achieved for compositions that do not contain group TMX silicone monomers in the reaction mixture (Example 4 - a mixture mPDMS and macromer, Examples 5-7 - mix formula HO-mPDMS). The best stability showed lenses of those Examples, the reaction mixture in which as siliconsamurai components included only the silicone components type PDMS (Examples 5-7).

Example 8

To a solution of 45.5 kg 3 allyloxy-2-hydroxypropylmethacrylate (AHM) and 3.4 g of butylated guy is roxicodone (BHT) under stirring was added 10 ml of divinyltetramethyldisiloxane Pt (0) in xylene (concentration of 2.25%Pt), and then 44,9 kg n-butyltrichlorosilane. The dissipation in the course of the reaction was controlled to maintain the temperature of the reaction mixture of approximately 20oC. After complete consumption of n-butyltrichlorosilane platinum catalyst was deactivated by the addition of 6.9 g of diethylethylenediamine. The resulting crude reaction mixture was extracted several times 181 kg of ethylene glycol until the residual content of AHM in the raffinate not dropped to <0.1 percent. Then to the resulting raffinate added 10 g of BHT, the mixture was mixed until dissolved and removed residues of ethylene glycol, having 64,5 kg OH-mPDMS. In the obtained liquid was added 6,45 g of 4-methoxyphenol (MeHQ), the solution was mixed and filtered, obtaining 64,39 kg final OH-mPDMS in the form of a colorless oil.

Example 9 and Comparative example 2

Listed in table 9 components (except PVP K90) were mixed in a vessel for at least 1 hour under stirring. In the resulting reaction mixture under stirring slowly added PVP K90, making sure that the add was not formed lumps. After adding just PVP the resulting reaction mixture was stirred for an additional 30 minutes. The vessel is then hermetically closed, placed on a roller mill and mixed at a speed of ~200 rpm overnight.

The reaction mixture is placed is in a vacuum dessicator (pressure of approximately 10 mm Hg) and was pumped for approximately 40 minutes. Plastic mold for molding lenses and syringes for dispensing monomers put into the atmosphere N2(<2% O2at least 12 hours. Part form for casting the rear surface of the lens manufactured from polypropylene 9544 part forms for molding the front surface of the lens made from a material Zeonor™. In each of the front parts put 50 ál of the reaction mixture and slowly lowered them back part before closing forms. The described process was carried out in nitrogen atmosphere (<2% O2).

The mixture of monomers was polymerizable under visible light (lamp Philips TLK 40W/03) in nitrogen atmosphere (approximately <2% O2)using the following profile of polymerization: 5±0.5 mW/cm2within about 10 minutes at a temperature of approximately 50±5°C.

Then, prying, separated rear molds for casting. The lens remained on the front parts of the forms, and to separate the dry lenses by forming the front surface of the front part forms turned, putting efforts.

The obtained dry lenses visually inspected. The last visual inspection lenses Packed in a blister with 950 ál of buffered borate solution for storage with the addition of 50 parts per million metilcellulose for each lens. Then lenses were sterilized at 121°C for 18 minutes

Table 9
Component% the weight.
Example 9Comparative example 2
HO-mPDMS5555
TEGDMA0,250,25
DMA16.78 in18,28
HEMA12,512,5
MAA1,50
PVP K-901212
CGI 8190,250,25
Norbloc1,71,7
Blue HEMA0,020,02

The level of absorption of lysozyme and lipocalin was measured as described above.

Lysozyme is gidrolizatami enzyme able to degrade the cell wall of gram-positive and some gram-negative bacteria. Splitting peptidoglycan walls by stitching ß1-4 between N-acetylglucosamine and N-atsetilgalaktozamin (muramoto) leads to the lysis of bacteria.

To determine the ability of the lens to keep the protein in native form measured the activity of lysozyme. The level of native lysozyme corresponds to the level of active lysozyme determined in accordance with the process described above.

The results are shown in table 10.

Table 10
Example No.[ion.] % the weight.[ion.]*Lysozyme (μg)Lipocalin (µg)% native
lysozyme
Absorption PQ1
91,50,017103+54,6±0,460±7,790
Comparative hydrated example 2006,6±0,36,5 ħ 0,630±36
Balafilcon And 10,00646±467,8±0,537±8,36
Etafilcon And1,980,023843±231,8±0,280±112
* Mol/100 grams Riccione-capable components

Material balafilcon And used for the manufacture of lenses Purevision®, commercially available from Bausch&Lomb

Material etafilcon And used for the manufacture of lenses ACUVUE®, ACUVUE®2, commercially available from Johnson&Johnson Vision Care, Inc.

Absorption of preservatives from solutions for the care of contact lenses can affect the characteristics of the lenses, in particular caused by the contact lens colouring of the cornea. The level of absorption of preservatives for the lens of Example 9, Comparative example 2 and Purevision lenses was measured by incubation of these lenses in 3 ml Opti-free® RepleniSH® for 72 hours at room temperature, using the procedure described above to determine the levels of absorption of lysozyme and lipocalin. The solution Opti-free® RepleniSH® contains about 0.001% weight. PQ1 as desing tiraumea tools and preservative and the concentration of citrate dihydrate and citric acid monohydrate in it are 0.56% 0,021% (wt./weight.). The level of absorption PQ1 was determined by HPLC-analysis comparing the levels of PQ1 in the source solution for soaking the lenses with the level of PQ1 after 72 hours of incubation in a solution of the test contact lenses. The results are shown in table 10.

Examples 10-18 & Comparative example 2

Compositions were prepared as described in Example 9, but changing the content of methacrylic acid, as shown in table 11 below. The levels of absorption of lysozyme and PQ1 was measured as described in Example 9, the results are shown in table 12 below. The obtained results are also presented graphically in figure 1.

Table 9
Component% the weight.
Comparative example 2Example 10Example 11Example 12Por what measures 13 Example 14Example 15Example 16Example 17Example 18
HO-mPDMS55555555555555555555
TEGDMA0,250,250,250,250,250,250,250,250,250,25
DMA18,2818,0817,8817,6817,4817,2817,0816.88 in16.78 in16,68
HEMA12,512,512,5 12,512,512,512,512,512,512,5
MAA00,20,40,60,81,01,21,41,51,6
PVP K-9012121212121212121212
CGI 8190,250,250,250,250,250,250,250,250,250,25
Norbloc1,71,7 1,71,71,71,71,71,71,71,7
Blue HEMA0,020,020,020,020,020,020,020,020,020,02

Table 10
Example No.MAA, % weight.[MAA]*PQ1 (%) on the lensLysozyme (mg/lens)
Comparative example 2000 (0)6,78 (0,48)
100,20,0020,014,23 (1,7)
110,40,0042,05 (2,0) 21,23 (2,31)
120,60,0070,36 (0,5)37,76 (3,51)
130,80,0090,038,41 (2,93)
1410,01212,92 (4,4)56,55 (accounted for 10.39)
151,20,01442,7
161,40,01651,5
171,50,01784,5 (7,8)83 (7,21)
181,60,01972,6
*Mol/100 grams of reactive components.

As can be seen from figure 5, it is possible to create compositions with the desired level of absorption of lysozyme and low absor the PQ1 of the existing solutions for the care of contact lenses. Thus, the ophthalmic device forming the subject of the present invention, exhibit balance the desired level of absorption of protein, compatibility with existing solutions for the care of contact lenses and thermal stability.

1. The polymer to obtain ionic silicone hydrogel formed from reactive components, which include at least one siliconsamurai component comprising at least one trimethylsilyloxy group, and at least one ionic component comprising at least one anionic group of the anionic group is introduced into the reaction mixture in an amount of from about 0.05 to about 0.8 wt%, and
where the product of the resistance representing the product of the percentage molar content of silicon in trimethylsilyloxy group specified silicone component and the percentage molar content of anionic groups in the specified ion component is less than approximately 0,0006,
where siliconsamurai component comprising at least one trimethylsilyloxy group, selected from
2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl) oxy] disiloxanyl]propoxy] propyl ester (SiGMA),
2-hydroxy-3-methacryloxypropyl-Tris(trimethylsiloxy)silane,
3-methacrylic iproperties(trimethylsiloxy)silane (TRIS),
3-methacryloxypropyl(trimethylsiloxy)methylsilane and
3-methacryloxypropyltrimethoxysilane,
and ion containing component is a carboxylic acid component.

2. The polymer according to claim 1, wherein said at least one siliconsamurai component further includes silicone without trimethylsilyloxy group, selected from compounds of the following formula:

where b is in the range from 0 to 100, R1represents a monovalent group containing at least one ethylene unsaturated fragment; each group R2independently represents a monovalent alkyl group or aryl group, which may optionally be substituted alcohol, amine, ketone, carboxyl or ester group; R3represents a monovalent alkyl group or aryl group, which may optionally be substituted alcohol, amine, ketone, carboxyl or ester group; R4independently represents an alkyl, an aromatic chain or a monovalent siloxane chain, containing from 1 to 100 repeating units of Si-O.

3. The polymer according to claim 4, wherein said at least one siliconsamurai component is selected from the group including polydiorganosiloxane end monomethacrylate is Noah and mono-n-alkyl groups, bis-3-aryloxy-2-hydroxypropylcellulose-dialkylzincs, polydiorganosiloxane with the end methacrylate-through group, polydiorganosiloxane with integral mono-(3-methacrylate-2-hydroxypropoxy), sawn and monoalkylphenol groups, and combinations thereof.

4. The polymer according to claim 1, wherein said at least one siliconsamurai component selected from the group comprising a polydimethylsiloxane with terminal manometrically and mono-n-butilkoi groups, bis-3-aryloxy-2-hydroxypropoxy-propyltrimethoxysilane and polydiorganosiloxane with integral mono-(3-methacrylate-2-hydroxypropoxy), sawn and monobutyl groups, and combinations thereof.

5. The polymer according to claim 1, wherein said at least one siliconsamurai component selected from the group comprising a polydimethylsiloxane with terminal manometrically and mono-n-butilkoi groups, bis-3-aryloxy-2-hydroxypropionitrile-polydimethylsiloxane, polydimethylsiloxane with terminal mono-methacryloxypropyl groups and polydimethylsiloxane with terminal mono-(3-methacrylate-2-hydroxypropoxy), sawn and monobutyl groups, and mixtures thereof.

6. The polymer according to claim 1, wherein said containing carboxylic acid component selected from the group capable of free radical polymers the tion carboxylic acid, containing from 1 to 8 carbon atoms.

7. The polymer of claim 8, wherein said containing carboxylic acid component selected from the group comprising (meth)acrylic acid, acrylic acid, taconova acid, crotonic acid, cinnamic acid, vinylbenzoic acid, fumaric acid, maleic acid, N-vinyloxycarbonyl, and mixtures thereof.

8. The polymer of claim 8, wherein said containing carboxylic acid component is a methacrylic acid.

9. The polymer to obtain ionic silicone hydrogel formed from reactive components, which include from about 0.1 to about 0.9 wt.% at least one anionic component which is a containing carboxylic acid component and at least one siliconsamurai component where used silicone component does not contain trimethylsilyloxy group and where at least one siliconsamurai component is selected from the group comprising reactive polydiorganosiloxane selected from compounds of the formula I:

where b is in the range from 2 to 20; end groups R1independently selected from monovalent groups containing at least one ethyleneamine fragment and monovalent alkyl GRU is p, containing from 2 to 16 carbon atoms, provided that one end group, R1contains Ethylenediamine fragment and the rest of the group R1are selected from monovalent alkyl groups containing from 1 to 16 carbon atoms.

10. A contact lens formed by polymerization of components, which include at least one siliconsamurai component and at least one ionic component comprising at least one anionic group of the anionic group is present in the specified polymer in an amount of from about 0.05 to about 0.8 wt%, and
where siliconsamurai component selected from silicone component not containing trimethylsilyloxy group and represents a reactive polydiorganosiloxane, or siliconsamurai component comprising at least one trimethylsilyloxy group and representing politiacal-siloxane comprising at least one ethylenediamino group,
where if at least one siliconsamurai component includes at least one trimethylsilyloxy group works sustainability, representing the product of the percentage molar content of silicon in trimethylsilyloxy group specified silicone component and the percentage molar content of anyonehelp in the specified ion component, is less than approximately 0,0006, and
where ion containing component is a carboxylic acid component, and
where this contact lens absorbs at least about 10 μg of lysozyme, less than about 5 μg of lipocalin, and at least 50% of all proteins absorbed in or on the surface of these contact lenses, is in the native form.

11. A contact lens of claim 10, in which the specified ion component contains at least one capable of polymerization group and from three to ten carbon atoms.

12. A contact lens of claim 10, in which the specified ion component contains from three to eight carbon atoms.

13. A contact lens of claim 10, in which the specified ion component contains at least one carboxylic acid group.

14. A contact lens of claim 10, in which the specified ionic component selected from the group comprising acrylic acid, methacrylic acid, fumaric acid, maleic acid, taconova acid, cretonne easy acid, cinnamic acid, vinylbenzoic acid, monetary fumaric acid, maleic acid, basis of itaconic acid and N-vinyloxycarbonyloxy (N-vinyloxycarbonyl-β-alanine), and homopolymers and copolymers.

15. Contact lens indicated in paragraph 12, in which the contact lens of absorbi is the duty to regulate at least about 50 μg of lysozyme, or at least about 100 μg of lysozyme, or at least about 200 μg of lysozyme, or at least about 500 μg of lysozyme, or at least about 800 μg of lysozyme.

16. A contact lens of claim 10, in which the contact lens absorbs approximately 3 µg or less of lipocalin.

17. A contact lens of claim 10, further having a water content of at least about 15%.

18. A contact lens of claim 10, further having a permeability to oxygen Dk of at least about 50.

19. A contact lens of claim 10, in which at least 60% of all proteins absorbed in or on the surface of these contact lenses, is in the native form or at least 75% of all proteins absorbed in or on the surface of these contact lenses, is in the native form.

20. A contact lens of claim 10, in which indicated at least one siliconsamurai component is selected from compounds of the following formula:

where b is in the range from 0 to 100, R1represents a monovalent group containing at least one ethylene unsaturated fragment; each group R2independently represents a monovalent alkyl group or aryl group, which optionally may be the substituted alcohol, amine, ketone, carboxyl, ether group or a combination thereof; R3represents a monovalent alkyl group or aryl group, which may optionally be substituted alcohol, amine, ketone, carboxyl, ether group or a combination thereof; and R4independently represents an alkyl, an aromatic chain or a monovalent siloxane chain, containing from 1 to 100 repeating units of Si-O.

21. A contact lens of claim 10, in which at least one siliconsamurai component is selected from compounds of the formula I:

where b is in the range from 2 to 20; at least one end group, R1represents a monovalent reactive group, and the other end group, R1represents a monovalent reactive group, or a monovalent alkyl group containing from 1 to 16 carbon atoms, and the remaining groups R1independently selected from monovalent alkyl groups containing from 1 to 16 carbon atoms.

22. Contact lens according to claim 20, in which indicated at least one siliconsamurai component is selected from the group including polydiorganosiloxane end of monomethacrylate-through and mono-n-alkyl groups, bis-3-aryloxy-2-hydroxypropylcellulose is Xan, polydiorganosiloxane with end methacryloxypropyl group, polydiorganosiloxane with integral mono-(3-methacrylate-2-hydroxypropoxy), sawn and monoalkylphenol groups, and combinations thereof.

23. Contact lens according to claim 20, in which indicated at least one siliconsamurai component is selected from the group comprising a polydimethylsiloxane end of monomethacrylate-through and mono-n-C1-4alkyl groups, bis-3-aryloxy-2-hydroxypropylmethylcellulose and polydiorganosiloxane with integral mono-(3-methacrylate-2-hydroxypropoxy), sawn and mono-C1-4alkyl groups, and combinations thereof, etc.

24. Contact lens according to claim 20, in which indicated at least one siliconsamurai component is selected from the group comprising a polydimethylsiloxane end of monomethacrylate-through and mono-n-butilkoi groups, bis-3-aryloxy-2-hydroxypropylmethylcellulose, polydimethylsiloxane with terminal methacryloxypropyl group and a polydimethylsiloxane with terminal mono-(3-methacrylate-2-hydroxypropoxy), sawn and monobutyl groups, and mixtures thereof.



 

Same patents:

FIELD: medicine.

SUBSTANCE: invention refers to ophthalmic devices and methods for preparing them. What is presented is a soft silicone hydrogel contact lens which possesses an ability to deliver a hydrophobic comfort-maintaining agent (phospholipid, glycolipid, glyceroglycolipid, sphingolipid, sphingoglycolipid, fatty alcohol containing 8 to 36 carbon atoms, or a mixture thereof) into the user's eye gradually releasing it from a polymer matrix consisting of hydrophobic chains formed of a silicon monomer or macromere, and hydrophilic chains formed of a hydrophilic monomer or macromere when in use. What is also presented is a method for making the above contact lens.

EFFECT: in the presented soft silicone contact lens, the hydrophobic comfort-maintaining agent is not covalently bond to the polymer matrix wherein it is distributed and can be released from the soft hydrogel contact lens into the user's eye when in use reliably for a long period of time and thereby reinforcing and stabilising a lipid layer of the lachrymal fluid film and reducing eye dryness.

16 cl, 2 tbl, 7 ex

FIELD: physics, optics.

SUBSTANCE: device has a base and a plurality of convex and concave structural elements arranged on the surface of the base with spacing which is equal to or less than the wavelength of visible light. The structural elements form a plurality of tracks and form a structure of a quadrangular or quasi-quadrangular array. In one version, each structural element has the shape of an elliptical or truncated elliptical cone, the long axis of which is parallel to the track. In another version, the ratio ((2r/P1)×100) of the diameter 2r to the spacing P1 is 127% or higher, where P1 is the spacing between structural elements on the same track, and 2r is the diameter of the lower surface of the structural element in the direction of the track. The method is carried out by forming a resist layer on the peripheral surface of a columnar or cylindrical standard mould, forming latent images via interrupted irradiation of the resist layer with a laser beam while rotating the standard mould with relative displacement of the laser beam spot parallel to its central axis, forming a resist structure via development thereof and forming structural elements by etching using the resist structure as a mask.

EFFECT: improved antireflection characteristics.

12 cl, 6 tbl, 67 dwg

FIELD: chemistry.

SUBSTANCE: initial raw material in the form of a briquette of a powder of aluminium-magnesium spinel with stoichiometric composition, alloyed with 1 wt % of lithium fluoride is sintered in vacuum at a temperature of 1100-1500°C. The obtained briquette with a diameter equal to the diameter of the mould is loaded into the mould, with its further compression at a temperature of 1550-1600°C for 5-30 minutes under pressure of 350-500 kg/cm2, kept for 30-55 minutes and cooled.

EFFECT: obtaining a polycrystalline optical material from aluminium-magnesium spinel.

1 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: described are novel derivatives of benzotriazole of general formula , where X is C3-C4 alkenylene, C3-C4 alkylene, CH2CH2CH2SCH2CH2 or CH2CH2CH2SCH2CH2CH2; Y is hydrogen, if X is C3-C4 alkenylene, or Y is -O-C(=O)-C(R1)=CH2, if X is C3-C4 alkylene, CH2CH2CH2SCH2CH2 or CH2CH2CH2SCH2CH2CH2; R1is CH3 or CH2CH3; R2 is C1-C4 alkyl, and R3is F, Cl, Br, I or CF3.

EFFECT: compounds are absorbers of UV/visible light and can be applied in production of materials for ophthalmological lenses.

5 cl, 3 dwg, 5 tbl, 6 ex

FIELD: physics, optics.

SUBSTANCE: invention relates to means of displaying on liquid crystals. The electroconductive optical device has a base element and a transparent electroconductive film formed on the base element. The structure of the surface of the transparent electroconductive film includes a plurality of bulging portions with antireflection properties and arranged with spacing equal to or less than the wavelength of visible light.

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16 cl, 57 dwg

FIELD: transport.

SUBSTANCE: invention relates to space engineering and concerns creation of a temperature-regulating material for applying to a space object (SO) surface. The temperature-regulating material contains a substrate in the form of an optically transparent glass, a highly-reflective layer of silver, a protective layer. The highly-reflective layer of silver has a width of 0.10÷0.15 micron. For the protective layer stainless steel with thickness of 0.10÷0.20 micron is used. On the protective layer an epoxy varnish with thickness of 20÷30 micron is applied. Prior to covering the substrate with the highly-reflective silver layer, the substrate chemical cleaning is performed with simultaneous ultrasound treating for 3 minutes. Then the substrate is removed from the solution, rinsed successively with warm, cold and distilled water, each time for 1-1.5 min, and dried in the air. The surface is treated with glow discharge for additional purification and activation of the substrate surface. Then, the highly-reflective layer and the protective layer is successively applied in a vacuum chamber by magnetron sputtering without the vacuum chamber unsealing in one technological cycle successively positioning the substrate under the sources with a silver target and a stainless steel target. On the substrate with the highly-reflective layer and protective layer, the epoxy varnish layer of 20÷30 micron in thickness is applied for additional protection against atmospheric corrosion and for better adhesion of the coated substrate to adhesive composition. During temperature-regulating material attachment, material bonding using an adhesive composition with an electroconductive filler is performed with the help of weights. As the electroconductive filler, aluminium or silver powder is used in a quantity of 20±5% and 10±5% respectively. This powder provides required electroconductive properties of the temperature-regulating material surface.

EFFECT: better radiant heat characteristics of material, higher processability of coating, higher adhesion values of the coated substrate to the SO body surface.

3 cl, 2 dwg

FIELD: physics, optics.

SUBSTANCE: anti-reflective optical element has a base and a plurality of structures situated on the surface of the base and in form of cuts or protrusions with a conical shape. The structures are arranged with a spacing which is less than or equal to the wavelength of light of the wavelength range in the ambient environment using said element. Lower portions of structures lying next to each other are connected to each other. The effective refraction index in the direction of the depth of the structures gradually increases in the direction of the base and corresponds to an S-shaped curved line. The structures have a single step on the lateral surface of the structures.

EFFECT: improved anti-reflective characteristics.

19 cl, 60 dwg, 1 tbl

Infrared reflector // 2510055

FIELD: chemistry.

SUBSTANCE: infrared reflector consists of a metal substrate, characterised by that it is coated with a layer of zirconium nitride and chromium nitride of general formula (ZrxCr1-x)1-yNy with x ranging from 0.15-0.7 and y ranging from 0.01 to 0.265. The method of production involves producing a metal substrate; depositing a layer of zirconium nitride and chromium nitride on said substrate by physical vapour deposition using a target which contains 15-70 wt % zirconium, with the remaining part consisting of chromium and impurities which are inevitable in the treatment process, and injecting nitrogen with a neutral carrier gas in ratio of 4/16 to 16/16 while simultaneously sputtering zirconium and chromium.

EFFECT: designing an infrared reflector, having high heat reflecting power and high resistance to high temperatures in corrosive or oxidative media.

17 cl

FIELD: physics.

SUBSTANCE: method involves defining surfaces of a glass structure to be made in form of alternating parallel and/or curvilinear strips, while also determining coefficients of reflection, transmission and absorption, refraction indices, geometric shapes and dimensions of the strips and the required change in said parameters both along and across the strips, as well as the need to distribute the strips into zones with different light transmission characteristics so that, at given angles or ranges of incidence angles of rays, only the required part of rays of the required wavelength range passes in a directed manner through the entire glass surface. For each angle of incidence in the 0-90° range, the total percentage of directed light transmission is calculated as a ratio of the total area of the output surface, through which rays pass, to the area of the whole first receiving surface, and strips are made on surfaces of the glass structure by further processing the outer surface of the glass and/or gluing a film with strips made in advance, and/or by placing in laminated glass between layers.

EFFECT: providing selective control, according to a predetermined law, of values of light flux and direction of rays passing through a glass structure depending on angles of incidence.

8 cl, 12 dwg

FIELD: chemistry.

SUBSTANCE: composition consists of 90-96 wt % of a base - mixture of polydimethylsiloxane (40-60 wt %) and polymethylphenylsiloxane (60-40 wt %) liquid with viscosity of 3000-40000 mm2/s at temperature of 20°C and 4-10 wt % thickener - silicon dioxide. The composition has a refraction index of 1.4100-1.4300, penetration value of 160-280 units, and operates in the temperature range from (-70°C) to (+300°C).

EFFECT: improved properties of the composition.

2 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a novel polysiloxane compound with five-membered cyclic carbonate and a method of its obtaining. Claimed is the polysiloxane compound with five-membered cyclic carbonate of formula (1), where A stands for or , where R1 stands for an alkylene group, containing from 1 to 12 carbon atoms and can be bound through an element O and/or -(C2H4O)b-, R2 stands for the direct bond or an alkylene group, containing from 2 to 20 carbon atoms, and, when R2 stands for the direct bond, carbon of an alkylene group R1 or carbon of a group -(C2H4O)b- is bound directly with Si, bound with R2 in formula (1), b stands for a number from 1 to 300, a stands for a number from 8.2 to 9.2. Also claimed is the method of obtaining the claimed compound.

EFFECT: claimed compound makes it possible to obtain polyhydroxypolyurethane resins with improved exploitation characteristics.

2 cl, 3 dwg, 1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to application of polyorganosiloxane with 3 or more elementary siloxane links, which contains one or more organic components R1, with R1 containing one or more carbon-carbon bonds and is selected from cycloalkenyl, alkenyl, vinyl, alkyl, norbornyl, (di)cyclopentyl or methacrylate or acrylate derivatives, and one or more hydrocarbon components R2, with R2 having chain length from 5 to 50 carbon atoms, as additive in rubber recycling, where recycling represents peroxide vulcanisation. Amount of applied polyorganosiloxane constitutes from 0.5 to 10 parts per 100 parts of rubber.

EFFECT: polyorganosiloxanes lead to reduction of viscosity in rubber recycling and in case of necessity to improvement of mechanical properties of vulcanised rubber.

16 cl, 6 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to modified with polysiloxane polyhydroxypolyurethane resins. Claimed is polyhydroxypolyurethane resin, modified with polysiloxane, characterised by the fact that it is obtained by interaction of polysiloxane compound with five-membered cyclic carbonate of formula (1) where, A stands for or and amine compound, and content of polysiloxane segments in resin molecule corresponds from 1 to 7 wt %. Also claimed is method of obtaining said resin, versions of claimed resin compositions, thermally sensitive recording material, artificial leather, leather-like material from thermoplastic polyolefin resin, material for sealant processing and sealant, in which said resin is used.

EFFECT: claimed resin can be obtained by environmentally friendly methods and possesses excellent exploitation characteristics (resistance to abrasive wearing, chemical and heat resistance, etc).

24 cl, 3 dwg, 10 tbl, 26 ex

FIELD: chemistry.

SUBSTANCE: invention relates to modified with polysiloxane polyhydroxypolyurethane resins. Claimed is polyhydroxypolyurethane resin, modified with polysiloxane, characterised by the fact that it is obtained in reaction between five-membered cyclic carbonate and polysiloxane compound, modified with amine, and content of polysiloxane segments in resin molecule constitutes from 1 to 75 wt %. Also claimed is method of its obtaining, versions of claimed resin compositions, thermally sensitive recording material, artificial leather, leather-like material from thermoplastic polyolefin resin, material for sealant processing and sealant, in which said resin is used.

EFFECT: claimed resin can be obtained by environmentally friendly methods and possesses excellent exploitation characteristics (resistance to abrasive wearing, chemical and heat resistance, antistatic properties, etc).

23 cl, 3 dwg, 8 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: invention relates to siloxane surfactant compositions. Disclosed is a surfactant composition which contains siloxane, having the formula: M1DM2, where M1=(R1)(R2)(R3)SiO1/2; M2=(R4)(R5)(R6)SiO1/2 and D=(R7)(Z)SiO2/2, where each of the substitutes R1, R2, R3, R4, R5, R6 and R7 is independently selected from a group consisting of monovalent hydrocarbon radicals containing 1-4 carbon atoms, aryl and a hydrocarbon group containing 4-9 carbons and containing an aryl group; Z is a side hydrophilic ionic group selected from a group consisting of R8-RA, R9-RC and R10-RZ, where RA is an anionic substitute, RC is a cationic substitute or RZ is zwitterionic substitute on group D. Also disclosed are aqueous and non-aqueous emulsions based on said surfactant composition.

EFFECT: said surfactant composition is resistant to hydrolysis in both a basic and an acidic medium.

25 cl, 3 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: surface of materials is successively coated with an aqueous or alcohol solution of oligo(aminopropyl)ethoxysiloxane, dried and then heat treated. Further, the modified surface is wetted with an alcohol solution of glycidol, followed by drying and heat treatment. A layer of a modifier which gives the surface of the materials hydrophilic properties is formed on the surface of the materials as a result. The modifier is formed directly on the surface by molecular assembly of organosiloxane coatings with N,N-bis(1,2-dihydroxypropyl)aminoalkyl groups.

EFFECT: invention enables to modify treated materials to obtain a micro- or nano-size coating with different hydrophilic properties on their surfaces.

5 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to field of production of liquid crystal cells for liquid crystal cell devices, which can be widely used in different information systems. Method of producing liquid crystal cell with specified angle of liquid crystal orientation consists in application on substrata of electrode current-conducting boards of orientation substance in form of solution, which includes polyorganosiloxne, solvent and catalysis gamma-aminopropyltriethoxysilane with further removal of solvent and hardening in presence of catalyst, polyorganosiloxane, and after that, assembly of cells with placement between electrode current-conducting boards of liquid crystal. As polyorganosiloxane used is oligodialkyl alkyl hydride siloxane of general formula (A): (l) [R'2Sio]n[R"HSio]m[R"'3siO0.5]2' (a), where R', R", R'" = CH3, C2H5, п = 4 - 8, m = 6 - 9, R', R" are different from each other. Microrelief, formed on substratum, has geometrical dimensions corresponding to geometrical dimensions of liquid crystal molecules and providing angle of surface orientation in the range from 0 to 90° depending on "m" and "n" values of polyorganosiloxane of formula (A).

EFFECT: invention ensures obtaining liquid crystal cells for liquid crystal devices with orientation of liquid crystal at definite specified angle.

3 cl, 4 dwg, 2 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: asymmetric organomodified disiloxane surfactant having the formula: MM' wherein M contains branched hydrocarbon substitutes and M' contains a cationic, anionic or zwitterionic substitute and a polyether substitute which may be combined as one fragment. Aqueous and non-aqueous emulsions contain said surfactant.

EFFECT: invention increases hydrolysis resistance of the surfactant in the pH range from 3 to 12.

25 cl, 4 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: disclosed are compounds of formula (I), where a is an integer from 0 to 200; b is an integer from 1 to 40; c is an integer from 1 to 40; n is an integer from 1 to 50; x is an integer from 0 to 21; and R corresponds to formula (II) or formula (III). Also disclosed are intermediate compounds which are formed when producing the disclosed compound of formula (I), a composition of a personal hygiene product and a composition of a household chemical, containing the disclosed alkyl quaternium silicone compound.

EFFECT: owing to their unique structure, the disclosed compounds enable to form unique microemulsions and provide unique hair conditioning properties.

31 cl, 6 tbl, 41 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel benzoxazine siloxanes of general formula , where R1 denotes trimethylsilyl, dimethylsilylpropyl-8-methoxy-N-R2-1,3-benzoxazine, pentamethylsiloxypropyl- N-1,3-benzoxazine; R2 denotes alkyl C1-C4, hydroxyethyl, phenyl; X denotes oxygen, methylene, isopropyl, hexafluoropropyl; m=0-8, n=0-32; at certain conditions, values of X, R1 and number links in benzoxazine siloxanes. Heat-curable compositions for heat-resistant adhesives, filling compounds and coatings are obtained from the benzoxazine siloxanes and epoxy resins. The composition contains (pts.wt) one or seven benzoxazine siloxane compounds in amount of 10-50; epoxy-diane or epoxy-phenol-formaldehyde resin in amount of 100-50; a curing agent - isomethyl tetrahydrophthalic anhydride in amount of 0-83; filler - boron or aluminium nitrides in amount of 0-15.

EFFECT: coatings and adhesives obtained based on the invention withstand high thermal action.

2 cl, 3 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: invention relates to versions of a nonionic copolymer of a polyether and a polyester used in a cement composition for prolonging workability and to versions of a cement composition. The nonionic copolymer contains residues of monomers A, B and/or C. Monomer A is at least one ethylenically unsaturated monomer of a carboxylic ester containing a moiety which hydrolyses in a cement mixture, where the hydrolysed monomer residue contains an active binding portion for a component of the cement mixture. Component A is a hydroxyalkyl monoester, a hydroxylalkyl diester or mixtures thereof. Monomer B is at least one ethylenically unsaturated alkylene ether monomer containing at least one C2-4 oxyalkylene side group consisting of 1-30 links. Monomer C is at least one ethylenically unsaturated alkylene ether monomer containing at least one C2-4 oxyalkylene side group consisting of 31-350 links. Molar ratio of monomer A to the sum of molar ratios of monomers B and C is equal to 1:1-10:1. The cement composition contains water cement, water and an additive which contains said copolymer.

EFFECT: invention enables to preserve workability of the cement mixture, provides high fluidity, high stability and wear resistance thereof.

39 cl, 10 dwg, 9 tbl, 36 ex

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