JP2002520456A - Contact lens material - Google Patents

Abstract

(57) Abstract: The present invention relates to polymers having high oxygen permeability, and to hydration compositions containing such polymers, especially in the form of contact lenses. The present invention relates to [a] N, N-dimethylacrylamide, and [b] a monomer of the formula (I): wherein n is an integer of 1 to 8, preferably 4 to 8, R ′ is an alkyl group, preferably Is a lower alkyl group containing up to 4 carbon atoms, more preferably ethyl or butyl, and R ″ is a hydrogen atom or an alkyl group the same as or different from R ′, preferably a hydrogen atom or lower alkyl containing up to 4 carbon atoms. Alkyl group, more preferably a hydrogen atom or methyl]. In addition, additional monomers such as 3- [tris (trimethylsilyloxy) silyl] propyl methacrylate [TRIS] may be included.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to polymers having high oxygen permeability and to hydration compositions comprising such polymers, especially in the form of contact lenses.

[0002]

[Prior art]

For optimal performance, hydrogel contact lens materials must have optical clarity, tear resistance and high oxygen permeability.

[0003] Poly (2-hydroxyethyl methacrylate) is hard enough to be easily manufactured by mechanical manufacturing and polishing in the dry state, yet soft enough to be mounted in a water swollen state, and It is used for hydrogel contact lenses because it is comfortable. Other hydrophilic monomers such as dimethylacrylamide (DMA) polymer with methacrylate and N-vinylpyrrolidone (NVP) polymer can also be used. The oxygen permeability of such hydrogel contact lenses is determined by the water content and the thickness of the lens and can be improved by increasing the water content or reducing the thickness. However, both methods result in lenses of insufficient strength that are easily damaged.

[0004] The incorporation of either siloxane or fluorinated groups improves oxygen permeability without compromising good mechanical properties. While siloxane groups provide slightly higher oxygen permeability, fluorinated groups have a higher dry hardness, thus enabling the production of more machine-friendly polymers while simultaneously reducing lipophilicity. ,
It is particularly desirable because it deposits formation on the hydrated polymer.

[0005] Fluorine is introduced into the polymerized material by polymerizing fluorinated styrene and methacrylate with hydrophilic monomers such as N-vinylpyrrolidone (NVP) and 2-hydroxyethyl methacrylate (HEMA). Was. In this case, the range of the transparent composition is limited and the fluorinated monomer is incorporated in relatively small amounts. In some cases, the fluorine-containing monomers were specially synthesized to achieve better solubility in NVP and HEMA.

US Pat. No. 5,011,275 to Mueller is based on a polymer consisting of 15-85% dimethylacrylamide and 15-85% fluorine-containing monomers, and optionally other acrylate or methacrylate and polyvinyl-functional crosslinkers. Is disclosed. This polymer forms a clear hydrogel with a water content of about 25-75%. Polymerization between DMA and methacrylate is generally easier than for NVP polymers because of the more favorable reaction ratios leading to a more random polymer structure for DMA polymers.

The fluorine-containing monomers of US Pat. No. 5,011,275 are of the group consisting of: acrylate or methacrylate esters of formula B1

Embedded image Wherein R ₁ is a hydrogen atom or methyl, n is an integer of 1-4, m is an integer of 0-11, X is a hydrogen atom or fluorine, provided that when m is 0, X is fluorine. Fluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, undecafluorocyclohexylmethyl methacrylate and 2,3,
It is selected from the group consisting of 4,5,6-pentafluorostyrene.

[0008]

SUMMARY OF THE INVENTION The present inventors have discovered a group of fluorine-containing sulfanomido monomers that when polymerized with dimethylacrylamide, provide a high water content and unexpectedly high oxygen permeability.

[0009]

Means for Solving the Problems and Embodiments of the Invention

 The present invention relates to: [a] N, N-dimethylacrylamide, and [b] a monomer of the formula (I):

Embedded image Wherein n is an integer of 1 to 8, preferably 4 to 8, R ′ is an alkyl group, preferably a lower alkyl group containing up to 4 carbon atoms, more preferably ethyl or butyl, and R ″ is hydrogen Atom or the same or different alkyl group as R ', preferably a hydrogen atom or a lower alkyl group containing up to 4 carbon atoms, more preferably a hydrogen atom or methyl].

[0010] Preferred polymers are 40-9 based on the total weight of monomers [a] and [b].
A polymer containing 0% by weight of component [a] and 10-60% by weight of component [b].

[0011] A second aspect of the present invention relates to a hydrated composition in the form of a contact lens comprising: [a] N, N-dimethylacrylamide; Become.

A preferred contact lens form of the hydrated composition has an oxygen permeability of at least 30 Dk.

A third aspect of the present invention relates to an ophthalmic prosthetic device, a medicament comprising: [a] N, N-dimethylacrylamide, and [b] a polymer containing a polymerized product of the monomer of the above formula (I). Consists of a hydration composition in the form of a transport device or bandage.

The polymer is preferably 2 to 50% by weight, based on the total weight of the polymer
May be included in the amount of additional monomer. Along with the DMA monomer and the monomer of formula (I), styrene and styrene derivatives, methacrylates, especially 3- [tris (trimethylsilyloxy) silyl] propyl methacrylate [TRIS], acrylate, acrylamide, methacrylamide, vinylpyrrolidone, phosphorylcholine functional groups And one or more further monomers selected from the group consisting of the vinyl monomers containing, and partially or fully fluorinated derivatives thereof.

[0015] The polymer may be formed in the presence or absence of a crosslinking agent. If crosslinking agents are used, these may be ethylene glycol dimethacrylate or 1,1,1-
Although a multifunctional vinyl compound such as trimethylolpropane trimethacrylate may be used, a wide range of commercial crosslinkers is available and any polymerizable crosslinker is suitable for use in such compositions. Crosslinking agents are preferably included in amounts up to 8% by weight, based on the total weight of the polymer.

A fourth aspect of the present invention comprises a hydrogel having an equilibrium water content in the range of 30 to 90% by weight, which hydrogel is suitable for use as a contact lens and has been separated from the hydrophilic phase. Including polymers having a hydrophobic phase rich in fluorine and / or siloxane. Preferably, the equilibrium water content of the hydrogel ranges from 40 to 80% by weight. The hydrophobic phase rich in fluorine and / or siloxane preferably comprises units of the monomer of formula (I) above, more preferably 2- (
N-butylperfluorooctanesulfonamido) ethyl acrylate, 2- (N-
It comprises units of ethyl perfluorooctanesulfonamido) ethyl acrylate, 2- (N-ethylperfluorooctanesulfonamido) ethyl methacrylate or a mixture of two or more thereof. The hydrophobic phase contains units of DMA. D
In addition to MA, the hydrophilic phase can be formed by other monomers known to those skilled in the art, such as methacrylic acid / acrylic acid and their ester derivatives, N-vinyl-2-pyrrolidone, acrylamide, methacrylamide and phosphorylcholine derivatives. It may include a functional zwitterionic monomer introduced to impart biocompatibility.

[0017] The polymer is prepared using a heat- or UV-activated initiator or a redox system.
Prepared by free radical polymerization, either in bulk, solution, suspension or emulsion. Alternatively, gamma radiation is used to initiate polymerization. A variety of initiators are used based on azo or peroxy compounds for thermal initiation systems, and photoinitiators based on benzoin derivatives or other compounds that can generate radicals that absorb in the UV or visible range.

The polymer is obtained by casting a monomer solution and conducting polymerization.
Alternatively, it can be prepared in a sheet form or a film form by casting a polymer solution on a mold. The polymer can also be produced in a spin casting process. For contact lens manufacturing, the polymer may be formed as a rod, button or sheet and then machined, cut and polished to its final form. For use as a hydrogel material,
This polymer is formed as a crosslinked material.

Any organic solvent can be used in the polymerization process as long as it prevents polymer precipitation and heterogeneity of the polymer product.

[0020]

【Example】

Example 1 Synthetic hydrogel based on a copolymer of dimethylacrylamide and fluorosulfonamide acrylate (methacrylate) Material N, N-dimethylacrylamide (DMA) (supplied by Sigma-Aldrich Pty. Ltd) is passed through a short column of basic alumina. To remove the inhibitor.

The fluorinated monomers were selected as follows: 2- (N-butylperfluorooctanesulfonamido) ethyl acrylate (B
FA) (FX189 supplied by 3M Chemical Co) 2- (N-ethylperfluorooctanesulfonamido) ethyl acrylate (E
FA) (FX13 supplied by 3M Chemical Co) 2- (N-ethylperfluorooctanesulfonamido) ethyl methacrylate (
(EFMA) (FX14 supplied by 3M Chemical Co).

The structures of these monomers are shown in FIG. BFA was distilled under reduced pressure and EFA and EFMA were recrystallized twice from ethanol. Ethylene glycol dimethacrylate (EDMA) was purified by column chromatography using silica gel as absorbent and n-hexane / ethyl acetate (7/3 vol / vol) as eluent. Normal (1N) saline was used for all swelling measurements.

Polymerization A monomer mixture was prepared gravimetrically, deoxygenated with nitrogen for 10 minutes, and irradiated in a sealed polypropylene ampoule. In each case, the γ-radiation dose was 1 Mrad obtained from a ⁶⁰ Co source and the dose rate was 0.01 Mrad h ^{-1 as} measured by a Fricke dosimeter. The resulting xerogel solid rod is 90
At 24 ° C. for 24 hours, and then lathe cut to obtain a thin disk (10 mm in diameter; 1 mm in thickness) for measurement of expansion and a thin disk (10 mm in diameter; 0.1 mm in thickness) for measurement of oxygen permeability. -0.5 mm).

In this example, the hydrogel is referred to on the basis of the corresponding xerogel. Compositions are given as% by weight. For example, the name BFA-20 / DMA-80 does not include a crosslinking agent and means that BFA / DMA is 20/80 (w / w).
The same ratio of BFA to DMA is BFA-20 / DMA-80 / EDMA-5
In the terpolymer indicated by However, here EDMA makes up 5% by weight of the total monomers (BFA + DMA + EDMA). Since the conversion in these polymerizations is close to 100%, the composition of the xerogel is actually the same as the composition of the feed mixture.

Equilibrium Moisture Ratio The dimensions of the dried discs and pellets were measured using a vernier caliper and the weighed sample was equilibrated in normal saline at room temperature. Time to reach equilibrium is 2-4
It was a week. During this time, the saline was frequently changed to remove water-soluble substances from the samples.

The equilibrium water content (EWC) of the hydrogel is defined as follows:

(Equation 1) Where m _s = amount of expanded sample m ₀ = amount of dry sample.

This EWC measurement must be based on the weight of the xerogel in the brine medium after sol fraction extraction.

(Equation 2) [Wherein, m _E = dry amount of extracted sample].

The volume fraction of the polymer in the hydrogel is given as follows:

[Equation 3] Where D and D ₀ are the diameters of the hydrogel and xerogel, respectively.

Oxygen Permeability Measurements were performed on expanded samples over a range of thicknesses (at least 3) on a JDF Dk1000 ^™ Coulometric Oxygen Permeator under wet cell conditions.

Thermal Analysis The glass transition temperature (T _g ) of the xerogel was determined using a TA Instruments DSC 2010 Differential S at a heating rate of 10 ° C. min ⁻¹ using a sample weight in the range of 5-10 mg.
It examined using the canning Calorimeter. The reported T _g measurements were obtained from the second heated run.

Results and Discussion Xerogel Synthesis and Properties The xerogel rods are lathe cut into disks and the visual appearance is shown in Figures (2a-c). The polymer containing EFMA, a methacrylate derivative, became hazy or opaque, indicating that the copolymer was unsuitable for contact lens applications. However, the addition of a crosslinker (eg, 1 wt% EDMA) allowed the production of a transparent material. All xerogels maintained clarity upon swelling.

The difference in optical appearance of xerogels is theorized to be due to composition drift and subsequent phase separation between fluorine-rich and non-fluorine-rich regions.

One of the surprising features of these copolymer systems is that clarity is maintained when swollen with water. This is despite the presence of long perfluorinated side chains that are expected to aggregate in an aqueous environment. This is because if agglomeration occurs (which is likely to occur with a high probability), domains that are small enough to impede the diffusion of visible light and / or water-rich regions and domains that are actually isorefractive To form.

It is noted that sometimes anisotropic expansion causes deformation of the discs and pellets. Xerogel rods often exhibit residual stress due to inhomogeneities in the mixing of the original monomers and / or the substantial gel effect observed in these reactions (as evidenced by observation between cross polarising lenses). As shown). It was observed that the main cause of residual stress was the gel (or Tromsdorf) effect. By carefully controlling the rate of polymerization and molecular weight, the production of a sample that isotropically expands and is suitable for lens production can be achieved.

Glass Transition Temperature The T _g value of the xerogel was determined and is shown in Table 1. In all three copolymer systems, two T _g were observed. A thermogram of the BFA / DMA series is shown in FIG. The higher T _g is the DMA component and the lower T _g is the BFA
It is assumed to be from the side chain. Random copolymers usually show only single T _g of given by the weighted average of the T _g of the two polymerization component. The observed T _g behavior is relatively unusual for random copolymers and is associated with graft copolymers whose graft chains are incompatible with the backbone polymer, or with inappropriate polymer blends. Long perfluorinated side chains may be long and flexible enough to form domains with a subatmospheric glass transition. The high T _g (corresponding to DMA) decreases with increasing fluoromonomer concentration, and there appears to be a concomitant reduction in the lower glass transition. The reduction in both T _g can be explained as follows. The structure of this copolymer is shown in FIG.
A high T _g corresponds to a backbone polymer chain region that contains both DMA and fluoromonomer segments. Thus, high DMA T _g is mediated by contributions from the fluoromonomer component. The low T _g derives from the flexible side chain furthest from the polymer backbone that forms the microdomain, and this value excludes the contribution from the immobilized polymer backbone, so the T _g obtained for the pure fluoropolymer Lower than.

It is surprising that these copolymers exhibit clarity, as it is clear that these copolymers are heterogeneous. It is speculated that some suitability is introduced from two sources. The pure fluoromonomer used in this study is in fact a mixture of monomers having side chains of different lengths, and thus the degree of incompatibility of the perfluoro side chains with DMA-rich regions acts as a compatibilizer. Is reduced by contributions from smaller side chains. It is also conceivable that the sulfonamide group in the perfluoro side chain acts to some extent as a compatible agent through a favorable interaction with the tertiary amide group in DMA.

Swelling Properties Non-Crosslinked Samples Table 2 shows the swelling data obtained for three different copolymer systems at selected compositions, prepared in the absence of a cross-linking agent. As expected, the presence of a higher fluorine concentration induces a reduction in the equilibrium expansion. Nevertheless, it is possible to achieve a high water content while maintaining a reasonable fluorine content. This is clearly shown by comparing PHEMA with an EWC of about 40% by weight to the new materials (a similar water content is achieved with 60% by weight of fluoromonomer in these new materials) ). The sol fractions were all low, indicating that most of the DMA was copolymerized. No significant difference is seen between the expansion behavior of the three different copolymer sets.

Crosslinked Samples Table 3 shows the swelling properties of the same copolymer system prepared with 1, 2 and 5% by weight of EDMA crosslinker. The increase in crosslinker concentration is consistent with previous observations on hydrogel materials, and (generally) lower sol fractions and lower E
WC value.

Oxygen permeability The oxygen permeability obtained for the uncrosslinked hydrogel is shown in Table 4. Each stated value is the average of at least three independent measurements. An important factor is the large oxygen permeability of these hydrogel materials compared to non-fluorinated materials. This can be clearly demonstrated by comparing these hydrogels with about 60% by weight of fluoromonomer (similar to PHEMA) having a water content of about 40% by weight. Oxygen permeability is about 5 times higher than PHEMA. This is because oxygen transport in these hydrogels is not only through oxygen dissolved in the aqueous phase, but also through another pathway (dominant): the fluorine-rich, co-continuous
) It is presumed to occur through the polymerization phase. This suggests that the morphology of these gels is an important determinant in achieving high oxygen permeability. Further hypotheses follow from this consideration. In other words, water plays a role in these materials, firstly as a direct source of oxygen flow through dissolved oxygen (a conventional hydrogel material), and secondly, to provide a second mechanism of oxygen transfer. It plays two important roles, inducing a continuous hydrophobic network (via hydrophobic interactions). The slight increase in oxygen permeability that occurs when the DMA content (and thus the water content) increases is derived from the increased contribution of dissolved oxygen to oxygen flow. In this case, it is shown that the second transmission pathway (via the fluorine-rich network) is maintained despite the reduced overall fluorine content of the gel. Alternatively, an increase in the alignment of the hydrophobic regions suggests that oxygen transmission defects caused by reduced fluorine content are compensated.

Conclusion Materials suitable for use as contact lenses have been developed. In the dry state, these materials are easily turned, yielding a xerogel that can later be expanded into a hydrogel. The substantial gel effect induces residual stress in the xerogel, leading to anisotropic swelling, which can be minimized by employing a suitable polymerization method. Hydrogel materials exhibit high oxygen permeability at high moisture contents and exhibit mechanical properties comparable to those given for existing contact lens materials. Cytotoxicity tests have shown that these materials are safe for contact lens applications.

Table 1: Glass transition temperatures of uncrosslinked xerogels.

[Table 1]

Table 2: Swelling properties of non-crosslinked hydrogel at 296K.

[Table 2]

Table 3: Swelling properties of the crosslinked hydrogel at 296K.

[Table 3]

Table 4: Oxygen permeability of the uncrosslinked hydrogel.

[Table 4]

Example 2 Synthetic hydrogel based on terpolymer of dimethylacrylamide, fluorosulfonamide acrylate, and 3- [tris (trimethylsiloxy) silyl] propyl methacrylate Materials N, N-dimethylacrylamide (DMA) (Sigma-Aldrich Pty. Ltd.) and 3- [tris (trimethylsilyloxy)] propyl methacrylate (TRIS
) (Also supplied by Sigma-Aldrich Pty. Ltd) was purified by passing through a short column of basic alumina to remove inhibitors. The fluorinated monomer was selected as follows: 2- (N-butylperfluorooctanesulfonamido) ethyl acrylate ("
BFA ") (FX189 supplied by 3M Chemical Co) and 2- (N-ethylperfluorooctanesulfonamido) ethyl acrylate ("
EFA ") (FX13 supplied by 3M Chemical Co). The structures of these monomers are shown in Figure 1. BFA was distilled under reduced pressure and EFA was recrystallized twice from ethanol. (1N) saline was used for all swelling measurements.

Polymerization The monomer mixture was prepared gravimetrically, deoxygenated with nitrogen for 10 minutes, and irradiated in a sealed polypropylene ampoule. In each case, the γ-radiation dose was 1 Mrad obtained from a ⁶⁰ Co source and the dose rate was 0.01 Mrad h ^{-1 as} measured by a Fricke dosimeter. The resulting xerogel solid rod is 90
At 24 ° C. for 24 hours, and then lathe cut to obtain a thin disk (10 mm in diameter; 1 mm in thickness) for measurement of expansion and a thin disk (10 mm in diameter; 0.1 mm in thickness) for measurement of oxygen permeability. -0.5 mm).

In this example, the hydrogel is referred to on the basis of the corresponding xerogel. Since the conversion in these polymerizations is close to 100%, the composition of the xerogel is actually the same as the composition of the feed mixture.

Equilibrium Moisture Ratio The dimensions of the dried discs and pellets were measured using a vernier caliper and the weighed sample was equilibrated in normal saline at room temperature. The time to reach equilibrium is 2-
4 weeks. During this time, the saline was frequently changed to remove water-soluble substances from the samples.

The equilibrium water content (EWC) of the hydrogel is defined as follows:

(Equation 4) Where m _s = amount of expanded sample m ₀ = amount of dry sample.

This EWC measurement needs to be based on the weight of the xerogel in the brine medium after sol fraction extraction.

(Equation 5) [Wherein, m _E = dry amount of extracted sample].

The volume fraction of the polymer in the hydrogel is given as follows:

(Equation 6) Where D and D ₀ are the diameters of the hydrogel and xerogel, respectively.

Oxygen permeability measurements were performed on expanded samples over a range of thicknesses (at least 3) on a JDF Dk1000 ^™ coulometric oxygen permeation apparatus under wet cell conditions.

Results and Discussion Xerogel Synthesis and Properties The xerogel rods were lathe cut into disks. All xerogels maintained clarity upon swelling.

TRIS Added Fluorinated Hydrogel Swelling Properties The terpolymer compositions in Tables (5) and (6) show (E)
FA or BFA + DMA), and for TRIS, based on the total moles, on a mole percent basis. For example, the notation DMA
-96 / BFA-4 / TRIS-1.4 is 96m when DMA is (DMA + BFA)
ol .-%, meaning that BFA contains 4 mol wt .-% of (DMA + BFA) and TRIS is present at a concentration of 1.4 mol .-% of (MMA + BFA + TRIS).

Table (5) shows the swelling data obtained for three different copolymer systems at selected compositions, prepared in the absence of crosslinker, using 5, 10 and 20% by weight of TRIS. As expected, higher concentrations of TRIS increase the overall amount of hydrophobic monomer in the terpolymer composition, leading to lower EWC values. However, it should be noted that the addition of 20 wt% (5.3 mol%) TRIS has the same effect on EWC as containing only 1 wt% ethylene glycol dimethacrylate (EDMA). No significant differences are seen between the swelling data of the different terpolymer systems.

Oxygen Permeability TRIS is used as a monomer to increase the oxygen permeability of the polymeric material. Consequently, it was presumed that TRIS incorporation improved the oxygen permeability of these hydrogels. In Example 1, the high oxygen permeability of the hydrogel (without TRIS) is due to two mechanisms of oxygen transfer: via the aqueous phase,
Moreover, it passed through a co-continuous polymerization phase rich in fluorine. Oxygen permeability results for TRIS containing terpolymers are given in Table 6. Each value listed is the average of at least three independent measurements. These results show that the addition of TRIS reduces the Dk value when the fluorinated monomer (BFA or EFA) is present at 4 mol% (20% by weight). This is consistent with reduced oxygen transfer due to reduced EWC. BFA-96 / DMA-4 / TRIS-1.4
Oxygen permeability results for these are very low compared to other data and are simply unusual results. Overall, this oxygen permeability data suggests that TRIS does not affect the second pathway through the F-rich polymerization phase and simply acts as a hydrophobic comonomer. When the fluorinated monomer (BFA or EFA) is present at 40% by weight, there is an initial small reduction in the Dk value upon addition of TRIS. As more TRIS is added, Dk slowly recovers to the original value obtained for the base copolymer formulation without TRIS. In this case, it suggests that the initial loss of Dk caused by low EWC is compensated to some extent by increasing the siloxane content of the terpolymer.

Hydrogels with Constant DMA Concentration In order to study the relative contribution of siloxane and fluorinated components in the gel to the oxygen transfer mechanism, terpolymer compositions were treated with a constant DMA concentration but with EFA or It was prepared by changing the molar ratio of TRIS to BFA. Thus, in Tables (7) and (8), the terpolymer compositions are defined in a slightly different manner. For example, the notation DMA-96 / BFA-3 / TRIS-1 is D
MA constitutes 96 mol% of (DMA + BFA + TRIS), and BFA constitutes (DMA
+ BFA + TRIS) and TRIS is (MMA + BFA)
+ TRIS) at a concentration of 1 mol%. A composition comprising 96 mol% and 90 mol% of DMA comprises 80% and 60% by weight of DMA
It is also noted that the compositions correspond to

Swelling As can be seen from the swelling data in Table (7), TRIS incorporation induces an increase in EWC and aqueous sol fraction.

Oxygen Permeability From Table (8), it is clear that the main pathway of oxygen transmission through such hydrogels is through a fluorine-rich polymer phase. As the fluorine-containing monomer is systematically replaced by TRIS, the oxygen permeability of the hydrogel is greatly diminished.
This is despite the known properties of high oxygen solubility in TRIS-based polymers. This situation should also be observed in view of the fact that TRIS-based hydrogels have a higher water content and this actually increases oxygen transfer via dissolved oxygen in the aqueous phase. These results indicate the importance of a second mechanism for oxygen transfer through the co-continuous polymeric phase. TRIS is known to impart high oxygen permeability to polymeric materials, but this is only effective where there is unimpeded passage of oxygen transfer. In a hydrophilic polymer matrix, this can be achieved by phase separation.

Conclusion Materials suitable for use as contact lenses have been developed. In the dry state, these materials are easily turned, yielding a xerogel that can later be expanded into a hydrogel. Hydrogel materials have high oxygen permeability at high moisture content, and
Shows mechanical properties comparable to existing contact lens materials. The data obtained is
The importance of optimizing the phase separation of planned hydrogels with high oxygen permeability is shown. Limited oxygen permeability can be achieved via the aqueous phase (commercial hydrogel material route), but this requires a co-continuous polymer phase (siloxane or F 2) to provide an additional route of oxygen transfer. Can be substantially increased by designing the polymer morphology to provide a polymer-based polymer).

Table 5: Swelling properties of TRIS added hydrogels at 296K.

[Table 5]

Table 6: Oxygen permeability of TRIS-loaded hydrogels.

[Table 6]

Table 7: Swelling properties of hydrogel with constant DMA at 296K.

[Table 7]

Table 8: Oxygen permeability of hydrogels with constant DMA.

[Table 8]

Industrial Applicability The polymers of the present invention can be used in ophthalmic devices such as soft contact lenses. They can also be used for various other applications that benefit from the high oxygen permeability and hydrophilicity of the polymer. These include, for example, oxygen permeable bandages, skin patches,
Carriers for controlled delivery of drugs, such as ingestible beads, bodily implants or ophthalmic inserts, and gas separation membranes.

It will be apparent to those skilled in the art that numerous variations and / or modifications may be made to the invention shown in particular embodiments without departing from the spirit or scope of the invention as broadly described. Would admit. Therefore, these embodiments are illustrative in all respects and not limiting.

[Brief description of the drawings]

FIG. 1 is a structure of a fluorine sulfonamide acrylic monomer used in Examples.

FIG. 2. Uncrosslinked xerogel [A is N, N-dimethylacrylamide (DM
A) Homopolymer and (a) BG is 2- (N-butylperfluorooctanesulfonamido) ethyl acrylate (BFA) / DMA copolymer (
(Continuously) containing 10, 20, 30, 40, 50 and 60% by weight of BFA)
, (B) HM is 2- (N-ethylperfluorooctanesulfonamido) ethyl acrylate (EFA) / DMA copolymer ((continuously) 10, 20, 30,
40, 50 and 60% by weight of EFA), (c) NS is 2- (N-ethylperfluorooctanesulfonamido) ethyl methacrylate (EFMA) /
2 is a photograph of a DMA copolymer (containing (continuously) 10, 20, 30, 40, 50 and 60% by weight of EFMA).

FIG. 3 is a thermogram of a non-crosslinked BFA / DMA xerogel. The vertical solid line shows the T _g values of the two glass transition homopolymers, where A is a DMA homopolymer, B is BFA-20 / DMA-80, C is BFA-40 / DMA-60, and D is BFA
-60 / DMA-40 and E are BFA homopolymers.

FIG. 4 BF showing the source of two different regions giving rise to two glass transition temperatures
A / DMA copolymer structure.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR , BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS , JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZWF term (reference) 2H006 BB03 BB05 BB08 BB09 4J100 AB00R AB02R AL02R AL08Q AL08R AL16Q AL62S AL63S AM15R AM19P AQ08R BA59Q BA80R BB18Q CA04 CA05 CA06 CA23 DA25 EA03 JA34

Claims (22)

[Claims] 1. [a] N, N-dimethylacrylamide, and [b] a monomer of the following formula: Wherein n is an integer from 1 to 8, preferably from 4 to 8, R ′ is an alkyl group, preferably a lower alkyl group containing up to 4 carbon atoms, more preferably ethyl or butyl, and R ″ is A hydrogen atom or an alkyl group the same as or different from R ', preferably a hydrogen atom or a lower alkyl group containing up to 4 carbon atoms, more preferably a hydrogen atom or methyl]. 2. A polymer according to claim 1, comprising 40-90% by weight of component [a] and 10-60% by weight of component [b], based on the total weight of monomers [a] and [b]. . 3. The polymer according to claim 1, wherein the polymerization product is formed in the presence of a crosslinking agent. 4. The polymer according to claim 3, wherein the crosslinking agent is present in an amount of up to 8% by weight, based on the total weight of the polymer. 5. The method according to claim 1, wherein the crosslinking agent is ethylene glycol dimethacrylate or 1,1,2.
The polymer according to claim 3, which is 1,1-trimethylolpropane trimethacrylate. 6. The polymer according to claim 1, wherein the polymerization product is formed in the presence of 1-5% by weight, based on the total weight of the polymer, of ethylene glycol dimethacrylate. 7. Based on the total weight of the monomers [a] and [b], [a] 40-90% by weight of N, N-dimethylacrylamide and [b] 10-60% by weight of the formula Monomer: embedded image Wherein n is an integer from 1 to 8, preferably from 4 to 8, R 'is ethyl and R''is methyl, wherein the polymer is based on the total weight of the polymer. A polymer formed in the presence of 1-5% by weight, based on ethylene glycol dimethacrylate. 8. [a] N, N-dimethylacrylamide, [b] a monomer of the following formula: Wherein n is an integer from 1 to 8, preferably from 4 to 8, R ′ is an alkyl group, preferably a lower alkyl group containing up to 4 carbon atoms, more preferably ethyl or butyl, and R ″ is A hydrogen atom or an alkyl group the same as or different from R ', preferably a hydrogen atom or a lower alkyl group containing up to 4 carbon atoms, more preferably a hydrogen atom or methyl], and [c] styrene, a styrene derivative, methacrylate, A polymer comprising a polymerized product of one or more monomers selected from the group consisting of acrylates, acrylamide, methacrylamide, vinylpyrrolidone, vinyl monomers containing phosphorylcholine functionality, and partially or fully fluorinated derivatives thereof. 9. The monomer [c] has a molecular weight of 2 to 5 based on the total weight of the polymer.
9. The polymer of claim 8, which is included in an amount of 0% by weight. 10. The method according to claim 1, wherein the monomer [c] is 3- [tris (trimethylsilyloxy)].
The polymer according to claim 8 or 9, which is [silyl] propyl methacrylate. 11. Based on the total weight of the monomers [a] and [b], [a] 60-80% by weight of N, N-dimethylacrylamide and [b] 40-60% by weight of the formula Monomer: embedded image Wherein n is an integer of 1 to 8, preferably 4 to 8, R ′ is ethyl or butyl, and R ″ is a hydrogen atom, and [c] 5-20% by weight based on the total weight of the polymer A polymer comprising a polymerization product of 3- [tris (trimethylsilyloxy) silyl] propyl methacrylate. A hydrated composition in the form of a contact lens, comprising the polymer according to any one of claims 1 to 11. 13. A hydrated composition in the form of a contact lens, comprising a polymer according to any one of claims 1 to 11, having an oxygen permeability of at least 30 Dk. 14. A hydrating composition in the form of an ophthalmic prosthetic device, a drug delivery device or a bandage, comprising a polymer according to any one of claims 1 to 11. 15. A hydrogel comprising the polymer according to claim 1 according to example 1. 16. A hydrogel comprising the polymer according to claim 8 according to example 2. 17. A hydrogel having an equilibrium water content in the range of 30 to 90% by weight, suitable for use as a contact lens, wherein the hydrophobic phase is rich in fluorine and / or siloxane separated from the hydrophilic phase. A hydrogel comprising a polymer having the formula: 18. The hydrogel according to claim 17, having an equilibrium water content in the range of 40 to 80% by weight. 19. The hydrogel according to claim 17, wherein the polymer has at least two glass transition temperatures. 20. The method of claim 1, wherein the hydrophobic phase is a monomer unit of the formula: Wherein n is an integer from 1 to 8, preferably from 4 to 8, R ′ is an alkyl group, preferably a lower alkyl group containing up to 4 carbon atoms, more preferably ethyl or butyl, and R ″ is A hydrogen atom or an alkyl group the same as or different from R ', preferably a hydrogen atom or a lower alkyl group containing up to 4 carbon atoms, more preferably a hydrogen atom or methyl]. 3. The hydrogel according to item 1. 21. The hydrophobic phase is 2- (N-butylperfluorooctanesulfonamido) ethyl acrylate, 2- (N-ethylperfluorooctanesulfonamido) ethyl acrylate, 2- (N-ethylperfluorooctanesulfonamide)
20) A hydrogel according to any one of claims 17 to 19, comprising units selected from the group consisting of: ethyl methacrylate and mixtures of two or more thereof. 22. A hydrogel according to claim 17, wherein the hydrophilic phase comprises units of N, N-dimethylacrylamide.