KR101987303B1 - Siloxane monomer, polymerization composition comprising this and silicone hydrogel lens manufactured by using this - Google Patents

Abstract

The present invention relates to a siloxane monomer, a polymer composition comprising the same, and a silicone hydrogel lens produced using the same. The silicone hydrogel lens of the present invention is a polymer composition comprising a novel siloxane monomer having a hydroxyl group at the terminal thereof, It has high wettability and improved physical properties such as water content and surface contact angle.

Description

 [0001] The present invention relates to a siloxane monomer, a polymer composition comprising the siloxane monomer, and a silicone hydrogel lens manufactured using the same.

The present invention relates to a siloxane monomer, a polymer composition containing the same, and a silicone hydrogel lens manufactured using the same. More particularly, the present invention relates to a novel siloxane monomer for producing a silicone hydrogel lens having excellent wettability, a silicone hydrogel A polymerization composition for producing a lens, and a silicone hydrogel lens produced using the same.

Contact lenses need to be in contact with the eye to maintain eye safety and efficacy while maintaining the transparency and wettability of the contact lens, so oxygen must be properly supplied from the atmosphere and the release of carbon dioxide from the cornea It should be appropriate.

In addition, the contact lens should be designed in consideration of the clinical aspects in which the flow of the tear layer should be smooth and excessive friction between the eyelid and the eye surface should be avoided. In addition, when used as a contact lens, it is desirable to use a material having a high refractive index such as tensile strength, biocompatibility, non toxicity, optical transparency of a material, refractive index, surface wettability, The conditions such as water content, swelling rate, and oxygen permeability suitable for the cornea should also be met.

Earlier contact lenses were made of hard materials and these lenses are still used in some applications, but they are not well suited for all patients because of their significantly reduced fit. Thereafter soft contact lenses based on hydrogels have been developed and are very popular today.

However, the 21st century, which is defined as the era of digital informatization, is threatened by the increase in the use time of various smart devices, and the health of the eyes is threatened. Furthermore, as a result of prolonged or continuous wearing, inconvenience to wearers, eye irritation, There are various problems such as adhesion of a lens to the cornea that may cause other damage, and there is an increasing demand for a contact lens having an improved physical property.

Therefore, various studies have been made on contact lenses having excellent oxygen permeability and wettability in order to maintain excellent wearing comfort even when worn for a long time.

For example, Korean Patent Registration No. 10-0594414 provides a method of improving the fit of a contact lens by increasing the hydrophilicity by plasma-treating the surface of an initial first generation silicone hydrogel contact lens.

However, there is still a demand for research on contact lenses having improved properties for easy wearing and safe wear for a long time.

Korean Patent No. 10-0594414

The present invention provides a novel siloxane monomer used in the production of a silicone hydrogel lens and a polymerization composition for the production of a silicone hydrogel lens containing the same.

The present invention also provides a silicone hydrogel lens having improved wettability by using the polymer composition comprising the siloxane monomer of the present invention.

The present invention provides a siloxane monomer for producing a silicone hydrogel lens having improved properties, particularly wettability and oxygen permeability, wherein the siloxane monomer of the present invention is represented by the following formula (1).

[Chemical Formula 1]

(In the formula 1,

R ₁ to R ₄ are independently of each other hydrogen or (C ₁ -C ₁₀ ) alkyl;

R _a1 to R _a8 are independently of each other hydrogen, hydroxy or (C ₁ -C ₁₀ ) alkyl, and any of R _a1 to R _a8 is necessarily hydroxy;

o, p, a and b are each independently an integer selected from 1 to 10;

q and c are each independently an integer selected from 0 to 10;

D ₁ and D ₂ are independently of each other a single bond, -NHCOO-, -NHCONH-, -OCONH-R _S -NHCOO-, -NHCONH-R _t -NHCONH- and -OCONH-R _z -NHCONH-, R _S , R _t and R _z are hydrocarbyl;

이며, R_b는 수소 또는 (C₁-C₁₀)알킬로, B₁ 및 B₂중 어느 하나는 반드시

이며B ₁ and B ₂ independently of one another are hydrocarbyl or

, R _b is hydrogen or (C ₁ -C ₁₀ ) alkyl, and either B ₁ or B ₂ is

And

A is any one selected from the following structural formulas.

[In the above formula,

이며, t는 0 내지 20의 정수이며;R ₅ to R ₁₀ independently of one another are hydrogen, (C ₁ -C ₁₀ ) alkyl, halo (C ₁ -C ₁₀ ) alkyl or

T is an integer from 0 to 20;

l, m and n are each independently an integer selected from 1 to 200.]

Preferably, R _a1 to R _a8 in the formula (1) according to an embodiment of the present invention are independently hydrogen or hydroxy, and any of R _a1 to R _a8 is necessarily hydroxy; q and c may be, independently of each other, an integer selected from 1 to 10. [

Preferably, Formula 1 according to an embodiment of the present invention may be represented by Formula 2 below.

(2)

(In the formula (2)

R ₁ to R ₄ are independently of each other hydrogen or (C ₁ -C ₁₀ ) alkyl;

R _a2 - R _a7 independently from each other are hydrogen or (C ₁ -C ₁₀ ) alkyl;

o, p, a and b are each independently an integer selected from 1 to 10;

q and c are each independently an integer selected from 0 to 10;

D ₁ and D ₂ are independently of each other a single bond, -NHCOO-, -NHCONH-, -OCONH-R _S -NHCOO-, -NHCONH-R _t -NHCONH- and -OCONH-R _z -NHCONH-, R _S , R _t and R _z are hydrocarbyl;

이며, R_b는 수소 또는 (C₁-C₁₀)알킬로, B₁ 및 B₂중 어느 하나는 반드시

이며B ₁ and B ₂ independently of one another are hydrocarbyl or

, R _b is hydrogen or (C ₁ -C ₁₀ ) alkyl, and either B ₁ or B ₂ is

And

A is any one selected from the following structural formulas.

[In the above formula,

이며, t는 0 내지 20의 정수이며;R ₅ to R ₁₀ independently of one another are hydrogen, (C ₁ -C ₁₀ ) alkyl, halo (C ₁ -C ₁₀ ) alkyl or

T is an integer from 0 to 20;

l, m and n are each independently an integer selected from 1 to 200.]

이며, t는 0 내지 20의 정수일 수 있으며, 보다 바람직하게는 R₅ 내지 R₁₀은 각각 독립적으로 수소, (C₁-C₁₀)알킬 또는 할로(C₁-C₁₀)알킬일 수 있다.Preferably, R ₅ to R ₁₀ in formula (2) according to an embodiment of the present invention each independently represents hydrogen, (C ₁ -C ₁₀ ) alkyl, halo (C ₁ -C ₁₀ )

, And t may be an integer from 0 to 20, more preferably R ₅ to R ₁₀ each independently may be hydrogen, (C ₁ -C ₁₀ ) alkyl or halo (C ₁ -C ₁₀ ) alkyl.

일 수 있다.Preferably, in Formula 2, R ₅ - R ₆ and R ₈ to R ₁₀ independently of one another are hydrogen or (C ₁ -C ₁₀ ) alkyl and R ₇ can be halo (C ₁ -C ₁₀ ) alkyl, more preferably 1, m, n are Each independently is an integer selected from 5 to 150, and R < ₅ > R ₆ and R ₈ to R ₁₀ are hydrogen or methyl; R ₆ is

Lt; / RTI >

Preferably R _a2 to in the general formula (2) of the present invention R _a7 is hydrogen; o, p, a and b are each independently an integer selected from 1 to 5; q and c may independently be an integer selected from 0 to 3. D ₁ and D ₂ may independently be a single bond.

The present invention also provides a polymerization composition for producing a silicone hydrogel lens comprising the siloxane monomer of the present invention and a reactive monomer.

Preferably, the polymerization composition for producing a silicone hydrogel lens of the present invention may contain 5 to 60% by weight of a siloxane monomer.

Preferably, the reactive monomer according to one embodiment of the present invention may be any one or a mixture of two or more selected from hydrophilic acrylic monomers and hydrophilic silicon acrylic monomers.

The present invention surprisingly improves the wettability of silicone hydrogel lenses by introducing one or more hydroxyl groups into the siloxane monomers used in the preparation of silicone hydrogel lenses.

Accordingly, the present invention relates to a silicone hydrogel lens prepared using a polymer composition containing a novel siloxane monomer, which has a high water permeability coefficient as well as a high water permeability coefficient and thus is excellent in long-term wearability and can prevent eye diseases such as dry eye syndrome and corneal edema have.

Hereinafter, the present invention will be described in more detail with reference to Examples. It should be understood, however, that the invention is not limited thereto and that various changes and modifications may be made without departing from the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention is merely intended to effectively describe a specific embodiment and is not intended to limit the invention.

The following terms used in accordance with the present invention and as used herein are defined in the following sense, unless expressly stated otherwise. Other terms are defined in the text or in some sense consistent with these uses.

The term " hydrogel " refers to a polymeric material that is swellable in water or swells by water, typically a network or matrix of polymer chains. The matrix may not be crosslinked or crosslinked. Hydrogels thus represent polymeric materials including contact lenses that are water-swellable or water-swellable. The hydrogel may be (i) unhydrated and water swellable, (ii) partially hydrated and swollen with water, or (iii) fully hydrated and swollen with water.

The term " polymeric composition " is understood to have the same meaning as the " polymeric mixture ", and may be understood to be prepolymerized or precurized suitable for polymerization. For example, in the case of a lens field, the polymeric composition may be a lens precursor composition. The polymerization composition may also be represented as a monomer mix.

Preferably, the polymeric composition or the lens precursor composition is not polymerized prior to curing or polymerization of the mixture or composition. However, the polymerization composition or the lens precursor composition may be partially polymerized prior to undergoing the curing process.

The term " monomer " refers to a compound that is polymerizable regardless of the molecular weight of the compound. Thus, the monomers may be low molecular weight monomers, such as the following, macromers.

The term "low molecular weight monomer" refers to a relatively low molecular weight compound that is polymerizable, for example, a compound having an average molecular weight of less than 700 daltons. In one example, the low molecular weight monomers may comprise a single unit of a molecule containing at least one functional group capable of being polymerized and combined with other molecules having the same or different structures as the low molecular weight monomers to form a polymer.

The term " macromer " refers to a medium or high molecular weight compound or polymer that may contain one or more functional groups that can be polymerized or further polymerized. For example, the macromer can be a compound or polymer having an average molecular weight of about 700 Daltons to about 2,000 Daltons.

The term " copolymer " refers to a material formed by the polymerization of one or more monomers, macromers, or mixtures thereof. Copolymers can not be polymerized, but can be crosslinked to other polymers that are present during the reaction of monomers, macromers, and mixtures thereof forming other polymers, for example, in the polymerizable composition or other polymers in the polymerizable composition Molecular < / RTI >

The present invention relates to a siloxane monomer used for producing a silicone hydrogel lens having improved wettability, and the siloxane monomer of the present invention is represented by the following formula (1).

[Chemical Formula 1]

(In the formula 1,

R ₁ to R ₄ are independently of each other hydrogen or (C ₁ -C ₁₀ ) alkyl;

R _a1 to R _a8 are independently of each other hydrogen, hydroxy or (C ₁ -C ₁₀ ) alkyl, and any of R _a1 to R _a8 is necessarily hydroxy;

o, p, a and b are each independently an integer selected from 1 to 10;

q and c are each independently an integer selected from 0 to 10;

D ₁ and D ₂ are independently of each other a single bond, -NHCOO-, -NHCONH-, -OCONH-R _S -NHCOO-, -NHCONH-R _t -NHCONH- and -OCONH-R _z -NHCONH-, R _S , R _t and R _z are hydrocarbyl;

이며, R_b는 수소 또는 (C₁-C₁₀)알킬로, B₁ 및 B₂중 어느 하나는 반드시

이며B ₁ and B ₂ independently of one another are hydrocarbyl or

, R _b is hydrogen or (C ₁ -C ₁₀ ) alkyl, and either B ₁ or B ₂ is

And

A is any one selected from the following structural formulas.

[In the above formula,

이며, t는 0 내지 20의 정수이며;R ₅ to R ₁₀ independently of one another are hydrogen, (C ₁ -C ₁₀ ) alkyl, halo (C ₁ -C ₁₀ ) alkyl or

T is an integer from 0 to 20;

l, m and n are each independently an integer selected from 1 to 200.]

The siloxane monomer represented by the formula (1) of the present invention has a high water content by dramatically increasing the wettability by introducing at least one hydroxy group into R _a1 to R _a8 in the formula (1), and has an oxygen permeability coefficient, an appropriate modulus of elasticity, Long-term wearability is high and it reduces the occurrence of eye disease.

In the siloxane monomer represented by the formula (1) of the present invention, R _a1 to R _a8 independently represent hydrogen or a hydroxy group, and any one of R _a1 to R _a8 is preferably hydroxy; q and c may be independently selected from 0 to 10 integers.

From the viewpoint of wettability and oxygen permeability, it is preferable that the formula (1) is represented by the following formula (2).

(2)

(In the formula (2)

R ₁ to R ₄ are independently of each other hydrogen or (C ₁ -C ₁₀ ) alkyl;

R _a2 - R _a7 independently from each other are hydrogen or (C ₁ -C ₁₀ ) alkyl;

o, p, a and b are each independently an integer selected from 1 to 10;

q and c are each independently an integer selected from 0 to 10;

D ₁ and D ₂ are independently of each other a single bond, -NHCOO-, -NHCONH-, -OCONH-R _S -NHCOO-, -NHCONH-R _t -NHCONH- and -OCONH-R _z -NHCONH-, R _S , R _t and R _z are hydrocarbyl;

이며, R_b는 수소 또는 (C₁-C₁₀)알킬로, B₁ 및 B₂중 어느 하나는 반드시

이며B ₁ and B ₂ independently of one another are hydrocarbyl or

, R _b is hydrogen or (C ₁ -C ₁₀ ) alkyl, and either B ₁ or B ₂ is

And

A is any one selected from the following structural formulas.

[In the above formula,

이며, t는 0 내지 20의 정수이며;R ₅ to R ₁₀ independently of one another are hydrogen, (C ₁ -C ₁₀ ) alkyl, halo (C ₁ -C ₁₀ ) alkyl or

T is an integer from 0 to 20;

l, m and n are each independently an integer selected from 1 to 200.]

이며, t는 0 내지 10의 정수일 수 있으며, 보다 바람직하게 각각 독립적으로 수소, (C₁-C₁₀)알킬 또는 할로(C₁-C₁₀)알킬일 수 있다.Preferably, R ₅ to R ₁₀ in Formula 2 are selected from the group consisting of hydrogen, (C ₁ -C ₁₀ ) alkyl, halo (C ₁ -C ₁₀ )

, T may be an integer from 0 to 10, and more preferably each independently may be hydrogen, (C ₁ -C ₁₀ ) alkyl or halo (C ₁ -C ₁₀ ) alkyl.

Preferably, in Formula 2, R ₅ - R ₆ and R ₈ to R ₁₀ independently of one another are hydrogen or (C ₁ -C ₁₀ ) alkyl and R ₇ can be halo (C ₁ -C ₁₀ ) alkyl, more preferably 1, m and n are Independently is an integer selected from 5 to 150,

일 수 있다. R ₅ - R ₆ and R ₈ to R ₁₀ are hydrogen or methyl; R ₆ is

Lt; / RTI >

In the above formula (2) in accordance with one embodiment of the invention R _a2 to R _a7 is hydrogen; o, p, a and b are each independently an integer selected from 1 to 5; q and c may be, independently of one another, an integer selected from 0 to 3; D ₁ and D ₂ may independently be a single bond.

The hydrocarbyl described in the present invention means a radical having one bonding position derived from a hydrocarbon.

The term "alkyl" as used in the present invention refers to a hydrocarbon chain having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, and more preferably 1 to 5 carbon atoms. Such a hydrocarbon chain is not necessarily saturated, but is preferably saturated, and may be branched or straight-chain, but usually a straight chain is preferable. Exemplary alkyl groups include methyl, ethyl, propyl, butyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 3-methylpentyl and the like.

The 'haloalkyl' means that the halogen is substituted at the hydrogen position of the alkyl, preferably fluorine.

Also, in the present invention, l, m, and n may be a block structure, and the block structure includes an irregular structure.

In one embodiment of the present invention, the formula (1) may be specifically selected from the following compounds. The following compounds 1 to 22 are specific examples of the compound of formula 1 of the present invention, but the present invention is not limited thereto.

[Compound 1]

(L, m and n are each independently an integer selected from 1 to 200)

[Compound 2]

(L, m and n are each independently an integer selected from 1 to 200)

[Compound 3]

(Wherein m is an integer selected from 1 to 200)

[Compound 4]

(Wherein n is an integer selected from 1 to 200).

[Compound 5]

(1 is an integer selected from 1 to 200)

[Compound 6]

(M and n are each independently an integer selected from 1 to 200)

[Compound 7]

(L and n are each independently an integer selected from 1 to 200).

[Compound 8]

(Wherein l and m are each independently an integer selected from 1 to 200)

[Compound 9]

(1 is an integer selected from 1 to 200)

[Compound 10]

(L and n are each independently an integer selected from 1 to 200).

[Compound 11]

(Wherein l and m are each independently an integer selected from 1 to 200)

[Compound 12]

(L, m and n are each independently an integer selected from 1 to 200)

[Compound 13]

(L, m and n are each independently an integer selected from 1 to 200)

[Compound 14]

(Wherein m is an integer selected from 1 to 200)

[Compound 15]

(Wherein n is an integer selected from 1 to 200).

[Compound 16]

(1 is an integer selected from 1 to 200)

[Compound 17]

(M and n are each independently an integer selected from 1 to 200)

[Compound 18]

(L and n are each independently an integer selected from 1 to 200).

[Compound 19]

(Wherein l and m are each independently an integer selected from 1 to 200)

[Compound 20]

(1 is an integer selected from 1 to 200)

[Compound 21]

(L and n are each independently an integer selected from 1 to 200).

[Compound 22]

(Wherein l and m are each independently an integer selected from 1 to 200)

Further, in one aspect of the present invention, the polymerization composition for producing the silicone hydrogel lens comprises the siloxane monomer of the present invention. The composition is not limited as long as it is a composition commonly used in a silicone hydrogel lens including the siloxane monomer of the present invention.

Further, in one embodiment of the present invention, the polymerization composition for producing the silicone hydrogel lens necessarily contains the siloxane monomer of the present invention represented by the above formula (1).

More specifically, one embodiment of the polymer composition of the present invention comprises at least one siloxane monomer and a reactive monomer represented by Formula 1 of the present invention, and may include a crosslinking agent, an initiator, and an additive.

The viscosity of the polymer composition for preparing a silicone hydrogel lens according to an embodiment of the present invention is preferably 10 to 20,000 cps, more preferably 100 to 15,000 cps, at 25 ° C. The above range is preferable because the productivity is high when injected into the mold parts.

The content of the siloxane monomer in the polymer composition of the present invention is preferably 5 to 60% by weight, more preferably 30 to 50% by weight in the polymer composition, but is not limited thereto. And excellent physical properties such as wettability can be achieved within the above range.

In one embodiment of the polymerization composition of the present invention, the reactive monomer is a monomer having a substituent capable of reacting with the siloxane monomer, and a hydrophilic monomer may be used. Here, the hydrophilic monomer is not particularly limited, May be used. For example, a hydrophilic acrylic monomer or a hydrophilic silicone acrylic monomer may be used.

Specific examples of the hydrophilic acrylic monomer include C ₁ -C ₁₅ hydroxyalkyl methacrylates substituted with 1 to 3 hydroxy groups, C ₁ -C ₁₅ hydroxyalkyl acrylates substituted with 1 to 3 hydroxy groups Acrylate, vinyl pyrrolidone, glycerol methacrylate, acrylic acid, and methacrylic acid, etc. [0035] The term " The hydrophilic acrylic polymer may be, for example, 2-hydroxyethyl methacrylate (HEMA), N, N-dimethyl acrylamide (DMA), N-vinyl And may be at least one selected from N-vinyl pyrrolidone (NVP), glycerol monomethacrylate (GMMA), and methacrylic acid (MAA).

In addition, the hydrophilic silicone acrylic monomer may include a polydimethylsiloxane-based compound or the like. Specific examples of the hydrophilic silicone acrylic monomer include tris (3-methacryloxypropyl) silane, 2- (trimethylsilyloxy) ethyl methacrylate, 3-tris (trimethylsilyloxy) silylpropyl methacrylate, 3- Methacryloxypropyltris (trimethylsilyl) silane (MPTS), 3-methacryloxy-2- (hydroxypropyloxy) propylbis (trimethylsiloxy) methylsilane and 4-methacryloxybutyl terminated polydimethylsiloxane And the like.

The hydrophobic monomer may be used together with the hydrophilic monomer in addition to the hydrophilic polymer. The hydrophobic monomer is not particularly limited and may be any of those conventionally used in the art. For example, a hydrophobic acrylic monomer may be used. have.

The hydrophobic acrylic monomers include alkyl acrylate monomers and alkyl methacrylate monomers. More specific examples thereof include methyl acrylate, methyl methacrylate, ethyl acrylate, N-propyl acrylate, n-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, N-butyl methacrylate, stearyl acylate, stearyl methacrylate, and the like. It is also possible to use monomers having a high glass transition temperature (T _g ) such as cyclohexyl methacrylate, tert-butyl methacrylate and isobornyl methacrylate, Etc. and mixtures thereof can also be used to enhance mechanical properties.

The reactive monomer is preferably 40 to 95% by weight in the polymer composition, but is not limited thereto. More specifically, it may be from 50 to 70% by weight, and the physical properties of the added reactive monomer may be expressed together while achieving the desired releasability in the above range.

In one embodiment of the polymeric composition of the invention, the cross-linking agent is selected from the group consisting of ethylene glycol dimethacrylate (EGDMA), diethylene glycol methacrylate (DGMA), divinylbenzene and trimethylolpropane trimethacrylate (TMPTMA) And the like can be used. In addition, the crosslinking agent is preferably 0.005 to 5% by weight, more specifically 0.010 to 3% by weight in the polymer composition.

In one embodiment of the polymeric composition of the present invention, the initiator is for polymerization, which is, for example, azodiisobutyronitrile (AIBN), benzoin methyl ether (BME), 2,5- -Di- (2-ethylhexanoylperoxy) hexane and dimethoxyphenylacetophenone (DMPA), and the like, but not limited thereto. The initiator is preferably 0.005 to 2.000 wt%, more preferably 0.010 to 1.500 wt%, in the polymerization composition, but is not limited thereto.

In one embodiment of the polymeric composition of the present invention, the additive may include a colorant, an ultraviolet blocking agent, a UV blocker, and the like. For example, colorants can be particularly helpful in visualizing contact lenses in aqueous liquids such as packaging solutions and the like. The additive is preferably 0.010 to 2% by weight, more preferably 0.05 to 1.5% by weight in the polymer composition, but is not limited thereto.

The present invention also provides a silicone hydrogel lens which is produced using the polymer composition of the present invention and has a water content of 25 to 70% and a contact angle of the surface of 40 째 or less by a trapped bubble method. Specifically, there is provided a silicone hydrogel lens having an excellent water content and a surface contact angle including a copolymer comprising at least one of a novel siloxane monomer and a reactive monomer of the present invention.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

The physical properties of the lens were measured by the following method.

(1) The contact angle of the surface

The contact angle () was measured by a captive air bubble method using a contact angle meter (DSA 100). The soft contact lens to be measured was attached to a holding base, immersed in saline at 25 ° C, and the bubbles were attached to the surface of the soft contact lens using a syringe to measure the angle between the soft contact lens and the bubbles in the saline solution. The smaller the measured value, the better the wettability.

(2) Moisture content

The water content (%) was evaluated by measuring the weight of the dry contact lens and the weight of the swollen contact lens after having been immersed in a 0.9 wt% sodium chloride (NaCl) aqueous solution for 24 hours, using the following equation. That is, the water content was evaluated by the ratio of the weight of the swollen contact lens (W _swell ) to the dry contact lens weight (W _dry ).

Water content (%) = (W _swell - W _dry ) / W _dry x 100

(3) Oxygen permeability coefficient (Dk value)

To determine the oxygen permeability (Dk), the specimens were stored at room temperature (35 ° C ± 0.5 ° C) for at least 2 hours. (Dk) was measured using an oxygen permeability meter (Model 201T, Rehder Development Co., West Lafayette, USA) under lens moisture saturation at 35 ° C ± 0.5 ° C and 98% Respectively.

(4) Weight average molecular weight

The weight average molecular weight was measured using a gel permeation chromatography (GPC) instrument manufactured by Waters. The equipment consists of a mobile pump (1515 Binary Pump), a column heater (1500 Series), a detector (2414 RI Detector) and an injector (2707 automatic injector). The analytical columns consist of Shodex KF-802, KF-802.5 and KF-803 Polystyrene (PS) SL-105 STD was used as a standard material. As the mobile phase solvent, HPLC grade tetrahydrofuran (THF) is used and the column heater temperature is 40 ° C and the mobile phase solvent flow rate is 1.0 mL / min. The siloxane monomer prepared for the sample analysis was dissolved in tetrahydrofuran (THF), a mobile phase solvent, and then injected into a GPC apparatus to measure the weight average molecular weight.

(5) Viscosity

The viscosity was measured using a Brookfield LVDV-2T viscometer. The siloxane monomer was placed in a container at 25 ° C at room temperature, and the viscosity was measured by rotating it at a speed of 10 rpm using a spindle.

[Example 1]

1) Synthesis of Siloxane Monomer

(1) Synthesis of siloxane monomer having Si-H: Synthesis step 1

145 g (0.49 mol) of octamethylcyclotetrasiloxane, 21 g (0.047 mol) of 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane, 5 g of 1,3,5,7-tetramethyl-cyclotetrasiloxane 7 g (0.014 mol) of 1,3-bis ((3-methacryloxy 2-hydroxypropoxypropyl) tetramethyldisiloxane), 180 g of chloroform, The mixture of 1.50 g of the sulfonic acid was stirred for 24 hours at 25 DEG C and then repeatedly washed with purified water until the pH of the mixture became neutral. After separating the water, chloroform and volatile components were removed under reduced pressure to obtain a clear viscous liquid The yield was 141 g (77.5%).

As a result of the analysis, the compound of the following formula 1-1 was synthesized.

The obtained product 400 MHz 1H magnetic resonance analysis, Si- at _{δ0.06 ~ 0.12 ppm CH 3, δ0.70} ppm Si- in the _{(t, 10H) CH 2 -CH} 2 - CF 3, δ2.07 ppm ( _{CH 2 - - CF 3, δ4.70} ppm (s, 6H) Si- H, δ5.60 ~ 6.15 ppm (dd, 4H) -CH = CH 2, δ1 in t, 10H) Si-CH ₂ in. 96 ppm (S, 6H) from _{-C CH 3 = CH 2, δ0.76} ppm (m, 4H) in _{Si- CH 2 -CH 2 -CH 2 -O} , Si- at δ 1.69 ppm (m, 4H) _{CH 2 - CH 2 -CH 2 -O} , δ 3.94 ppm (m, 4H) in the _{Si-CH 2 -CH 2 - CH} 2 -O, δ3.60 ~ O- CH at _{3.80 ppm (m, 5H) 2} - It was confirmed a peak of _{CH -OH, O-CH 2 -CH-} CH 2 - CH-OH, O-CH 2. Viscosity was measured with a viscometer to confirm the viscosity of 130 cP. GPC analysis revealed a weight average molecular weight of 12,799 g / mol.

(3)

[Formula 1-1]

(In the above formula, l = 6, m = 140 and n = 10).

(2) Synthesis of siloxane monomer having PEG functional group: Synthesis step 2

A mixture of 125 g of the siloxane monomer of the formula (1-1) synthesized above, 33 g (0.09 mol) of polyethylene glycol allyl methyl ether of the following formula (4), 250 g of isopropyl alcohol and 6.3 ml of a platinum catalyst was placed in a flask equipped with a reflux condenser , And heated under reflux for 6 hours with stirring. The reaction mixture was filtered, isopropanol was removed under reduced pressure, and washed several times with a mixture of acetone and water at a volume ratio of 1: 1. A volatile component was further removed under vacuum to obtain a transparent viscous liquid. The yield was 124 g, and the yield was 84.2%. As a result of the analysis, a compound represented by Formula 1-2 was synthesized.

As a result of the 400 MHz hydrogen nuclear magnetic resonance analysis of the obtained product, it was confirmed that O- CH ₂ CH ₂ - peak was generated at δ 3.15 to 3.90 ppm. Viscosity was measured with a viscometer to confirm the viscosity of 302 cP. GPC analysis revealed a weight average molecular weight of 15,232 g / mol.

[Chemical Formula 4]

[Formula 1-2]

(Where l = 6, m = 140, n = 10).

2) Preparation of polymeric composition

53.0 g of the siloxane monomer of formula 1-2 prepared in 1) above, 42.0 g of N-vinylpyrrolidone (NVP, Aldrich product, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, , 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich product, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The polymer composition was injected into a female mold for cast molding, and a male mold was assembled into the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 DEG C and polymerized for 1 hour, after which the mold was separated to obtain a lens. The resulting lens was immersed in ethyl alcohol for 1 hour, immersed in deionized water for 1 hour, and then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The release properties and physical properties of the prepared lens were measured and are shown in Table 1 below.

[Example 2]

1) Synthesis of Siloxane Monomer

(1) Synthesis of siloxane monomer having Si-H: Synthesis step 1

147 g (0.49 mol) of octamethylcyclotetrasiloxane, 5 g (0.021 mol) of 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-bis ((3-methacryloxy 2-hydroxypropyl Phenoxypropyl) A mixture of 7 g (0.014 mol) of tetramethyldisiloxane, 180 g of chloroform and 1.5 g of trifluoromethanesulfonic acid was stirred at 25 ° C for 24 hours and then repeated with purified water until the pH of the mixture became neutral After separating the water, chloroform and volatile components were removed under reduced pressure to obtain a clear viscous liquid. 131 g, and the yield was 82.0%.

As a result of the analysis, the compound of the following formula 1-3 was synthesized.

The obtained product 400 MHz 1H magnetic resonance analysis, δ0.06 ~ 0.12 ppm in _{Si- CH 3, δ4.70 ppm (s} , 6H) Si- H, δ5.60 ~ 6.15 ppm (dd, 4H) from -CH = CH ₂ ,? 1.96 ppm (S, 6H), -C CH ₃ = CH ₂ , δ0.76 ppm (m, 4H) In _{Si- CH 2 -CH 2 -CH 2 -O} , δ 1.69 ppm (m, 4H) Si-CH 2 in the _{- CH 2 -CH 2 -O, δ} 3.94 ppm (m _{CH 2 -O, δ3.60 ~ 3.80 ppm} (m, 5H) O- CH 2 -CH-OH, O-CH 2 in the - - CH -OH, O-CH , 4H) Si-CH 2 -CH 2 in ₂ -CH-CH ₂ . Viscosity was measured with a viscometer to confirm the viscosity of 105 cP. GPC analysis revealed a weight average molecular weight of 12,310 g / mol.

[Formula 1-3]

(In the above formula, l = 6, m = 140).

(2) Synthesis of siloxane monomer having PEG functional group: Synthesis step 2

A mixture of 125 g of the siloxane monomer of the formula 1-3 synthesized above, 38 g (0.10 mol) of polyethylene glycol allyl methyl ether, 250 g of isopropyl alcohol and 6.3 ml of a platinum catalyst was placed in a flask equipped with a reflux condenser, ≪ / RTI > with stirring. The reaction mixture was filtered, isopropanol was removed under reduced pressure, and washed several times with a mixture of acetone and water at a volume ratio of 1: 1. A volatile component was further removed under vacuum to obtain a transparent viscous liquid. The yield was 123 g, and the yield was 81.8%. As a result of the analysis, a compound represented by Formula 1-4 was synthesized.

As a result of the 400 MHz hydrogen nuclear magnetic resonance analysis of the obtained product, it was confirmed that O- CH ₂ CH ₂ - peak was generated at δ 3.15 to 3.90 ppm. Viscosity was measured with a viscometer to confirm the viscosity of 260 cP. GPC analysis revealed a weight average molecular weight of 13,268 g / mol.

[Formula 1-4]

(In the above formula, l = 6, m = 140).

2) Preparation of polymeric composition

53 g of the siloxane monomer of the formula 1-4 prepared in 1) above, 42.0 g of N-vinylpyrrolidone (NVP, Aldrich product, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, , 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich product, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The polymer composition was injected into a female mold for cast molding, and a male mold was assembled into the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 DEG C and polymerized for 1 hour, after which the mold was separated to obtain a lens. The obtained lens was immersed in deionized water for 1 hour, and then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The release properties and physical properties of the prepared lens were measured and are shown in Table 1 below.

[Example 3]

1) Synthesis of Siloxane Monomer

147 g (0.49 mol) of octamethylcyclotetrasiloxane, 22 g (0.047 mol) of 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane, 1,3-bis ((3-methacryloxy- Propoxypropyl) A mixture of 7 g (0.014 mol) of tetramethyldisiloxane, 180 g of chloroform and 1.5 g of trifluoromethanesulfonic acid was stirred at 25 DEG C for 24 hours and then poured into purified water After separating the water, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The yield was 142 g and the yield was 80.3%.

As a result of the analysis, the following Formula 1-5 was synthesized.

As a result of the 400 MHz hydrogen nuclear magnetic resonance analysis, the obtained product showed Si- CH ₂ -CH ₂ -CF ₃ at δ0.06 to 0.12 ppm, Si- CH ₃ at δ0.70 ppm (t, 20H) in _{t, 20H) Si-CH 2} - CH 2 -CF 3, at δ5.60 ~ 6.15 ppm (dd, 4H ) -CH = CH 2, δ5.87 ppm (dd, 2H) from - CH = CH _2, δ0.76 ppm (m, 4H) in _{Si- CH 2 -CH 2 -CH 2 -O} , δ 1.69 ppm (m, 4H) Si-CH 2 in the _{- CH 2 -CH 2 -O, δ} 3.94 ppm (m _{CH 2 -O, δ3.60 ~ 3.80 ppm} (m, 5H) O- CH 2 -CH-OH, O-CH 2 in the - - CH -OH, O-CH , 4H) Si-CH 2 -CH 2 in ₂ was confirmed -CH- CH ₂ peak. Viscosity was measured with a viscometer to confirm the viscosity of 131 cP. GPC analysis revealed a weight average molecular weight of 12,953 g / mol.

[Formula 1-5]

(Wherein m = 140 and n = 10).

2) Preparation of polymeric composition

42.0 g of the siloxane monomer of formula 1-5 prepared in 1) above, 53.0 g of N-vinylpyrrolidone (NVP, Aldrich product, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, , 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich product, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The polymer composition was injected into a female mold for cast molding, and a male mold was assembled into the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 DEG C and polymerized for 1 hour, after which the mold was separated to obtain a lens. The obtained lens was immersed in deionized water for 1 hour, and then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The release properties and physical properties of the prepared lens were measured and are shown in Table 1 below.

[Example 4]

1) Synthesis of Siloxane Monomer

147 g (0.49 mol) of octamethylcyclotetrasiloxane, 22 g (0.047 mol) of 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane, 5 g of 1,3,5,7-tetramethyl-cyclotetrasiloxane (0.014 mol) of 1,3-bis ((3-methacryloxy-2-hydroxypropoxy) propyl) tetramethyldisiloxane, 180 g of chloroform and 1.50 g of trifluoromethanesulfonic acid After stirring for 24 hours at 25 DEG C, the mixture was repeatedly washed with purified water until the pH of the mixture became neutral. After separating the water, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. g (84.1%).

As a result of the analysis, the compound of the following formula 1-1 was synthesized.

The obtained product 400 MHz 1H magnetic resonance analysis, δ0.06 ~ 0.12 ppm in Si- _{Si- CH 3, δ4.70 ppm (s} , 6H) Si- H, δ0.70 ppm (t, 10H) in _{CH 2 -CH 2 - CF 3,} δ2.07 ppm (t, 10H) Si-CH 2 in the _{- CH 2 - CF 3, δ5.60} ~ 6.15 ppm (dd, 4H) -CH = CH 2, δ1 in. 96 ppm (S, 6H) from _{-C CH 3 = CH 2, δ0.76} ppm (m, 4H) in _{Si- CH 2 -CH 2 -CH 2 -O} , Si- at δ 1.69 ppm (m, 4H) _{CH 2 - CH 2 -CH 2 -O} , δ 3.94 ppm (m, 4H) in the _{Si-CH 2 -CH 2 - CH} 2 -O, δ3.60 ~ O- CH at _{3.80 ppm (m, 5H) 2} - It was confirmed a peak of _{CH -OH, O-CH 2 -CH-} CH 2 - CH-OH, O-CH 2. Viscosity was measured with a viscometer to confirm the viscosity of 130 cP. GPC analysis revealed a weight average molecular weight of 13,214 g / mol.

[Formula 1-1]

(In the above formula, l = 6, m = 140 and n = 10).

2) Preparation of polymeric composition

53 g of the siloxane monomer of formula 1-1 prepared in 1) above, 42.0 g of N-vinylpyrrolidone (NVP, Aldrich product, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, , 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich product, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The polymer composition was injected into a female mold for cast molding, and a male mold was assembled into the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 DEG C and polymerized for 1 hour, after which the mold was separated to obtain a lens. The obtained lens was immersed in deionized water for 1 hour, and then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The release properties and physical properties of the prepared lens were measured and are shown in Table 1 below.

[Example 5]

1) Synthesis of Siloxane Monomer

147 g (0.49 mol) of octamethylcyclotetrasiloxane, 5 g (0.021 mol) of 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-bis ((3-methacryloxy 2-hydroxypropyl Phenoxypropyl) A mixture of 7 g (0.014 mol) of tetramethyldisiloxane, 180 g of chloroform and 1.5 g of trifluoromethanesulfonic acid was stirred at 25 ° C for 24 hours and then repeated with purified water until the pH of the mixture became neutral After separating the water, chloroform and volatile components were removed under reduced pressure to obtain a clear viscous liquid. 127 g, and the yield was 79.5%.

As a result of the analysis, the following compounds of Formulas 1-6 were synthesized.

The obtained product 400 MHz 1H magnetic resonance analysis, δ0.06 ~ 0.12 ppm in _{Si- CH 3, δ4.70 ppm (s} , 6H) Si- H, δ5.60 ~ 6.15 ppm (dd, 4H) from _{-CH = CH 2, δ1.96 ppm (} S, 6H) from _{-C CH 3 = CH 2, δ0.76} ppm (m, 4H) in _{Si- CH 2 -CH 2 -CH 2 -O} , δ 1.69 ppm _{CH 2 -O, δ3.60 ~ 3.80 ppm} (m, - CH 2 -CH 2 -O, δ 3.94 ppm (m, 4H) Si-CH 2 -CH 2 in the - (m, 4H) Si- CH 2 from 5H) from _{O- CH 2 -CH-OH, O} -CH 2 - was confirmed that the peak of the _{CH -OH, O-CH 2 -CH-} CH 2. Viscosity was measured with a viscometer to confirm a viscosity of 106 cP. GPC analysis revealed a weight average molecular weight of 11,630 g / mol.

[Chemical Formula 1-6]

(In the above formula, l = 6, m = 140).

2) Preparation of polymeric composition

30.0 g of the siloxane monomer of formula 1-6 prepared in 1) above, 65.0 g of N-vinylpyrrolidone (NVP, Aldrich product, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, , 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich product, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The polymer composition was injected into a female mold for cast molding, and a male mold was assembled into the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 DEG C and polymerized for 1 hour, after which the mold was separated to obtain a lens. The obtained lens was immersed in deionized water for 1 hour, and then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The release properties and physical properties of the prepared lens were measured and are shown in Table 1 below.

[Example 6]

1) Synthesis of Siloxane Monomer

76 g (0.25 mol) of octamethylcyclotetrasiloxane, 27 g (0.051 mol) of 1,3-bis ((3-methacryloxy 2-hydroxypropoxypropyl) tetramethyldisiloxane, 180 g of chloroform, Methanesulfonic acid (0.7 g) was stirred for 24 hours at 25 DEG C and then repeatedly washed with purified water until the pH of the mixture became neutral. After separating the water, chloroform and volatile components were removed under reduced pressure to obtain a clear viscous liquid The yield was 81 g, and the yield was 78.3%.

As a result of the analysis, the following compounds of Formulas 1-7 were synthesized.

The obtained product 400 MHz 1H magnetic resonance analysis, Si- at _{δ0.06 ~ 0.12 ppm CH 3, δ5.60} ~ 6.15 ppm (dd, 4H) from _{-CH = CH 2, δ1.96 ppm (} S, 6H ) from _{-C CH 3 = CH 2, δ0.76} ppm (m, 4H) in _{Si- CH 2 -CH 2 -CH 2 -O} , δ 1.69 ppm (m, 4H) Si-CH 2 in the - CH ₂ - _{CH 2 -O, δ 3.94 ppm (} m, 4H) in the _{Si-CH 2 -CH 2 - CH} 2 -O, δ3.60 ~ 3.80 ppm (m, 5H) from O- CH ₂ -CH-OH, O- CH ₂ - was confirmed that the peak of the _{CH -OH, O-CH 2 -CH-} CH 2. Viscosity was measured with a viscometer to confirm the viscosity of 76 cP. GPC analysis revealed a weight average molecular weight of 1,977 g / mol.

[Chemical Formula 1-7]

(In the above formula, m = 20.)

2) Preparation of polymeric composition

20 g of the siloxane monomer of the formula 1-7 prepared in 1) above, 75.0 g of N-vinylpyrrolidone (NVP, Aldrich product, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, , 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich product, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The polymer composition was injected into a female mold for cast molding, and a male mold was assembled into the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 DEG C and polymerized for 1 hour, after which the mold was separated to obtain a lens. The obtained lens was immersed in deionized water for 1 hour, and then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The release properties and physical properties of the prepared lens were measured and are shown in Table 1 below.

[Example 7]

1) Synthesis of Siloxane Monomer

71 g (0.15 mol) of 1,3,5-trimethyltrifluoropropyl cyclotrisiloxane, 24 g (0.046 mol) of 1,3-bis ((3-methacryloxy 2-hydroxypropoxypropyl) tetramethyldisiloxane mol), 180 g of chloroform and 0.7 g of trifluoromethanesulfonic acid was stirred for 24 hours at 25 DEG C and then repeatedly washed with purified water until the pH of the mixture became neutral. After separating the water, The chloroform and volatile components were removed to give a clear viscous liquid. 82 g, and the yield was 85.7%.

As a result of the analysis, the following compounds of Formulas 1-8 were synthesized.

The obtained product 400 MHz 1H magnetic resonance analysis, Si- at _{δ0.06 ~ 0.12 ppm CH 3, δ0.70} ppm Si- in the _{(t, 10H) CH 2 -CH} 2 - CF 3, δ2.07 ppm ( _{CH 2 - - CF 3, δ5.60} ~ 6.15 ppm (dd, 4H) -C in the _{-CH = CH 2, δ1.96 ppm (} S, 6H) in _{CH 3 = CH t, 10H)} Si-CH 2 from _{2, δ0.76 ppm (m, 4H} ) in _{Si- CH 2 -CH 2 -CH 2 -O} , δ 1.69 ppm (m, 4H) Si-CH 2 in the _{- CH 2 -CH 2 -O, δ} 3.94 ppm _{CH 2 -O, δ3.60 ~ 3.80 ppm} (m, 5H) O- CH 2 -CH-OH, O-CH 2 in the - - CH -OH, O (m , 4H) Si-CH 2 -CH 2 in The peak of -CH ₂ -CH- CH ₂ was confirmed. Viscosity was measured with a viscometer to confirm the viscosity of 105 cP. GPC analysis revealed a weight average molecular weight of 2,323 g / mol.

[Chemical Formula 1-8]

(Where n = 10).

2) Preparation of polymeric composition

15 g of the siloxane monomer of the formula 1-8 prepared in 1) above, 80.0 g of N-vinylpyrrolidone (NVP, Aldrich product, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, , 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich product, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The polymer composition was injected into a female mold for cast molding, and a male mold was assembled into the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 DEG C and polymerized for 1 hour, after which the mold was separated to obtain a lens. The obtained lens was immersed in deionized water for 1 hour, and then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The release properties and physical properties of the prepared lens were measured and are shown in Table 1 below.

[Example 8]

1) Synthesis of Siloxane Monomer

(1) Synthesis of siloxane monomer having Si-H: Synthesis step 1

70 g (0.29 mol) of 1,3,5,7-tetramethyl-cyclotetrasiloxane and 31 g (0.059 mol) of 1,3-bis ((3-methacryloxy 2-hydroxypropoxypropyl) tetramethyldisiloxane ), 180 g of chloroform and 0.7 g of trifluoromethanesulfonic acid was stirred for 24 hours at 25 DEG C and then repeatedly washed with purified water until the pH of the mixture became neutral. After separating the water, chloroform And volatile components were removed to obtain a transparent viscous liquid. The yield was 81 g, and the yield was 79.2%.

As a result of the analysis, the following compounds of Formulas 1-9 were synthesized.

The obtained product 400 MHz 1H magnetic resonance analysis, δ0.06 ~ 0.12 ppm in _{Si- CH 3, δ4.70 ppm (s} , 20H) Si- H, δ5.60 ~ 6.15 ppm (dd, 4H) from _{-CH = CH 2, δ1.96 ppm (} S, 6H) from _{-C CH 3 = CH 2, δ0.76} ppm (m, 4H) in _{Si- CH 2 -CH 2 -CH 2 -O} , δ 1.69 ppm _{CH 2 -O, δ3.60 ~ 3.80 ppm} (m, - CH 2 -CH 2 -O, δ 3.94 ppm (m, 4H) Si-CH 2 -CH 2 in the - (m, 4H) Si- CH 2 from 5H) from _{O- CH 2 -CH-OH, O} -CH 2 - was confirmed that the peak of the _{CH -OH, O-CH 2 -CH-} CH 2. Viscosity was measured with a viscometer to confirm the viscosity of 97 cP. GPC analysis revealed a weight average molecular weight of 1,795 g / mol.

[Chemical Formula 1-9]

(In the above formula, l = 20).

(2) Synthesis of siloxane monomer having PEG functional group: Synthesis step 2

A mixture of 75 g of the siloxane monomer of the formula 1-9 synthesized in the foregoing, 492 g (1.30 mol) of polyethylene glycol allyl methyl ether, 600 g of isopropyl alcohol and 3.83 ml of a platinum catalyst was charged into a flask equipped with a reflux condenser, ≪ / RTI > The reaction mixture was filtered, isopropanol was removed under reduced pressure, and washed several times with a mixture of acetone and water at a volume ratio of 1: 1. A volatile component was further removed under vacuum to obtain a transparent viscous liquid, the yield being 324 g, and the yield being 80.3%. As a result of the analysis, a compound represented by the following Formula 1-10 was synthesized.

As a result of the 400 MHz hydrogen nuclear magnetic resonance analysis of the obtained product, it was confirmed that O- CH ₂ CH ₂ - peak was generated at δ 3.15 to 3.90 ppm. Viscosity was measured with a viscometer to confirm the viscosity of 156 cP. GPC analysis revealed a weight average molecular weight of 9,564 g / mol.

[Chemical Formula 1-10]

(In the above formula, l = 20).

2) Preparation of polymeric composition

50 g of the siloxane monomer of the formula 1-10 prepared in 1) above, 45.0 g of N-vinylpyrrolidone (NVP, Aldrich product, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, , 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich product, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The polymer composition was injected into a female mold for cast molding, and a male mold was assembled into the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 DEG C and polymerized for 1 hour, after which the mold was separated to obtain a lens. The obtained lens was immersed in deionized water for 1 hour, and then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The release properties and physical properties of the prepared lens were measured and are shown in Table 1 below.

[Example 9]

1) Synthesis of Siloxane Monomer

(1) Synthesis of siloxane monomer having Si-H: Synthesis step 1

89 g (0.37 mol) of 1,3,5,7-tetramethyl-cyclotetrasiloxane, 15 g (0.030 mol) of 1,3-bis ((3-methacryloxy 2-hydroxypropoxypropyl) tetramethyldisiloxane ), 100 g of chloroform and 0.8 g of trifluoromethanesulfonic acid was stirred for 24 hours at 25 DEG C and then repeatedly washed with purified water until the pH of the mixture became neutral. After separating the water, chloroform And volatile components were removed to give a clear viscous liquid. 82 g, and the yield was 77.8%.

As a result of the analysis, the compound of Formula 1-11 was synthesized.

The obtained product 400 MHz 1H magnetic resonance analysis, δ0.06 ~ 0.12 ppm in _{Si- CH 3, δ4.70 ppm (s} , 50H) Si- H, δ5.60 ~ 6.15 ppm (dd, 4H) from _{-CH = CH 2, δ1.96 ppm (} S, 6H) from _{-C CH 3 = CH 2, δ0.76} ppm (m, 4H) in _{Si- CH 2 -CH 2 -CH 2 -O} , δ 1.69 ppm _{CH 2 -O, δ3.60 ~ 3.80 ppm} (m, - CH 2 -CH 2 -O, δ 3.94 ppm (m, 4H) Si-CH 2 -CH 2 in the - (m, 4H) Si- CH 2 from 5H) from _{O- CH 2 -CH-OH, O} -CH 2 - was confirmed that the peak of the _{CH -OH, O-CH 2 -CH-} CH 2. Viscosity was measured with a viscometer to confirm a viscosity of 106 cP. GPC analysis revealed a weight average molecular weight of 3,721 g / mol.

[Formula 1-11]

(In the above formula, l = 50).

(2) Synthesis of siloxane monomer having PEG functional group: Synthesis step 2

A mixture of 75 g of the siloxane monomer of the formula (1-11) synthesized in the foregoing, 604 g (1.60 mol) of polyethylene glycol allyl methyl ether, 700 g of isopropyl alcohol and 3.8 ml of a platinum catalyst was charged into a flask equipped with a reflux condenser, ≪ / RTI > The reaction mixture was filtered, isopropanol was removed under reduced pressure, and washed several times with a mixture of acetone and water at a volume ratio of 1: 1. A volatile component was further removed under vacuum to obtain a transparent viscous liquid. The yield was 381 g, and the yield was 79.8%. As a result of the analysis, a compound represented by the following formula 1-12 was synthesized.

As a result of the 400 MHz hydrogen nuclear magnetic resonance analysis of the obtained product, it was confirmed that O- CH ₂ CH ₂ - peak was generated at δ 3.15 to 3.90 ppm. Viscosity was measured with a viscometer to confirm a viscosity of 234 cP. GPC analysis revealed a weight average molecular weight of 21,654 g / mol.

[Formula 1-12]

(In the above formula, l = 50).

2) Preparation of polymeric composition

60.0 g of the siloxane monomer of formula 1-12 prepared in 1) above, 35.0 g of N-vinylpyrrolidone (NVP, Aldrich product, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, , 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich product, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The polymer composition was injected into a female mold for cast molding, and a male mold was assembled into the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 DEG C and polymerized for 1 hour, after which the mold was separated to obtain a lens. The obtained lens was immersed in deionized water for 1 hour, and then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The release properties and physical properties of the prepared lens were measured and are shown in Table 1 below.

[Comparative Example 1]

1) Synthesis of Siloxane Monomer

(1) Synthesis of siloxane monomer having Si-H: Synthesis step 1

147 g (0.50 mol) of octamethylcyclotetrasiloxane, 22 g (0.047 mol) of 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane, 5 g of 1,3,5,7-tetramethyl-cyclotetrasiloxane (0.021 mol), a mixture of 5 g (0.014 mol) of 1,3-bis ((methacryloxypropyl) tetramethyldisiloxane), 180 g of chloroform and 1.5 g of trifluoromethanesulfonic acid, The mixture was stirred for 24 hours and then repeatedly washed with purified water until the pH of the mixture became neutral. After separation of water, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. , And the yield was 79.9%.

As a result of the analysis, the compound of formula (6-1) was synthesized.

The obtained product 400MHz 1H magnetic resonance analysis, in Si- _{Si- CH 3, δ0.70 ppm (m} , 20H) at _{δ0.06 ~ 0.12 ppm CH 2 -CH 2} - CF 3, δ2.07 ppm (m _{CH 2 -CF 3, δ4.70 ppm (} s, 6H) Si- H, δ5.60 ~ 6.15 ppm (dd, 4H) -CH = CH 2, δ1.96 from -, 20H) in the Si-CH ₂ ppm (S, 6H) from _{-C CH 3 = CH 2, δ0.76} ppm (m, 4H) in _{Si- CH 2 -CH 2 -CH 2 -O} , δ 1.69 ppm (m, 4H) Si-CH in ₂ - _{CH 2 -CH 2 -O, δ 3.94} ppm (m, 4H) Si-CH 2 -CH 2 - CH 2 -O peak was confirmed. Viscosity was measured with a viscometer to confirm the viscosity of 125 cP. GPC analysis revealed a weight average molecular weight of 12,545 g / mol.

[Chemical Formula 5]

[Formula 6-1]

(In the above formula, l = 6, m = 140 and n = 10).

(2) Synthesis of siloxane monomer having PEG functional group: Synthesis step 2

A mixture of 100 g of the siloxane monomer of the formula (6-1) synthesized above, 26 g (0.07 mol) of polyethylene glycol allyl methyl ether, 200 g of isopropyl alcohol and 5.1 ml of a platinum catalyst was placed in a flask equipped with a reflux condenser, ≪ / RTI > with stirring. The reaction mixture was filtered, isopropanol was removed under reduced pressure, and washed several times with a mixture of acetone and water at a volume ratio of 1: 1. A volatile component was further removed under vacuum to obtain a transparent viscous liquid. The yield was 99 g, and the yield was 83.9%. As a result of the analysis, a compound represented by the following formula (6-2) was synthesized.

As a result of the 400 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was confirmed to produce an O- CH ₂ CH ₂ - peak at δ 3.15 to 3.90 ppm. Viscosity was measured with a viscometer to confirm the viscosity of 287 cP. GPC analysis revealed a weight average molecular weight of 15,244 g / mol.

[Formula 6-2]

(Where l = 6, m = 140, n = 10).

2) Preparation of polymeric composition

53 g of the siloxane monomer of Formula 6-2 prepared in 1) above, 42.0 g of N-vinylpyrrolidone (NVP, Aldrich product, V3409) as a hydrophilic monomer, 2 g of 2-hydroxyethyl methacrylate (HEMA, , 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich product, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The polymer composition was injected into a female mold for cast molding, and a male mold was assembled into the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 DEG C and polymerized for 1 hour, after which the mold was separated to obtain a lens. The obtained lens was immersed in deionized water for 1 hour, and then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

[Comparative Example 2]

1) Synthesis of Siloxane Monomer

(1) Synthesis of siloxane monomer having Si-H: Synthesis step 1

147 g (0.50 mol) of octamethylcyclotetrasiloxane, 5 g (0.021 mol) of 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-bis ((methacryloxypropyl) ) A mixture of 5 g (0.014 mol) of tetramethyldisiloxane, 180 g of chloroform and 1.5 g of trifluoromethanesulfonic acid was stirred at 25 DEG C for 24 hours and then repeatedly washed with purified water until the pH of the mixture became neutral After separating the water, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The yield was 136 g, and the yield was 86.3%.

As a result of the analysis, the compound of formula (6-3) was synthesized.

The obtained product 400 MHz 1H magnetic resonance analysis, δ0.06 ~ 0.12 ppm in _{Si- CH 3, δ4.70 ppm (s} , 6H) Si- H, δ5.60 ~ 6.15 ppm (dd, 4H) from _{-CH = CH 2, δ1.96 ppm (} S, 6H) from _{-C CH 3 = CH 2, δ0.76} ppm (m, 4H) in _{Si- CH 2 -CH 2 -CH 2 -O} , δ 1.69 ppm CH ₂ -O confirmed the peak - Si-CH ₂ -CH ₂ in _{CH 2 -CH 2 -O, δ 3.94} ppm (m, 4H) - (m, 4H) Si-CH 2 in. Viscosity was measured with a viscometer to confirm the viscosity of 105 cP. GPC analysis revealed a weight average molecular weight of 11,345 g / mol.

[Formula 6-3]

(In the above formula, l = 6, m = 140 and).

(2) Synthesis of siloxane monomer having PEG functional group: Synthesis step 2

A mixture of 100 g of the siloxane monomer of the formula (6-3) synthesized above, 30 g (0.08 mol) of polyethylene glycol allyl methyl ether, 200 g of isopropyl alcohol and 5.1 ml of a platinum catalyst was placed in a flask equipped with a reflux condenser, ≪ / RTI > with stirring. The reaction mixture was filtered, isopropanol was removed under reduced pressure, and washed several times with a mixture of acetone and water at a volume ratio of 1: 1. A volatile component was further removed under vacuum to obtain a transparent viscous liquid. The yield was 94 g, and the yield was 78.1%. As a result of the analysis, the compound represented by Formula 6-4 was synthesized.

As a result of the 400 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was confirmed to produce an O- CH ₂ CH ₂ - peak at δ 3.15 to 3.90 ppm. Viscosity was measured with a viscometer to confirm the viscosity of 249 cP. GPC analysis revealed a weight average molecular weight of 13,217 g / mol.

[Formula 6-4]

(In the above formula, l = 6, m = 140).

2) Preparation of polymeric composition

53.0 g of the siloxane monomer of Formula 6-4 prepared in 1) above, 42.0 g of N-vinylpyrrolidone (NVP, Aldrich product, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, , 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich product, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The polymer composition was injected into a female mold for cast molding, and a male mold was assembled into the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 DEG C and polymerized for 1 hour, after which the mold was separated to obtain a lens. The obtained lens was immersed in deionized water for 1 hour, and then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The physical properties of the polymer composition and the silicone hydrogel contact lens were measured, and the results are shown in Table 1 below.

[Comparative Example 3]

1) Synthesis of Siloxane Monomer

147 g (0.50 mol) of octamethylcyclotetrasiloxane, 22 g (0.047 mol) of 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane, 1,3-bis ((methacryloxy Propyl) A mixture of 5 g (0.014 mol) of tetramethyldisiloxane, 180 g of chloroform and 1.5 g of trifluoromethanesulfonic acid was stirred at 25 DEG C for 24 hours and then washed repeatedly with purified water until the pH of the mixture became neutral After separating the water, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The yield was 129 g and the yield was 73.9%.

As a result of the analysis, the following compound of formula (6-5) was synthesized.

The obtained product 400 MHz 1H magnetic resonance analysis, Si- at _{δ0.06 ~ 0.12 ppm CH 3, δ0.70} ppm (m, 20H) Si- CH 2 -CH 2 in the - CF _3, δ2.07 ppm ( _{CH 2 -CF 3, δ5.60 ~ 6.15} ppm (dd, 4H) -C in the _{-CH = CH 2, δ1.96 ppm (} S, 6H) in _{CH 3 = CH - m, 20H} ) Si-CH 2 from _{2, δ0.76 ppm (m, 4H} ) in _{Si- CH 2 -CH 2 -CH 2 -O} , δ 1.69 ppm (m, 4H) Si-CH 2 in the _{- CH 2 -CH 2 -O, δ} 3.94 ppm CH ₂ -O confirmed the peak - Si-CH ₂ -CH ₂ in the (m, 4H). Viscosity was measured with a viscometer to confirm a viscosity of 108 cP. GPC analysis revealed a weight average molecular weight of 12,653 g / mol.

[Formula 6-5]

(In the above formula, l = 10, m = 140).

2) Preparation of polymeric composition

42 g of the siloxane monomer of Formula 6-5 prepared in 1) above, 53.0 g of N-vinylpyrrolidone (NVP, Aldrich product, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, , 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich product, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The polymer composition was injected into a female mold for cast molding, and a male mold was assembled into the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 DEG C and polymerized for 1 hour, after which the mold was separated to obtain a lens. The obtained lens was immersed in deionized water for 1 hour, and then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The release properties and physical properties of the prepared lens were measured and are shown in Table 1 below.

[Comparative Example 4]

1) Synthesis of Siloxane Monomer

147 g (0.50 mol) of octamethylcyclotetrasiloxane, 22 g (0.047 mol) of 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane, 5 g of 1,3,5,7-tetramethyl-cyclotetrasiloxane (0.021 mol) of the compound of Formula 5, 5 g (0.014 mol) of 1,3-bis ((methacryloxypropyl) tetramethyldisiloxane, 180 g of chloroform and 1.5 g of trifluoromethanesulfonic acid) The mixture was stirred for 24 hours and then repeatedly washed with purified water until the pH of the mixture became neutral. After separating the water, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. , And the yield was 82.9%.

As a result of the analysis, the compound of formula (6-1) was synthesized.

The obtained product 400MHz 1H magnetic resonance analysis, in Si- _{Si- CH 3, δ0.70 ppm (m} , 20H) at _{δ0.06 ~ 0.12 ppm CH 2 -CH 2} - CF 3, δ2.07 ppm (m _{CH 2 -CF 3, δ4.70 ppm (} s, 6H) Si- H, δ5.60 ~ 6.15 ppm (dd, 4H) -CH = CH 2, δ1.96 from -, 20H) in the Si-CH ₂ ppm (S, 6H) from _{-C CH 3 = CH 2, δ0.76} ppm (m, 4H) in _{Si- CH 2 -CH 2 -CH 2 -O} , δ 1.69 ppm (m, 4H) Si-CH in ₂ - _{CH 2 -CH 2 -O, δ 3.94} ppm (m, 4H) Si-CH 2 -CH 2 - CH 2 -O peak was confirmed. Viscosity was measured with a viscometer to confirm the viscosity of 119 cP. GPC analysis revealed a weight average molecular weight of 15,478 g / mol.

[Formula 6-1]

(In the above formula, l = 6, m = 140 and n = 10).

2) Preparation of polymeric composition

30 g of the siloxane monomer of Formula 6-1 prepared in 1) above, 65.0 g of N-vinylpyrrolidone (NVP, Aldrich product, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, , 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich product, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The polymer composition was injected into a female mold for cast molding, and a male mold was assembled into the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 DEG C and polymerized for 1 hour, after which the mold was separated to obtain a lens. The obtained lens was immersed in deionized water for 1 hour, and then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The release properties and physical properties of the prepared lens were measured and are shown in Table 1 below.

[Comparative Example 5]

1) Synthesis of Siloxane Monomer

147 g (0.50 mol) of octamethylcyclotetrasiloxane, 5 g (0.021 mol) of 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-bis ((methacryloxypropyl) ) A mixture of 5 g (0.014 mol) of tetramethyldisiloxane, 180 g of chloroform and 1.5 g of trifluoromethanesulfonic acid was stirred at 25 DEG C for 24 hours and then repeatedly washed with purified water until the pH of the mixture became neutral After separating the water, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The yield was 131 g and the yield was 83.1%.

As a result of the analysis, the following Formula 6-6 was synthesized.

The obtained product 400 MHz 1H magnetic resonance analysis, δ0.06 ~ 0.12 ppm in _{Si- CH 3, δ4.70 ppm (s} , 6H) Si- H, δ5.60 ~ 6.15 ppm (dd, 4H) from _{-CH = CH 2, δ1.96 ppm (} S, 6H) from _{-C CH 3 = CH 2, δ0.76} ppm (m, 4H) in _{Si- CH 2 -CH 2 -CH 2 -O} , δ 1.69 ppm CH ₂ -O confirmed the peak - Si-CH ₂ -CH ₂ in _{CH 2 -CH 2 -O, δ 3.94} ppm (m, 4H) - (m, 4H) Si-CH 2 in. Viscosity was measured with a viscometer to confirm the viscosity of 104 cP. GPC analysis revealed a weight average molecular weight of 10,783 g / mol.

[Formula 6-6]

(In the above formula, l = 6, m = 140).

2) Preparation of polymeric composition

30 g of the siloxane monomer of Formula 6-6 prepared in 1) above, 65.0 g of N-vinylpyrrolidone (NVP, Aldrich product, V3409) as a hydrophilic monomer, 2 g of 2-hydroxyethyl methacrylate (HEMA, , 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich product, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The polymer composition was injected into a female mold for cast molding, and a male mold was assembled into the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 DEG C and polymerized for 1 hour, after which the mold was separated to obtain a lens. The obtained lens was immersed in deionized water for 1 hour, and then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The release properties and physical properties of the prepared lens were measured and are shown in Table 1 below.

[Comparative Example 6]

1) Synthesis of Siloxane Monomer

82 g (0.28 mol) of octamethylcyclotetrasiloxane, 21 g (0.056 mol) of 1,3-bis ((methacryloxypropyl) tetramethyldisiloxane as the compound of the above formula 5, 180 g of chloroform and 50 g of trifluoromethanesulfonic acid 0.8 g of the mixture was stirred for 24 hours at 25 DEG C and then repeatedly washed with purified water until the pH of the mixture became neutral. After separating the water, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid The yield was 82.5 g and the yield was 78.9%.

As a result of the analysis, the compound of Formula 6-7 was synthesized.

The obtained product 400 MHz 1H magnetic resonance analysis, Si- at _{δ0.06 ~ 0.12 ppm CH 3, δ5.60} ~ 6.15 ppm (dd, 4H) from _{-CH = CH 2, δ1.96 ppm (} S, 6H ) from _{-C CH 3 = CH 2, δ0.76} ppm (m, 4H) in _{Si- CH 2 -CH 2 -CH 2 -O} , δ 1.69 ppm (m, 4H) Si-CH 2 in the - CH ₂ - _{CH 2 -O, δ 3.94 ppm (} m, 4H) Si-CH 2 -CH 2 in the -. CH ₂ -O confirmed the peak were confirmed by measuring the viscosity of 81 cP in viscosity viscometer. GPC analysis revealed a weight average molecular weight of 1,761 g / mol.

[Formula 6-7]

(In the above formula, m = 20.)

2) Preparation of polymeric composition

20 g of the siloxane monomer of formula 6-7 prepared in 1) above, 75 g of N-vinylpyrrolidone (NVP, Aldrich product, V3409) as a hydrophilic monomer, 2 g of 2-hydroxyethyl methacrylate (HEMA, , 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich product, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The polymer composition was injected into a female mold for cast molding, and a male mold was assembled into the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 DEG C and polymerized for 1 hour, after which the mold was separated to obtain a lens. The obtained lens was immersed in deionized water for 1 hour, and then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The release properties and physical properties of the prepared lens were measured and are shown in Table 1 below.

[Comparative Example 7]

1) Synthesis of Siloxane Monomer

72 g (0.15 mol) of 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane, 17 g (0.046 mol) of 1,3-bis ((methacryloxypropyl) tetramethyldisiloxane, , 180 g of chloroform and 0.8 g of trifluoromethanesulfonic acid was stirred at 25 DEG C for 24 hours and then repeatedly washed with purified water until the pH of the mixture became neutral. After separating the water, chloroform The volatile components were removed to give a clear viscous liquid. 73 g, and the yield was 81.3%.

As a result of the analysis, the following compound of formula (6-8) was synthesized.

The obtained product 400 MHz 1H magnetic resonance analysis, Si- at _{δ0.06 ~ 0.12 ppm CH 3, δ0.70} ppm (m, 20H) Si- CH 2 -CH 2 in the - CF _3, δ2.07 ppm ( _{CH 2 -CF 3, δ5.60 ~ 6.15} ppm (dd, 4H) -C in the _{-CH = CH 2, δ1.96 ppm (} S, 6H) in _{CH 3 = CH - m, 20H} ) Si-CH 2 from _{2, δ0.76 ppm (m, 4H} ) in _{Si- CH 2 -CH 2 -CH 2 -O} , δ 1.69 ppm (m, 4H) Si-CH 2 in the _{- CH 2 -CH 2 -O, δ} 3.94 ppm CH ₂ -O confirmed the peak - Si-CH ₂ -CH ₂ in the (m, 4H). Viscosity was measured with a viscometer to confirm the viscosity of 95 cP. GPC analysis revealed a weight average molecular weight of 1,863 g / mol.

[Formula 6-8]

(Where n = 10).

2) Preparation of polymeric composition

15 g of the siloxane monomer of formula 6-8 prepared in 1) above, 80.0 g of N-vinylpyrrolidone (NVP, Aldrich product, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, , 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich product, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The polymer composition was injected into a female mold for cast molding, and a male mold was assembled into the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 DEG C and polymerized for 1 hour, after which the mold was separated to obtain a lens. The obtained lens was immersed in deionized water for 1 hour, and then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The release properties and physical properties of the prepared lens were measured and are shown in Table 1 below.

[Comparative Example 8]

1) Synthesis of Siloxane Monomer

(1) Synthesis of siloxane monomer having Si-H: Synthesis step 1

75 g (0.31 mol) of 1,3,5,7-tetramethyl-cyclotetrasiloxane, 24 g (0.063 mol) of 1,3-bis ((methacryloxypropyl) tetramethyldisiloxane, 180 g of chloroform and 0.8 g of trifluoromethanesulfonic acid was stirred for 24 hours at 25 DEG C and then repeatedly washed with purified water until the pH of the mixture became neutral. After separating the water, chloroform and volatile The components were removed to give a clear viscous liquid. The yield was 78 g, and the yield was 78.7%.

As a result of the analysis, the following compound of formula (6-9) was synthesized.

The obtained product 400 MHz 1H magnetic resonance analysis, δ0.06 ~ 0.12 ppm in _{Si- CH 3, δ4.70 ppm (s} , 20H) Si- H, δ5.60 ~ 6.15 ppm (dd, 4H) from _{-CH = CH 2, δ1.96 ppm (} S, 6H) from _{-C CH 3 = CH 2, δ0.76} ppm (m, 4H) in _{Si- CH 2 -CH 2 -CH 2 -O} , δ 1.69 ppm CH ₂ -O confirmed the peak - Si-CH ₂ -CH ₂ in _{CH 2 -CH 2 -O, δ 3.94} ppm (m, 4H) - (m, 4H) Si-CH 2 in. Viscosity was measured with a viscometer to confirm the viscosity of 93 cP. GPC analysis revealed a weight average molecular weight of 1,521 g / mol.

[Formula 6-9]

(In the above formula, l = 20).

(2) Synthesis of siloxane monomer having PEG functional group: Synthesis step 2

A mixture of 75 g of the siloxane monomer of the formula 16-9 synthesized in the foregoing, 539 g (1.42 mol) of polyethylene glycol allyl methyl ether, 600 g of isopropyl alcohol and 3.8 ml of the platinum catalyst was placed in a flask equipped with a reflux condenser, ≪ / RTI > with stirring. The reaction mixture was filtered, isopropanol was removed under reduced pressure, and washed several times with a mixture of acetone and water at a volume ratio of 1: 1. A volatile component was further removed under vacuum to obtain a transparent viscous liquid. The yield was 367 g and the yield was 84.6%. As a result of the analysis, a compound represented by the following formula 6-10 was synthesized.

As a result of the 400 MHz hydrogen nuclear magnetic resonance analysis of the obtained product, it was confirmed that O- CH ₂ CH ₂ - peak was generated at δ 3.15 to 3.90 ppm. Viscosity was measured with a viscometer to confirm the viscosity of 149 cP. GPC analysis revealed a weight average molecular weight of 9,185 g / mol.

[Chemical Formula 6-10]

(In the above formula, l = 20).

2) Preparation of polymeric composition

50 g of the siloxane monomer of Formula 6-10 prepared in 1) above, 45.0 g of N-vinylpyrrolidone (NVP, product of Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, , 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich product, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The polymer composition was injected into a female mold for cast molding, and a male mold was assembled into the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 DEG C and polymerized for 1 hour, after which the mold was separated to obtain a lens. The obtained lens was immersed in deionized water for 1 hour, and then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The release properties and physical properties of the prepared lens were measured and are shown in Table 1 below.

[Comparative Example 9]

1) Synthesis of Siloxane Monomer

(1) Synthesis of siloxane monomer having Si-H: Synthesis step 1

89 g (0.37 mol) of 1,3,5,7-tetramethyl-cyclotetrasiloxane, 11 g (0.30 mol) of 1,3-bis ((methacryloxypropyl) tetramethyldisiloxane, 180 g of chloroform and 0.9 g of trifluoromethanesulfonic acid was stirred for 24 hours at 25 DEG C and then repeatedly washed with purified water until the pH of the mixture became neutral. After separating the water, chloroform and volatile The components were removed to give a clear viscous liquid. The yield was 75 g, and the yield was 74.9%.

As a result of the analysis, the compound of the following formula (6-11) was synthesized.

The obtained product 400 MHz 1H magnetic resonance analysis, δ0.06 ~ 0.12 ppm in _{Si- CH 3, δ4.70 ppm (s} , 50H) Si- H, δ5.60 ~ 6.15 ppm (dd, 4H) from _{-CH = CH 2, δ1.96 ppm (} S, 6H) from _{-C CH 3 = CH 2, δ0.76} ppm (m, 4H) in _{Si- CH 2 -CH 2 -CH 2 -O} , δ 1.69 ppm Si-CH ₂ -CH ₂ in _{CH 2 -CH 2 -O, δ 3.94} ppm (m, 4H) - - (m, 4H) Si-CH 2 in. CH ₂ -O peak was confirmed by measuring the viscosity viscometer And a viscosity of 102 cP was confirmed. GPC analysis revealed a weight average molecular weight of 3,197 g / mol.

[Chemical Formula 6-11]

(In the above formula, l = 50).

(2) Synthesis of siloxane monomer having PEG functional group: Synthesis step 2

A mixture of 75 g of the siloxane monomer of the formula (6-11) synthesized above, 630 g (1.66 mol) of polyethylene glycol allyl methyl ether, 700 g of isopropyl alcohol and 3.8 ml of the platinum catalyst was placed in a flask equipped with a reflux condenser, ≪ / RTI > with stirring. The reaction mixture was filtered, isopropanol was removed under reduced pressure, and washed several times with a mixture of acetone and water at a volume ratio of 1: 1. A volatile component was further removed under vacuum to obtain a transparent viscous liquid. The yield was 418 g and the yield was 84.4%. As a result of analysis, a compound represented by the following formula 6-12 was synthesized.

As a result of the 400 MHz hydrogen nuclear magnetic resonance analysis of the obtained product, it was confirmed that O- CH ₂ CH ₂ - peak was generated at δ 3.15 to 3.90 ppm. Viscosity was measured with a viscometer to confirm the viscosity of 245 cP. GPC analysis revealed a weight average molecular weight of 22,648 g / mol.

[Chemical Formula 6-12]

(In the above formula, l = 50).

2) Preparation of polymeric composition

60 g of the siloxane monomer of the formula 6-12 prepared in 1) above, 35.0 g of N-vinylpyrrolidone (NVP, Aldrich product, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, , 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich product, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The polymer composition was injected into a female mold for cast molding, and a male mold was assembled into the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 DEG C and polymerized for 1 hour, after which the mold was separated to obtain a lens. The obtained lens was immersed in deionized water for 1 hour, and then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The physical properties of the manufactured lens were measured and are shown in Table 1 below.

Moisture content (%) Surface contact angle (˚) Oxygen permeability coefficient Example 1 54 37.5 112 Example 2 55 36.7 107 Example 3 61 37.2 85 Example 4 47 36.5 117 Example 5 61 36.4 75 Example 6 63 35.2 61 Example 7 65 37.6 51 Example 8 49 39.5 90 Example 9 45 37.1 128 Comparative Example 1 52 49.5 111 Comparative Example 2 54 47.5 104 Comparative Example 3 60 50.1 111 Comparative Example 4 47 52.1 108 Comparative Example 5 62 48.6 79 Comparative Example 6 63 48.1 66 Comparative Example 7 64 49.5 50 Comparative Example 8 50 50.3 85 Comparative Example 9 46 50.7 122

As can be seen from the above table, in Examples 1 to 9 according to the present invention, the water content and oxygen permeability coefficient are similar to each other, but the surface contact angle is significantly lower than that of Comparative Examples 1 to 9.

This is because the wettability was extremely improved by the hydroxyl groups introduced at the ends of the siloxane monomers of Examples 1 to 9, and the surface contact angle was lowered, and the results were very excellent in comparison with the comparative example not containing such specific functional groups.

Claims (10)

A siloxane monomer represented by the following formula (1).
[Chemical Formula 1]

(In the formula 1,
R ₁ to R ₄ are independently of each other hydrogen or (C ₁ -C ₁₀ ) alkyl;
R _a1 to R _a8 are independently of each other hydrogen, hydroxy or (C ₁ -C ₁₀ ) alkyl, and any of R _a1 to R _a8 is necessarily hydroxy;
o, p, a and b are each independently an integer selected from 1 to 10;
q and c are each independently an integer selected from 0 to 10;
D ₁ and D ₂ are independently of each other a single bond;
B ₁ and B ₂ are independently of each other

And R _b is hydrogen or (C ₁ -C ₁₀ ) alkyl;
A is any one selected from the following structural formulas.

[In the above formula,
R ₅ is hydrogen or

Lt;
R ₆ , R ₇ , R ₈ and R ₁₀ are independently of each other (C ₁ -C ₁₀ ) alkyl,
R ₉ is halo (C ₁ -C ₁₀ ) alkyl,
t is an integer from 0 to 20;
l, m and n are each independently an integer selected from 1 to 200.] The method according to claim 1,
Wherein R _a1 to R _a8 are each independently hydrogen or hydroxy, and any one of R _a1 to R _a8 is necessarily hydroxy;
and q and c are each independently an integer selected from 1 to 10. The method according to claim 1,
Wherein the siloxane monomer represented by the formula (1) is represented by the following formula (2).
(2)

(In the formula (2)
R ₁ to R ₄ are independently of each other hydrogen or (C ₁ -C ₁₀ ) alkyl;
R _a2 - R _a7 independently from each other are hydrogen or (C ₁ -C ₁₀ ) alkyl;
o, p, a and b are each independently an integer selected from 1 to 10;
q and c are each independently an integer selected from 0 to 10;
D ₁ and D ₂ are independently of each other a single bond;
B ₁ and B ₂ are independently of each other

And R _b is hydrogen or (C ₁ -C ₁₀ ) alkyl;
A is any one selected from the following structural formulas.

[In the above formula,
R ₅ is hydrogen or

Lt;
R ₆ , R ₇ , R ₈ and R ₁₀ are independently of each other (C ₁ -C ₁₀ ) alkyl,
R ₉ is halo (C ₁ -C ₁₀ ) alkyl,
t is an integer from 0 to 20;
l, m and n are each independently an integer selected from 1 to 200.] The method of claim 3,
In formula (2), l, m and n are each independently an integer selected from 5 to 150. The method of claim 3,
In the formula (2), R _a2 - R _a7 is hydrogen; o, p, a and b are each independently an integer selected from 1 to 5; q and c are independently of each other an integer selected from 1 to 3; D ₁ and D ₂ are independently of each other a single bond. 6. The method of claim 5,
Siloxane monomers selected from compounds 1, 2 and 5 to 11 below.
[Compound 1]

(L, m and n are each independently an integer selected from 1 to 200)
[Compound 2]

(L, m and n are each independently an integer selected from 1 to 200)
[Compound 5]

(1 is an integer selected from 1 to 200)
[Compound 6]

(M and n are each independently an integer selected from 1 to 200)
[Compound 7]

(L and n are each independently an integer selected from 1 to 200).
[Compound 8]

(Wherein l and m are each independently an integer selected from 1 to 200)
[Compound 9]

(1 is an integer selected from 1 to 200)
[Compound 10]

(L and n are each independently an integer selected from 1 to 200).
[Compound 11]

(Wherein l and m are each independently an integer selected from 1 to 200)
delete A polymer composition for producing a silicone hydrogel lens comprising a siloxane monomer of any one of claims 1 to 6 and a reactive monomer. 9. The method of claim 8,
Wherein the composition comprises 5 to 60% by weight of a siloxane monomer. 9. The method of claim 8,
Wherein the reactive monomer is any one or a mixture of two or more selected from a hydrophilic acrylic monomer and a hydrophilic silicone acrylic monomer.