WO2018097622A2 - Siloxane monomer, polymer composition comprising same, and silicone hydrogel lens prepared using same - Google Patents

Abstract

The present invention relates to a siloxane monomer, a polymer composition comprising the same and a silicone hydrogel lens prepared using the same. The silicone hydrogel lens of the present invention can be produced by using a polymer composition comprising a novel siloxane monomer having a hydroxyl group introduced into the terminal thereof and thus has high wettability, thereby providing improved physical properties such as water content and surface contact angle, etc.

Description

Siloxane monomer, polymerization composition comprising the same, and silicone hydrogel lens manufactured using the same

The present invention relates to a siloxane monomer, a polymerization composition comprising the same, and a silicone hydrogel lens prepared using the same, in particular, a novel siloxane monomer for producing a silicone hydrogel lens having excellent wettability, and a silicone hydrogel comprising the same. It provides a polymer composition for producing a lens and a silicone hydrogel lens prepared using the same.

Contact lenses must be in direct contact with the eye to maintain the safety and efficacy of the eyes while maintaining the transparency and surface wettability of the contact lenses, so that oxygen must be adequately supplied from the atmosphere and the release of carbon dioxide from the cornea Should be appropriate.

In addition, the contact lens should be designed in consideration of the clinical aspects such that the tear layer flows smoothly and avoids excessive friction between the eyelid and the eye surface. In addition, it can be used as a contact lens for the material's mechanical strength, biocompatibility, non-toxicity, optical transparency of the material, refractive index, surface wettability, Conditions such as water content, swelling rate and oxygen permeability suitable for the cornea must also be met.

Early contact lenses were made of hard materials and these lenses are still used in some applications today, but they are not suitable for all patients because of a significant decrease in fit. Since then, soft contact lenses based on hydrogels have been developed and are very popular today.

However, the 21st century, which is defined as the digital information age, is threatening eye health as the usage time of various smart devices increases, and furthermore, it is uncomfortable for the wearer, prolonged or continuous wearing, eye irritation, corneal pigmentation and / or eye damage. Various problems, such as the attachment of the lens to the cornea, which may cause other damage, have increased the demand for contact lenses having innovatively improved properties.

Therefore, various studies have been conducted on contact lenses having excellent oxygen transmittance and wettability, so that excellent wearing comfort can be maintained even for long time wearing.

For example, the Republic of Korea Patent No. 10-0594414 provides a method of increasing the wear of the contact lens by increasing the hydrophilicity by plasma treatment of the surface of the first generation silicon-based hydrogel contact lens.

However, there is still a need for a study on contact lenses having improved properties for comfortable and safe wearing for a long time.

The present invention provides a novel siloxane monomer used in the manufacture of a silicone hydrogel lens and a polymer composition for preparing the silicone hydrogel lens including the same.

In addition, the present invention provides a silicone hydrogel lens having improved wettability by being prepared using a polymerization composition including the siloxane monomer of the present invention.

The present invention provides a siloxane monomer for preparing a silicone hydrogel lens having excellent properties, in particular, wettability and oxygen permeability, wherein the siloxane monomer of the present invention is represented by the following Chemical Formula 1.

[Formula 1]

(In 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, wherein any one 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 independently integers selected from 0 to 10;

D ₁ and D ₂ are each independently 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;

B ₁ and B ₂ are independently of each other hydrocarbyl or

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

And

A is any one selected from the following structural formulas.

[In the above structural formula,

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 in Formula 1 according to an embodiment of the present invention, R _a1 to R _a8 are independently of each other hydrogen or hydroxy, any one of R _a1 to R _a8 is necessarily hydroxy; q and c may be integers selected from 1 to 10 independently of each other.

Preferably, Formula 1 according to an embodiment of the present invention may be represented by the following formula (2).

[Formula 2]

(In Formula 2,

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

R _a2 to R _a7 is independently of each other 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 independently integers selected from 0 to 10;

D ₁ and D ₂ are each independently 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;

B ₁ and B ₂ are independently of each other hydrocarbyl or

Is,

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

And

A is any one selected from the following structural formulas.

[In the above structural formula,

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 ₅ to R ₁₀ in Formula 2 according to an embodiment of the present invention are each independently hydrogen, (C ₁ -C ₁₀ ) alkyl, halo (C ₁ -C ₁₀ ) alkyl or

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

Preferably in Formula 2, R ₅ to R ₆ and R ₈ to R ₁₀ are independently of each other hydrogen or (C ₁ -C ₁₀ ) alkyl, R ₇ may be halo (C ₁ -C ₁₀ ) alkyl, more preferably l, m, n are Each independently represent an integer selected from 5 to 150, and R ₅ to R ₆ and R ₈ to R ₁₀ are hydrogen or methyl; R ₆ is

Can be.

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

The present invention also provides a polymer composition for preparing a silicone hydrogel lens including the siloxane monomer and the reactive monomer of the present invention.

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

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

The present invention has surprisingly improved the wettability of silicone hydrogel lenses by introducing one or more hydroxyl groups into the siloxane monomers used to make the silicone hydrogel lenses.

Therefore, the present invention is a silicone hydrogel lens prepared using a polymer composition containing a novel siloxane monomer is excellent in long-term wearability, high oxygen permeability coefficient as well as moisture content, it is possible to prevent eye diseases such as dry eye, corneal edema, etc. have.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following specific examples or examples are only one reference for describing the present invention in detail, but the present invention is not limited thereto and may be implemented in various forms.

Also, unless defined otherwise, all technical and scientific terms have the same meanings as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used in the description in the present invention are only for effectively describing specific embodiments and are not intended to limit the present invention.

The following terms according to the invention and as used herein are defined with the following meanings, unless expressly stated otherwise. Other terms are defined in the text or in a sense consistent with these uses.

The term 'hydrogel' denotes a polymeric material, typically a network or matrix of polymer chains, swellable in water or swelled by water. The matrix may or may not be crosslinked. Hydrogels thus represent polymeric materials, including water swellable or water swelled contact lenses. The hydrogel may be (i) unhydrated and water swellable, or (ii) partially hydrated and swelled with water, or (iii) fully hydrated and swelled with water.

The term 'polymerization composition' is understood to have the same meaning as 'polymerization mixture' and may be understood as being prepolymerized or precured to suit the polymerization. For example, in the field of lenses, the polymeric composition may be a lens precursor composition. The polymerization composition may be represented as a monomer mix.

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

The term 'monomer' refers to a compound that is polymerizable regardless of the molecular weight of the compound. Thus, the monomer may be a low molecular weight monomer, a macromer as described below.

The term 'low molecular weight monomers' refers to polymerizable relatively low molecular weight compounds, for example compounds having an average molecular weight of less than 700 Daltons. In one example, the low molecular weight monomer may comprise a single unit of molecule containing one or more functional groups that can be polymerized to combine with other molecules having the same or different structure as the low molecular weight monomer to form a polymer.

The term 'macromer' refers to a compound or polymer of medium molecular weight and high molecular weight, which may contain one or more functional groups which can be polymerized or further polymerized. For example, the macromer may 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. The copolymer may not be polymerized but may be crosslinked with other polymers, such as polymers present in the polymerizable composition or during the reaction of monomers, macromers and mixtures thereof forming other polymers in the polymerizable composition. It is understood to refer to a molecule.

The present invention is a siloxane monomer used in the preparation of the silicone hydrogel lens with improved wettability, the siloxane monomer of the present invention is represented by the following formula (1).

[Formula 1]

(In 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, wherein any one 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 integers selected from 0 to 10 independently of each other.

D ₁ and D ₂ are each independently 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;

B ₁ and B ₂ are independently of each other hydrocarbyl or

Is,

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

And

A is any one selected from the following structural formulas.

[In the above structural formula,

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 Formula 1 of the present invention has a high moisture content by significantly increasing wettability by introducing one or more hydroxy groups to R _a1 to R _a8 in Formula 1, and has an oxygen permeability coefficient, an appropriate elastic modulus, and corneal fixation of the lens. It does not occur, it is long-term wearability and reduces the occurrence of eye diseases.

Preferably, in the siloxane monomer represented by Formula 1, in Formula 1, R _a1 to R _a8 are each independently hydrogen or a hydroxy group, and any one of R _a1 to R _a8 is necessarily hydroxy; q and c may be integers selected from 0 to 10 independently of each other.

In view of wettability and oxygen permeability, preferably, Chemical Formula 1 may be represented by the following Chemical Formula 2.

[Formula 2]

(In Formula 2,

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

R _a2 to R _a7 is independently of each other 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 independently integers selected from 0 to 10;

D ₁ and D ₂ are each independently 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;

B ₁ and B ₂ are independently of each other hydrocarbyl or

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

And

A is any one selected from the following structural formulas.

[In the above structural formula,

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 in Formula 2 R ₅ to R ₁₀ is hydrogen, (C ₁ -C ₁₀ ) alkyl, halo (C ₁ -C ₁₀ ) alkyl or

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

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

R ₅ to R ₆ and R ₈ to R ₁₀ are hydrogen or methyl; R ₆ is

Can be.

In Formula 2 according to an embodiment of the present invention R _a2 to R _a7 is hydrogen; o, p, a and b are integers independently selected from 1 to 5; q and c may be integers selected from 0 to 3 independently of each other; D ₁ and D ₂ may be a single bond independently of each other.

Hydrocarbyl described in the present invention means a radical having one binding position derived from hydrocarbon.

'Alkyl' described in the present invention represents a hydrocarbon chain having 1 to 10 carbon atoms, preferably 1 to 7, more preferably 1 to 5 carbon atoms. Such hydrocarbon chains are not necessarily saturated but are preferably saturated and may be branched or straight chains, although straight chains are usually preferred. 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 in the hydrogen position of the alkyl, preferably may be fluorine.

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

In one embodiment of the present invention, Formula 1 may be specifically selected from the following compounds. Compounds 1 to 22 below are only one embodiment specifically illustrating Formula 1 of the present invention, but the present invention is not limited thereto.

[Compound 1]

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

[Compound 2]

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

[Compound 3]

(The m is an integer selected from 1 to 200.)

[Compound 4]

(N is an integer selected from 1 to 200.)

[Compound 5]

(L 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]

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

[Compound 9]

(L 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]

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

[Compound 12]

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

[Compound 13]

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

[Compound 14]

(The m is an integer selected from 1 to 200.)

[Compound 15]

(N is an integer selected from 1 to 200.)

[Compound 16]

(L 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]

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

[Compound 20]

(L 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]

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

In addition, 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 siloxane monomer of the present invention is not limited so long as it is a composition generally used in silicone hydrogel lenses.

In addition, in one aspect of the present invention, the polymerization composition for producing a silicone hydrogel lens necessarily includes the siloxane monomer of the present invention represented by the formula (1).

More specifically, one aspect of the polymerization composition of the present invention includes at least one siloxane monomer and a reactive monomer represented by Formula 1 of the present invention, it may be made by including a crosslinking agent, an initiator and an additive.

The polymer composition for preparing a silicone hydrogel lens according to an embodiment of the present invention preferably has a viscosity measured at 25 ° C. of 10 to 20,000 cps, and more preferably 100 to 15000 cps. Since the productivity is excellent when injected into the mold parts in the above range is preferable.

The content of the siloxane monomer included in the polymerization composition of the present invention is preferably 5 to 60% by weight in the polymerization composition, more preferably 30 to 50% by weight, but is not limited thereto. It is possible to achieve excellent physical properties such as wettability in the above range.

In one aspect of the polymerizing composition of the present invention, the reactive monomer may be a monomer having a substituent capable of reacting with the siloxane monomer, and a hydrophilic monomer may be used, in which the hydrophilic monomer is not particularly limited, which is usually used in the art. What is used 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, for example, C ₁ -C ₁₅ hydroxyalkyl methacrylate substituted with 1 to 3 hydroxyl groups, and C ₁ -C ₁₅ hydroxyalkyl acrylic substituted with 1 to 3 hydroxyl groups. At least one selected from the group consisting of acrylate, acrylamide, vinyl pyrrolidone, glycerol methacrylate, acrylic acid, methacrylic acid, and the like. The hydrophilic acrylic polymer is, for example, 2-hydroxyethyl methacrylate (HEMA), N, N-dimethyl acrylamide (N, N-dimethyl acrylamide, DMA), N-vinyl It may be at least one selected from pyrrolidone (N-vinyl pyrrolidone, NVP), glycerol monomethacrylate (GMMA), methacrylic acid (MAA) and the like.

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

In addition, hydrophobic monomers may be used together as necessary in addition to the hydrophilic multimer, and in this case, the hydrophobic monomers are not particularly limited, and those commonly used in the art may be used, for example, hydrophobic acrylic monomers may be used. have.

The hydrophobic acrylic monomers include alkyl acrylate monomers and alkyl methacrylate monomers, and more specific examples thereof include methyl acrylate, methyl methacrylate, ethyl acrylate, Ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, n-butyl acrylate, n-butyl meth N-butyl methacrylate, stearyl acrylate, stearyl methacrylate and the like. In addition, monomers having high glass transition temperature (T _g ), for example cyclohexyl methacrylate, tert-butyl methacrylate and isobornyl methacrylate And the like and mixtures thereof may also be used to enhance mechanical properties.

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

In one aspect of the polymeric composition of the present invention, the crosslinking agent is for example ethylene glycol dimethacrylate (EGDMA), diethylene glycol methacrylate (DGMA), divinylbenzene and trimethylolpropane trimethacrylate (TMPTMA) One or more selected from the like. In addition, the crosslinking agent is preferably 0.005 to 5% by weight, more specifically 0.010 to 3% by weight in the polymerization composition.

In one aspect of the polymerization composition of the invention, the initiator is for polymerization, which is for example azodiisobutylonitrile (AIBN), benzoin methyl ether (BME), 2,5-dimethyl-2,5 One or more selected from -di- (2-ethylhexanoylperoxy) hexane and dimethoxyphenyl acetophenone (DMPA) and the like can be used, but is not limited thereto. The initiator is preferably 0.005 to 2.000 wt% in the polymerization composition, and more specifically 0.010 to 1.500 wt%, but is not limited thereto.

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

In another aspect, the present invention provides a silicone hydrogel lens produced using the polymerization composition of the present invention, the water content is 25 to 70%, the contact angle of the surface is 40 ° or less by the trapping bubble method. Specifically, it provides a silicone hydrogel lens having an excellent water content and a contact angle of the surface comprising a copolymer obtained by polymerizing one or more of the novel siloxane monomer and the 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 measuring device (DSA 100). The soft contact lens to be measured was attached to a holding table, immersed in saline at 25 ° C., and a bubble was attached to the soft contact lens surface using a syringe to measure the angle formed by the soft contact lens and the bubble in saline. The smaller the measured value indicates the better wettability.

(2) moisture content

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

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

(3) oxygen transmission coefficient (Dk value)

To determine the oxygen permeability (Dk), the specimens were immersed in PBS solution at room temperature for 24 hours and then stored at 35 ° C. ± 0.5 ° C. for at least 2 hours at room temperature. In the incubator, the oxygen permeability (Dk) was measured using an oxygen permeability measuring instrument [Model 201T, Rehder Development Co., West Lafayette, USA] under a lens water saturation at a temperature of 35 ° C. ± 0.5 ° C. and a humidity of 98%. Measured.

(4) Weight average molecular weight

The weight average molecular weight was measured using a gel permeation chromatography (GPC) equipment manufactured by Waters. The instrument consists of a 1515 Binary Pump, a Column Heater (1500 Series), a Detector (2414 RI Detector), and an Injector (2707 Autoinjector) .The analysis column uses Shodex's KF-802, KF-802.5 and KF-803. Polystyrene (PS) SL-105 STD was used as a standard. HPLC grade tetrahydrofuran (THF) was used as the mobile phase solvent, and the temperature was measured under a column heater temperature of 40 ° C. and a mobile phase solvent flow rate of 1.0 mL / min. The siloxane monomer prepared for sample analysis was dissolved in tetrahydrofuran (THF), which is a mobile phase solvent, and then injected into a GPC device to determine the weight average molecular weight.

(5) viscosity

Viscosity was measured using a Brookfield LVDV-2T viscometer. Viscosity was measured by rotating the siloxane monomer in a container at 25 ℃ room temperature 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 (0.021 mol), 7 g (0.014 mol) of 1,3-bis ((3-methacryloxy2-hydroxypropoxypropyl) tetramethyldisiloxane, a compound of Formula 3, 180 g of chloroform and trifluoromethane A mixture of 1.50 g of sulfonic acid was stirred for 24 hours at 25 ° C. and then washed repeatedly with purified water until the pH of the mixture was neutral, after separating the water, the chloroform and volatile components were removed under reduced pressure to give a clear viscous liquid. Yield was 141 g (77.5%).

The compound of formula 1-1 was synthesized as a result of the analysis.

The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance analysis, Si- CH ₃ at δ0.06 ~ 0.12 ppm, Si- CH ₂ -CH ₂ -CF ₃ , δ2.07 ppm (at δ0.70 ppm (t, 10H) _{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. -C CH ₃ = CH ₂ at 96 ppm (S, 6H), Si- CH ₂ -CH ₂ -CH ₂ -O at δ 0.76 ppm (m, 4H), δ at 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. The viscosity was measured with a viscometer to confirm the viscosity of 130 cP. The weight average molecular weight 12,799 g / mol was confirmed through GPC analysis.

[Formula 3]

[Formula 1-1]

Where l = 6, m = 140 and n = 10.

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

A mixture of 125 g of the siloxane monomer of Formula 1-1, 33 g (0.09 mol) of polyethylene glycol Allylmethyl ether of Formula 4, 250 g of isopropyl alcohol, and 6.3 ml of platinum catalyst was charged into a flask with a reflux condenser. Heated under reflux for 6 h. After the reaction mixture was filtered, isopropanol was removed under reduced pressure, and then washed several times with a mixture of acetone and water in a 1: 1 volume ratio. The volatile components were further removed under vacuum to yield a clear viscous liquid, yield 124 g, yield 84.2%. As a result, a compound represented by Chemical Formula 1-2 was synthesized.

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

[Formula 4]

[Formula 1-2]

(Wherein, 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), 42.0 g of N-vinylpyrrolidone (NVP, Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, Aldrich, 128635) 4.5 g, 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

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

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

Example 2

1) Synthesis of siloxane monomer

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

Octamethylcyclotetrasiloxane 147 g (0.49 mol), 1,3,5,7-tetramethyl-cyclotetrasiloxane 5 g (0.021 mol), 1,3-bis ((3-methacryloxy2-hydroxypro Foxipropyl) Tetramethyldisiloxane 7 g (0.014 mol), 180 g chloroform and 1.5 g trifluoromethane sulfonic acid were stirred at 25 ° C. for 24 h and then repeated with purified water until the pH of the mixture became neutral. After water was separated, chloroform and volatile components were removed under reduced pressure to give a clear viscous liquid. 131 g, the yield was 82.0%.

The compound of formula 1-3 was synthesized as a result of the analysis.

The resulting product was analyzed at 400 MHz hydrogen nuclear magnetic resonance (SEM) at δ0.06 to 0.12 ppm, at Si- CH ₃ , at δ4.70 ppm (s, 6H), at Si- H and at δ5.60 to 6.15 ppm (dd, 4H). -CH = CH ₂ , -C CH ₃ = CH ₂ , at δ 1.96 ppm (S, 6H) 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 - CH ₂ -O, δ3.60-3.80 ppm (m, 5H) at O- CH ₂ -CH-OH, O-CH ₂ - CH -OH, O-CH _2, it was confirmed a peak of CH ₂ -CH-. The viscosity was measured with a viscometer to confirm the viscosity of 105 cP. GPC analysis confirmed the weight average molecular weight 12,310 g / mol.

[Formula 1-3]

(Wherein l = 6 and m = 140)

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

A mixture of 125 g of the siloxane monomer of Formula 1-3, 38 g (0.10 mol) of polyethylene glycol allylmethyl ether, 250 g of isopropyl alcohol, and 6.3 ml of platinum catalyst was added to a flask with a reflux condenser, and under reflux 6 Heated with stirring for hours. After the reaction mixture was filtered, isopropanol was removed under reduced pressure, and then washed several times with a mixture of acetone and water in a 1: 1 volume ratio. Further removal of the volatile components under vacuum gave a clear viscous liquid, yield 123 g, yield 81.8%. As a result, a compound represented by Chemical Formula 1-4 was synthesized.

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

[Formula 1-4]

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

2) Preparation of Polymeric Composition

53 g of the siloxane monomer of Formula 1-4 prepared in 1), 42.0 g of N-vinylpyrrolidone (NVP, Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, Aldrich, 128635) 4.5 g, 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The prepared polymer composition was injected into a female mold for cast molding, and a male mold was assembled to the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 ° 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 subjected to autoclaving in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

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

Example 3

1) Synthesis of siloxane monomer

Octamethylcyclotetrasiloxane 147 g (0.49 mol), 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane 22 g (0.047 mol), 1,3-bis ((3-methacryloxy2-hydroxy A mixture of 7 g (0.014 mol) of propoxypropyl) tetramethyldisiloxane, 180 g of chloroform and 1.5 g of trifluoromethane sulfonic acid was stirred at 25 ° C. for 24 hours, then with purified water until the pH of the mixture became neutral. After repeated washings, the water was separated and the chloroform and volatile components were removed under reduced pressure to give a clear viscous liquid, yield 142 g, yield 80.3%.

As a result, a compound of Formula 1-5 was synthesized.

The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance analysis, Si- CH ₃ , δ0.70 ppm (t, 20H) at δ0.06 ~ 0.12 ppm, and Si- CH ₂ -CH ₂ -CF ₃ , δ2.07 ppm ( t, 20H), Si-CH ₂ -CH ₂ -CF ₃ , at -5.60-6.65 ppm (dd, 4H) -CH = CH ₂ , at δ5.87 ppm (dd, 2H) -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 , 4H), Si-CH ₂ -CH ₂ - CH ₂ -O, δ3.60-3.80 ppm (m, 5H) at O- CH ₂ -CH-OH, O-CH ₂ - CH -OH, O-CH _{The 2} -CH-CH ₂ peak was confirmed. The viscosity was measured with a viscometer to confirm the viscosity of 131 cP. The weight average molecular weight 12,953 g / mol was confirmed through GPC analysis.

[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), 53.0 g of N-vinylpyrrolidone (NVP, Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, Aldrich, 128635) 4.5 g, 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The prepared polymer composition was injected into a female mold for cast molding, and a male mold was assembled to the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 ° 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 subjected to autoclaving in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The releasability and physical properties of the manufactured lens were measured and 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 (0.021 mol), a mixture of 1,3-bis ((3-methacryloxy2-hydroxypropoxypropyl) tetramethyldisiloxane, 7 g (0.014 mol), 180 g of chloroform and 1.50 g of trifluoromethane sulfonic acid After stirring for 24 hours at 25 ° C., the mixture was washed repeatedly with purified water until the pH of the mixture became neutral, after separating the water, the chloroform and volatile components were removed under reduced pressure to obtain a clear viscous liquid. g (84.1%).

The compound of formula 1-1 was synthesized as a result of the analysis.

The obtained product was Si- CH ₃ at δ0.06 to 0.12 ppm, Si- H at δ4.70 ppm (s, 6H), Si- H at δ0.70 ppm (t, 10H), and the result of 400 MHz hydrogen nuclear magnetic resonance analysis. _{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. -C CH ₃ = CH ₂ at 96 ppm (S, 6H), Si- CH ₂ -CH ₂ -CH ₂ -O at δ 0.76 ppm (m, 4H), δ at 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. The viscosity was measured with a viscometer to confirm the viscosity of 130 cP. The weight average molecular weight 13,214 g / mol was confirmed through GPC analysis.

[Formula 1-1]

Where 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), 42.0 g of N-vinylpyrrolidone (NVP, Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, Aldrich, 128635) 4.5 g, 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The prepared polymer composition was injected into a female mold for cast molding, and a male mold was assembled to the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 ° 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 subjected to autoclaving in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

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

Example 5

1) Synthesis of siloxane monomer

Octamethylcyclotetrasiloxane 147 g (0.49 mol), 1,3,5,7-tetramethyl-cyclotetrasiloxane 5 g (0.021 mol), 1,3-bis ((3-methacryloxy2-hydroxypro Foxipropyl) Tetramethyldisiloxane 7 g (0.014 mol), 180 g chloroform and 1.5 g trifluoromethane sulfonic acid were stirred at 25 ° C. for 24 h and then repeated with purified water until the pH of the mixture became neutral. After water was separated, chloroform and volatile components were removed under reduced pressure to give a clear viscous liquid. 127 g, the yield was 79.5%.

The compound of formula 1-6 was synthesized as a result of the analysis.

The resulting product was analyzed at 400 MHz hydrogen nuclear magnetic resonance (SEM) at δ0.06 to 0.12 ppm, at Si- CH ₃ , at δ4.70 ppm (s, 6H), at Si- H and at δ5.60 to 6.15 ppm (dd, 4H). _{-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. The viscosity was measured with a viscometer to confirm the viscosity of 106 cP. The weight average molecular weight 11,630 g / mol was confirmed through GPC analysis.

[Formula 1-6]

(Wherein l = 6 and m = 140)

2) Preparation of Polymeric Composition

30.0 g of the siloxane monomer of Formula 1-6 prepared in 1), 65.0 g of N-vinylpyrrolidone (NVP, Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, Aldrich, 128635) 4.5 g, 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The prepared polymer composition was injected into a female mold for cast molding, and a male mold was assembled to the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 ° 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 subjected to autoclaving in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

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

Example 6

1) Synthesis of siloxane monomer

Octamethylcyclotetrasiloxane 76 g (0.25 mol), 1,3-bis ((3-methacryloxy2-hydroxypropoxypropyl) tetramethyldisiloxane 27 g (0.051 mol), 180 g chloroform and trifluoro A mixture of 0.7 g of methane sulfonic acid was stirred for 24 hours at 25 ° C. and then washed repeatedly with purified water until the pH of the mixture became neutral, after separating the water, removing chloroform and volatile components under reduced pressure to give a clear viscous liquid. Yield. 81 g, yield 78.3%.

The compound of formula 1-7 was synthesized as a result of the analysis.

The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance analysis, Si- CH ₃ at δ0.06 ~ 0.12 ppm, -CH = CH ₂ , δ1.96 ppm (S, 6H) at δ5.60 ~ 6.15 ppm (dd, 4H). ) -C CH ₃ = CH ₂ , δ 0.76 ppm (m, 4H) at Si- CH ₂ -CH ₂ -CH ₂ -O, δ 1.69 ppm (m, 4H) at Si-CH ₂ - CH _2- CH ₂ -O, δ 3.94 ppm (m, 4H) Si-CH ₂ -CH ₂ - CH ₂ -O, δ 3.60 to 3.80 ppm (m, 5H) O- CH ₂ -CH-OH, O- CH ₂ - was confirmed that the peak of the _{CH -OH, O-CH 2 -CH-} CH 2. The viscosity was measured with a viscometer to confirm the viscosity of 76 cP. GPC analysis confirmed a weight average molecular weight of 1,977 g / mol.

[Formula 1-7]

(Wherein m = 20)

2) Preparation of Polymeric Composition

20 g of the siloxane monomer of Formula 1-7 prepared in 1), 75.0 g of N-vinylpyrrolidone (NVP, Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, Aldrich, 128635) 4.5 g, 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The prepared polymer composition was injected into a female mold for cast molding, and a male mold was assembled to the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 ° 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 subjected to autoclaving in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

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

Example 7

1) Synthesis of siloxane monomer

71 g (0.15 mol) of 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane, 1,3-bis ((3-methacryloxy2-hydroxypropoxypropyl) tetramethyldisiloxane 24 g (0.046 mol), 180 g of chloroform and 0.7 g of trifluoromethane sulfonic acid were stirred for 24 hours at 25 ° C., and then washed repeatedly with purified water until the pH of the mixture was neutral. Chloroform and volatile components were removed to give a clear viscous liquid. 82 g, the yield was 85.7%.

The compound of formula 1-8 was synthesized as a result of the analysis.

The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance analysis, Si- CH ₃ at δ0.06 ~ 0.12 ppm, Si- CH ₂ -CH ₂ -CF ₃ , δ2.07 ppm (at δ0.70 ppm (t, 10H) _{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. The viscosity was measured with a viscometer to confirm the viscosity of 105 cP. The weight average molecular weight 2,323 g / mol was confirmed through GPC analysis.

[Formula 1-8]

(Where n = 10)

2) Preparation of Polymeric Composition

15 g of the siloxane monomer of Formula 1-8 prepared in 1), 80.0 g of N-vinylpyrrolidone (NVP, Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, Aldrich, 128635) 4.5 g, 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The prepared polymer composition was injected into a female mold for cast molding, and a male mold was assembled to the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 ° 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 subjected to autoclaving in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The releasability and physical properties of the manufactured lens were measured and 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, 31 g (0.059 mol) of 1,3-bis ((3-methacryloxy2-hydroxypropoxypropyl) tetramethyldisiloxane ), A mixture of 180 g of chloroform and 0.7 g of trifluoromethane sulfonic acid was stirred at 25 ° C. for 24 hours, and then washed repeatedly with purified water until the pH of the mixture became neutral, after which water was separated and chloroform under reduced pressure. And volatile components were removed to give a clear viscous liquid, yield 81 g, yield 79.2%.

The compound of formula 1-9 was synthesized as a result of the analysis.

The resulting product was analyzed at 400 MHz hydrogen nuclear magnetic resonance (SEM) at δ0.06 to 0.12 ppm, at Si- CH ₃ , at δ4.70 ppm (s, 20H), at Si- H and at δ5.60 to 6.15 ppm (dd, 4H). _{-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. The viscosity was measured by a viscometer to confirm the viscosity of 97 cP. The weight average molecular weight 1,795 g / mol was confirmed through GPC analysis.

[Formula 1-9]

(Wherein l = 20)

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

A mixture of 75 g of the siloxane monomer of Formula 1-9, 492 g (1.30 mol) of polyethylene glycol allylmethyl ether, 600 g of isopropyl alcohol, and 3.83 ml of platinum catalyst were added to a flask with a reflux condenser and refluxed for 6 hours. Heated with stirring. After the reaction mixture was filtered, isopropanol was removed under reduced pressure, and then washed several times with a mixture of acetone and water in a 1: 1 volume ratio. The volatile components were further removed under vacuum to yield a clear viscous liquid, yield 324 g, yield 80.3%. As a result, a compound represented by Chemical Formula 1-10 was synthesized.

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

[Formula 1-10]

(Wherein l = 20)

2) Preparation of Polymeric Composition

50 g of the siloxane monomer of Formula 1-10 prepared in 1), 45.0 g of N-vinylpyrrolidone (NVP, Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, Aldrich, 128635) 4.5 g, 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The prepared polymer composition was injected into a female mold for cast molding, and a male mold was assembled to the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 ° 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 subjected to autoclaving in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The releasability and physical properties of the manufactured lens were measured and 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-methacryloxy2-hydroxypropoxypropyl) tetramethyldisiloxane ), 100 g of chloroform and 0.8 g of trifluoromethane sulfonic acid were stirred for 24 hours at 25 ° C., and then washed repeatedly with purified water until the pH of the mixture was neutral. And volatile components were removed to obtain a clear viscous liquid. 82 g, yield 77.8%.

The compound of formula 1-11 was synthesized as a result of the analysis.

The resulting product was analyzed at 400 MHz hydrogen nuclear magnetic resonance (SEM) at δ0.06 to 0.12 ppm, at Si- CH ₃ , at δ4.70 ppm (s, 50H), at Si- H and at δ5.60 to 6.15 ppm (dd, 4H). _{-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. The viscosity was measured with a viscometer to confirm the viscosity of 106 cP. The weight average molecular weight 3,721 g / mol was confirmed through GPC analysis.

[Formula 1-11]

(Wherein, l = 50)

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

A mixture of 75 g of the siloxane monomer of Formula 1-11, polyethylene glycol allylmethyl ether, 604 g (1.60 mol), 700 g isopropyl alcohol, and 3.8 ml of the platinum catalyst synthesized above was added to a flask with a reflux condenser and refluxed for 6 hours. Heated with stirring. After the reaction mixture was filtered, isopropanol was removed under reduced pressure, and then washed several times with a mixture of acetone and water in a 1: 1 volume ratio. The volatile components were further removed under vacuum to yield a clear viscous liquid, yield 381 g, yield 79.8%. As a result, a compound represented by the following Chemical Formula 1-12 was synthesized.

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

[Formula 1-12]

(Wherein, l = 50)

2) Preparation of Polymeric Composition

60.0 g of the siloxane monomer of Formula 1-12 prepared in 1), 35.0 g of N-vinylpyrrolidone (NVP, Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, Aldrich, 128635) 4.5 g, 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The prepared polymer composition was injected into a female mold for cast molding, and a male mold was assembled to the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 ° 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 subjected to autoclaving in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The releasability and physical properties of the manufactured lens were measured and 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, a compound of formula 5, 180 g of chloroform and 1.5 g of trifluoromethane sulfonic acid After stirring for 24 hours, the mixture was washed repeatedly with purified water until the pH of the mixture was neutral, after separating the water, the chloroform and volatile components were removed under reduced pressure to obtain a clear viscous liquid. , The yield was 79.9%.

The compound of formula 6-1 was synthesized as a result of the analysis.

The obtained product was Si- CH ₃ at δ0.06 ~ 0.12 ppm, Si- CH ₂ -CH ₂ -CF ₃ , δ2.07 ppm (m) at δ0.06 ~ 0.12 ppm , 20H), Si-CH ₂ -CH ₂ -CF ₃ , δ 4.70 ppm (s, 6H), Si- H , δ5.60-6.15 ppm (dd, 4H), -CH = CH ₂ , δ1.96 -C CH ₃ = CH ₂ at ppm (S, 6H), Si- CH ₂ -CH ₂ -CH ₂ -O at δ 0.76 ppm (m, 4H), Si-CH at 1.69 ppm (m, 4H) ₂ - _{CH 2 -CH 2 -O, δ 3.94} ppm (m, 4H) Si-CH 2 -CH 2 - CH 2 -O peak was confirmed. The viscosity was measured with a viscometer to confirm the viscosity of 125 cP. The weight average molecular weight 12,545 g / mol was confirmed through GPC analysis.

[Formula 5]

[Formula 6-1]

(Wherein, l = 6, m = 140 and n = 10).

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

A mixture of 100 g of the siloxane monomer of Formula 6-1, 26 g (0.07 mol) of polyethylene glycol allylmethyl ether, 200 g of isopropyl alcohol, and 5.1 ml of platinum catalyst was charged to a flask with a reflux condenser, and the mixture was refluxed under 6 Heated with stirring for hours. After the reaction mixture was filtered, isopropanol was removed under reduced pressure, and then washed several times with a mixture of acetone and water in a 1: 1 volume ratio. Further removal of the volatile components under vacuum gave a clear viscous liquid, yielding 99 g, yield 83.9%. As a result, a compound represented by Chemical Formula 6-2 was synthesized.

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

[Formula 6-2]

(Wherein, l = 6, m = 140, n = 10)

2) Preparation of Polymeric Composition

53 g of the siloxane monomer of Formula 6-2 prepared in 1), 42.0 g of N-vinylpyrrolidone (NVP, Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, Aldrich, 128635) 4.5 g, 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The prepared polymer composition was injected into a female mold for cast molding, and a male mold was assembled to the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 ° 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 subjected to autoclaving 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

Octamethylcyclotetrasiloxane 147 g (0.50 mol), 1,3,5,7-tetramethyl-cyclotetrasiloxane 5 g (0.021 mol), 1,3-bis ((methacryloxypropyl A mixture of 5 g (0.014 mol) of tetramethyldisiloxane, 180 g of chloroform and 1.5 g of trifluoromethane sulfonic acid was stirred at 25 ° C. for 24 hours and then washed repeatedly with purified water until the pH of the mixture became neutral. After water was separated, chloroform and volatile components were removed under reduced pressure to give a clear viscous liquid, yield 136 g, yield 86.3%.

The compound of formula 6-3 was synthesized as a result of the analysis.

The resulting product was analyzed at 400 MHz hydrogen nuclear magnetic resonance (SEM) at δ0.06 to 0.12 ppm, at Si- CH ₃ , at δ4.70 ppm (s, 6H), at Si- H and at δ5.60 to 6.15 ppm (dd, 4H). _{-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. The viscosity was measured with a viscometer to confirm the viscosity of 105 cP. The weight average molecular weight 11,345 g / mol was confirmed through GPC analysis.

[Formula 6-3]

Where l = 6, m = 140 and

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

A mixture of 100 g of the siloxane monomer of Formula 6-3, 30 g (0.08 mol) of polyethylene glycol allylmethyl ether, 200 g of isopropyl alcohol, and 5.1 ml of platinum catalyst was added to a flask with a reflux condenser, followed by 6 at reflux. Heated with stirring for hours. After the reaction mixture was filtered, isopropanol was removed under reduced pressure, and then washed several times with a mixture of acetone and water in a 1: 1 volume ratio. Further removal of the volatile components under vacuum gave a clear viscous liquid, yield 94 g, yield 78.1%. As a result, a compound represented by Chemical Formula 6-4 was synthesized.

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

[Formula 6-4]

(Wherein l = 6 and m = 140)

2) Preparation of Polymeric Composition

53.0 g of the siloxane monomer of Formula 6-4 prepared in 1), 42.0 g of N-vinylpyrrolidone (NVP, Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, Aldrich, 128635) 4.5 g, 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The prepared polymer composition was injected into a female mold for cast molding, and a male mold was assembled to the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 ° 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 subjected to autoclaving in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The physical properties of the prepared polymerized 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

Octamethylcyclotetrasiloxane 147 g (0.50 mol), 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane 22 g (0.047 mol), 1,3-bis ((methacryloxy Propyl) Tetramethyldisiloxane 5 g (0.014 mol), 180 g of chloroform and 1.5 g of trifluoromethane sulfonic acid were stirred at 25 ° C. for 24 hours and then washed repeatedly with purified water until the pH of the mixture became neutral. After water was separated, chloroform and volatile components were removed under reduced pressure to give a clear viscous liquid, yield 129 g, yield 73.9%.

The compound of formula 6-5 was synthesized as a result of the analysis.

The obtained product was Si- CH ₃ at δ0.06 ~ 0.12 ppm, Si- CH ₂ -CH ₂ - C F ₃ , δ2.07 ppm at δ0.06 ~ 0.12 ppm Si-CH ₂ -CH ₂ -CF ₃ at (m, 20H), -CH = CH ₂ at δ5.60 to 6.15 ppm (dd, 4H), -C CH ₃ at δ 1.96 ppm (S, 6H) = _{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 in ppm (m, 4H) Si- CH 2 -CH 2 - CH ₂ -O peak was confirmed. The viscosity was measured by a viscometer to confirm the viscosity of 108 cP. The weight average molecular weight 12,653 g / mol was confirmed through GPC analysis.

[Formula 6-5]

(Wherein l = 10 and m = 140)

2) Preparation of Polymeric Composition

42 g of the siloxane monomer of Chemical Formula 6-5 prepared in 1), 53.0 g of N-vinylpyrrolidone (NVP, Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, Aldrich, 128635) 4.5 g, 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The prepared polymer composition was injected into a female mold for cast molding, and a male mold was assembled to the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 ° 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 subjected to autoclaving in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The releasability and physical properties of the manufactured lens were measured and 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), a mixture of 5 g (0.014 mol) of 1,3-bis ((methacryloxypropyl) tetramethyldisiloxane, the compound of Formula 5, 180 g of chloroform and 1.5 g of trifluoromethane sulfonic acid was 25 ° C. After stirring for 24 h at rt, the mixture was washed repeatedly with purified water until the pH became neutral, after separating the water, the chloroform and volatile components were removed under reduced pressure to give a clear viscous liquid. The yield was 82.9%.

The compound of formula 6-1 was synthesized as a result of the analysis.

The obtained product was Si- CH ₃ at δ0.06 ~ 0.12 ppm, Si- CH ₂ -CH ₂ -CF ₃ , δ2.07 ppm (m) at δ0.06 ~ 0.12 ppm , 20H), Si-CH ₂ -CH ₂ -CF ₃ , δ 4.70 ppm (s, 6H), Si- H , δ5.60-6.15 ppm (dd, 4H), -CH = CH ₂ , δ1.96 -C CH ₃ = CH ₂ at ppm (S, 6H), Si- CH ₂ -CH ₂ -CH ₂ -O at δ 0.76 ppm (m, 4H), Si-CH at 1.69 ppm (m, 4H) ₂ - _{CH 2 -CH 2 -O, δ 3.94} ppm (m, 4H) Si-CH 2 -CH 2 - CH 2 -O peak was confirmed. The viscosity was measured with a viscometer to confirm the viscosity of 119 cP. GPC analysis confirmed a weight average molecular weight of 15,478 g / mol.

[Formula 6-1]

Where 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), 65.0 g of N-vinylpyrrolidone (NVP, Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, Aldrich, 128635) 4.5 g, 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The prepared polymer composition was injected into a female mold for cast molding, and a male mold was assembled to the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 ° 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 subjected to autoclaving in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

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

[Comparative Example 5]

1) Synthesis of siloxane monomer

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

The compound of formula 6-6 was synthesized as a result of the analysis.

The resulting product was analyzed at 400 MHz hydrogen nuclear magnetic resonance (SEM) at δ0.06 to 0.12 ppm, at Si- CH ₃ , at δ4.70 ppm (s, 6H), at Si- H and at δ5.60 to 6.15 ppm (dd, 4H). _{-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. The viscosity was measured with a viscometer to confirm the viscosity of 104 cP. GPC analysis confirmed the weight average molecular weight 10,783 g / mol.

[Formula 6-6]

(Wherein l = 6 and m = 140)

2) Preparation of Polymeric Composition

30 g of the siloxane monomer of Formula 6-6 prepared in 1), 65.0 g of N-vinylpyrrolidone (NVP, Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, Aldrich, 128635) 4.5 g, 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The prepared polymer composition was injected into a female mold for cast molding, and a male mold was assembled to the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 ° 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 subjected to autoclaving in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The releasability and physical properties of the manufactured lens were measured and 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, a compound of Formula 5, 180 g of chloroform and trifluoromethane sulfonic acid 0.8 g of the mixture was stirred for 24 hours at 25 ° C. and then washed repeatedly with purified water until the pH of the mixture was neutral, after separating the water, chloroform and volatile components were removed under reduced pressure to give a clear viscous liquid. The yield was 82.5 g and the yield was 78.9%.

The compound of formula 6-7 was synthesized as a result of the analysis.

The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance analysis, Si- CH ₃ at δ0.06 ~ 0.12 ppm, -CH = CH ₂ , δ1.96 ppm (S, 6H) at δ5.60 ~ 6.15 ppm (dd, 4H). ) -C CH ₃ = CH ₂ , δ 0.76 ppm (m, 4H) at Si- CH ₂ -CH ₂ -CH ₂ -O, δ 1.69 ppm (m, 4H) at Si-CH ₂ - 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. The weight average molecular weight 1,761 g / mol was confirmed through GPC analysis.

[Formula 6-7]

(Wherein m = 20)

2) Preparation of Polymeric Composition

20 g of the siloxane monomer of Formula 6-7 prepared in 1), 75 g of N-vinylpyrrolidone (NVP, Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, Aldrich, 128635) 4.5 g, 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The prepared polymer composition was injected into a female mold for cast molding, and a male mold was assembled to the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 ° 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 subjected to autoclaving in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The releasability and physical properties of the manufactured lens were measured and 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, a compound of Formula 5 , A mixture of 180 g of chloroform and 0.8 g of trifluoromethane sulfonic acid was stirred at 25 ° C. for 24 hours, and then washed repeatedly with purified water until the pH of the mixture became neutral. The volatile components were removed to give a clear viscous liquid. 73 g, the yield was 81.3%.

The compound of formula 6-8 was synthesized as a result of the analysis.

The obtained product was found to be Si- CH ₃ at δ0.06 ~ 0.12 ppm, Si- CH ₂ -CH ₂ -CF ₃ , δ2.07 ppm (at δ0.06 ~ 0.12 ppm). _{CH 2 -CF 3, δ5.60 ~ 6.15} ppm (dd, 4H) -C in _{-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). The viscosity was measured with a viscometer to confirm the viscosity of 95 cP. The weight average molecular weight 1,863g / mol was confirmed through GPC analysis.

[Formula 6-8]

(Where n = 10)

2) Preparation of Polymeric Composition

15 g of the siloxane monomer of Formula 6-8 prepared in 1), 80.0 g of N-vinylpyrrolidone (NVP, Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, Aldrich, 128635) 4.5 g, 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The prepared polymer composition was injected into a female mold for cast molding, and a male mold was assembled to the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 ° 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 subjected to autoclaving in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The releasability and physical properties of the manufactured lens were measured and 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, which is a compound of Formula 5, A mixture of 180 g of chloroform and 0.8 g of trifluoromethane sulfonic acid was stirred at 25 ° C. for 24 hours, and then washed repeatedly with purified water until the pH of the mixture was neutral. The components were removed to give a clear viscous liquid. 78 g, yield 78.7%.

The compound of formula 6-9 was synthesized as a result of the analysis.

The obtained product was analyzed at 400 MHz hydrogen nuclear magnetic resonance (SEM) at δ0.06 to 0.12 ppm, at Si- CH ₃ , at δ4.70 ppm (s, 20H), at Si- H and at δ5.60 to 6.15 ppm (dd, 4H). _{-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. The viscosity was measured with a viscometer to confirm the viscosity of 93 cP. GPC analysis confirmed a weight average molecular weight of 1,521 g / mol.

[Formula 6-9]

(Wherein l = 20)

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

A mixture of 75 g of the siloxane monomer of Formula 16-9, 539 g (1.42 mol) of polyethylene glycol allylmethyl ether, 600 g of isopropyl alcohol, and 3.8 ml of platinum catalyst was introduced into a flask equipped with a reflux condenser, and refluxed under 6 Heated with stirring for hours. After the reaction mixture was filtered, isopropanol was removed under reduced pressure, and then washed several times with a mixture of acetone and water in a 1: 1 volume ratio. Further removal of the volatile components under vacuum gave a clear viscous liquid, yield 367 g, yield 84.6%. As a result, a compound represented by Chemical Formula 6-10 was synthesized.

As a result of the 400 MHz hydrogen nuclear magnetic resonance analysis, the obtained product was confirmed to generate an O- CH ₂ CH ₂ -peak at δ 3.15 to 3.90 ppm. The viscosity was measured by a viscometer to confirm the viscosity of 149 cP. A weight average molecular weight of 9,185 g / mol was confirmed through GPC analysis.

[Formula 6-10]

(Wherein l = 20)

2) Preparation of Polymeric Composition

50 g of the siloxane monomer of Formula 6-10 prepared in 1), 45.0 g of N-vinylpyrrolidone (NVP, Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, Aldrich, 128635) 4.5 g, 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The prepared polymer composition was injected into a female mold for cast molding, and a male mold was assembled to the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 ° 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 subjected to autoclaving in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

The releasability and physical properties of the manufactured lens were measured and 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, which is a compound of Formula 5, A mixture of 180 g of chloroform and 0.9 g of trifluoromethane sulfonic acid was stirred for 24 hours at 25 ° C., and then washed repeatedly with purified water until the pH of the mixture was neutral. The components were removed to give a clear viscous liquid. 75 g, yield 74.9%.

The compound of formula 6-11 was synthesized as a result of the analysis.

The resulting product was analyzed at 400 MHz hydrogen nuclear magnetic resonance (SEM) at δ0.06 to 0.12 ppm, at Si- CH ₃ , at δ4.70 ppm (s, 50H), at Si- H and at δ5.60 to 6.15 ppm (dd, 4H). _{-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 To confirm the viscosity of 102 cP. The weight average molecular weight 3,197 g / mol was confirmed through GPC analysis.

[Formula 6-11]

(Wherein, l = 50)

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

A mixture of 75 g of the siloxane monomer of Formula 6-11, 630 g (1.66 mol) of polyethylene glycol allylmethyl ether, 700 g of isopropyl alcohol, and 3.8 ml of platinum catalyst was introduced into a flask with a reflux condenser, and the mixture was refluxed under 6 Heated with stirring for hours. After the reaction mixture was filtered, isopropanol was removed under reduced pressure, and then washed several times with a mixture of acetone and water in a 1: 1 volume ratio. Further removal of the volatile components under vacuum gave a clear viscous liquid, yield 418 g, yield 84.4%. As a result, a compound represented by Chemical Formula 6-12 was synthesized.

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

[Formula 6-12]

(Wherein, l = 50)

2) Preparation of Polymeric Composition

60 g of the siloxane monomer of Formula 6-12 prepared in 1), 35.0 g of N-vinylpyrrolidone (NVP, Aldrich, V3409) as a hydrophilic monomer, 2-hydroxyethyl methacrylate (HEMA, Aldrich, 128635) 4.5 g, 0.5 g of ethylene glycol dimethacrylate (EGDMA, Aldrich, 335681) as a crosslinking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymerization composition.

The prepared polymer composition was injected into a female mold for cast molding, and a male mold was assembled to the female mold. Next, the assembled mold was placed in a heat oven maintained at 100 ° 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 subjected to autoclaving in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

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

	Moisture content (%)	Surface contact angle (˚)	Oxygen transmission 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 shown in the table, it can be seen that Examples 1 to 9 according to the present invention are similar in water content and oxygen permeability coefficient, but the surface contact angle is significantly lower than Comparative Examples 1 to 9.

This resulted in extremely improved wettability due to the hydroxyl group introduced into the siloxane monomer terminals of Examples 1 to 9, resulting in a low surface contact angle, resulting in a very comfortable fit compared to the comparative example which does not include such a specific functional group.

Claims (10)

1. The siloxane monomer represented by following formula (1).

   [Formula 1]

   

   (In 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, wherein any one 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 independently integers selected from 0 to 10;

   D ₁ and D ₂ are each independently 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;

   B ₁ and B ₂ are independently of each other hydrocarbyl or

   

   Is,

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

   

   And

   A is any one selected from the following structural formulas.

   

   

   

   [In the above structural formula,

   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.]
2. The method of claim 1,

   In Formula 1, R _a1 to R _a8 are independently of each other hydrogen or hydroxy, and any one of R _a1 to R _a8 is necessarily hydroxy;

   q and c are independently of each other a siloxane monomer being an integer selected from 1 to 10.
3. The method of claim 1,

   Formula 1 is a siloxane monomer represented by the following formula (2).

   [Formula 2]

   

   (In Formula 2,

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

   R _a2 to R _a7 is independently of each other 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 independently integers selected from 0 to 10;

   D ₁ and D ₂ are each independently 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;

   B ₁ and B ₂ are independently of each other hydrocarbyl or

   

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

   

   And

   A is any one selected from the following structural formulas.

   

   

   

   [In the above structural formula,

   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.]
4. The method of claim 1,

   In Chemical Formula 2,

   R ₅ to R ₁₀ are each independently hydrogen, (C ₁ -C ₁₀ ) alkyl or halo (C ₁ -C ₁₀ ) alkyl.
5. The method of claim 4, wherein

   In Chemical Formula 2, R ₅ to R ₆ and R ₈ to R ₁₀ are independently of each other hydrogen or (C ₁ -C ₁₀ ) alkyl, and R ₇ is halo (C ₁ -C ₁₀ ) alkyl.
6. The method of claim 5,

   In Formula 2, l, m and n are each independently an integer selected from 5 to 150,

   R ₅ to R ₆ and R ₈ to R ₁₀ are each independently hydrogen or methyl; R ₆ is

   

   Phosphorus siloxane monomer.
7. The method of claim 1,

   In Formula 2, R _a2 to R _a7 is hydrogen;

   o, p, a and b are integers independently selected from 1 to 5;

   q and c are independently integers selected from 1 to 3;

   D ₁ and D ₂ are siloxane monomers independently of one another.
8. A polymer composition for producing a silicone hydrogel lens comprising the siloxane monomer and the reactive monomer of any one of claims 1 to 7.
9. The method of claim 8,

   The composition is a polymer composition for preparing a silicone hydrogel lens containing 5 to 60% by weight of siloxane monomer.
10. The method of claim 8,

    The reactive monomer is any one or a mixture of two or more selected from a hydrophilic acrylic monomer, a hydrophilic silicone acrylic monomer polymerization composition for producing a silicone hydrogel lens.