Siloxane monomer, composition for preparation of silicone hydrogel lens containing same, and silicone hydrogel lens

Abstract

The present invention relates to a siloxane monomer used in the production of a silicone hydrogel lens, a composition for the preparation of a lens containing the same, and a silicone hydrogel lens prepared from the same, wherein the silicone hydrogel lens according to the present invention has a feature of easy release from a component of a mold.

Claims

1. A siloxane monomer represented by Chemical Formula 1 below and used in preparation of a silicone hydrogel lens: ##STR00080## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently selected from hydrogen and C.sub.1-C.sub.10 alkyl, A is selected from the group consisting of ##STR00081## l, m and n are each independently an integer selected from 5 to 150, R.sub.5 is hydrogen or ##STR00082## q is an integer of 5 to 15, R.sub.6 is methyl, R.sub.7 and R.sub.8 are methyl, R.sub.9 is ##STR00083## R.sub.10is methyl, X.sub.1 and X.sub.2 are each independently a substituent represented by Chemical Formula 3 below: ##STR00084## o and p are each independently an integer selected from 1 to 10, B is C.sub.6-C.sub.10 arylene, and R.sub.11 is hydrogen or a methyl group.

2. The siloxane monomer of claim 1, wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are methyl groups, X.sub.1 and X.sub.2 are each independently a substituent represented by Chemical Formula 3-1 below: ##STR00085## in Chemical Formula 3-1, R.sub.11 is hydrogen or methyl, and o and p are each independently an integer selected from 1 to 5.

3. A polymeric composition for preparing a silicone hydrogel lens comprising the siloxane monomer of claim 1.

4. The polymeric composition of claim 3, wherein the polymeric composition includes the siloxane monomer, a reactive monomer, a cross-linking agent, and an initiator.

5. The polymeric composition of claim 4, wherein the polymeric composition includes 5 to 60 wt% of the siloxane monomer, 35 to 90 wt% of the reactive monomer, 0.005 to 5 wt% of the cross-linking agent, and 0.005 to 2 wt% of the initiator.

6. The polymeric composition of claim 5, wherein the polymeric composition has a viscosity of 10 to 20,000 cP measured at 25 C.

7. The polymeric composition of claim 4, wherein the reactive monomer is any one or a mixture of two or more selected from the group consisting of a hydrophilic acrylic monomer and a hydrophilic silicone acrylic monomer.

8. The polymeric composition of claim 7, wherein the hydrophilic acrylic monomer is any one or a mixture of two or more selected from the group consisting of C.sub.1-C.sub.15 hydroxyalkyl methacrylate substituted with 1 to 3 hydroxy groups, C.sub.1-C.sub.15 hydroxyalkyl acrylate substituted with 1 to 3 hydroxyl groups, acrylamide, vinyl pyrrolidone, glycerol methacrylate, acrylic acid, and methacrylic acid, and the hydrophilic silicone acrylic monomer is any one or a mixture of two or more selected from the group consisting of 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-methacryioxybutyl-terminated polydimethylsiloxane.

9. A silicone hydrogel lens comprising a copolymer obtained by polymerizing the polymeric composition of claim 4.

10. The silicone hydrogel lens of claim 9, wherein when the polymeric composition is cured in a mold to prepare a lens and is then sucked with a suction having the degree of vacuum of 5 to 50 mmHg, a separation yield according to Equation 1 below is 80% or more
Separation yield=(number of lenses_separating from mold after suction/total number of lenses cured in mold)100.[Equation 1]

11. A silicone hydrogel lens comprising the siloxane monomer unit of claim 1 and having a separation yield according to Equation 1 below of 80% or more when sucked with a suction haying the degree of vacuum of 5 to 50 mmHg
Separation yield=(number of lenses separating from mold after suction/total number of lenses cured in mold)100.[Equation 1]

12. A method for making a contact lens, comprising: providing a composition comprising a siloxane monomer represented by Chemical Formula 1; injecting the composition into a contact lens mold; causing the siloxane monomer to polymerize in the contact lens mold to form a contact lens; and releasing the contact lens from the mold, ##STR00086## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently selected from hydrogen, C.sub.1-C.sub.10 alkyl A is selected from the group consisting of ##STR00087## l, m and n are each independently an integer selected from 5 to 150, R.sub.5 is hydrogen or ##STR00088## q is an integer of 5 to 15, R.sub.6 is methyl, R.sub.7 and R.sub.8 are methyl, R.sub.9 is ##STR00089## R.sub.10 is methyl, X.sub.1 and X.sub.2 are each independently a substituent represented by Chemical Formula 3: ##STR00090## o and p are each independently an integer selected from 1 to 10, B is C.sub.6-C.sub.10 arylene, and R.sub.11 is hydrogen or a methyl group.

Description

EXAMPLE 1

(1) 1) Synthesis of Siloxane Monomer

(2) (1) Synthesis of Siloxane Monomer having SiH: Synthesis Step 1

(3) A mixture of 145.3 g (0.49 mol) of octamethylcyclotetrasiloxane, 21.9 g (0.047 mol) of 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane, 5.1 g (0.021 mol) of 1,3,5,7-tetramethyl-cyclotetrasiloxane, 7.4 g (0.014 mol) of 1,3-bis((acryloxymethyl)phenylethyl)tetramethyldisiloxane which is a compound represented by Chemical Formula 4 below, 180 g of chloroform, and 1.50 g of trifluoromethanesulfonic acid was stirred at 25 C. for 48 hours, and then repeatedly washed with purified water until the pH of the mixture became neutral. After the water was separated, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The obtained amount was 131 g (82.3%).

(4) As a result of the analysis, the compound represented by Chemical Formula 1-1 below was synthesized.

(5) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonace, and as a result, SiCH.sub.3 peak at 0.06 to 0.12 ppm, SiCH.sub.2CH.sub.2CF.sub.3 peak at 0.70 ppm (t, 20H), SiCH.sub.2CH.sub.2CF.sub.3 peak at 2.07 ppm (t, 20H), SiH peak at 4.70 ppm (s, 6H), SiCH.sub.2CH.sub.2Ar peak at 0.55 ppm (t, 4H), SiCH.sub.2CH.sub.2Ar peak at 2.71 ppm (t, 4H), ArH peak at 7.55 ppm (m, 8H), ArCH.sub.2O peak at 4.81 ppm (s, 4H), CHCH.sub.2 peak at 5.60 to 6.15 ppm (dd, 4H), and CHCH.sub.2 peak at 5.87 ppm (dd, 2H) were confirmed. The viscosity was measured with a viscometer to confirm that the viscosity was 132 cP. The weight average molecular weight was confirmed to be 12,835 g/mol by GPC analysis.

(6) ##STR00054##

(7) in Chemical Formula above, l=6, m=140, and n=10.

(8) (2) Synthesis of Siloxane Monomer Having PEG Functional Group: Synthesis Step 2

(9) A mixture of 125 g of the above-synthesized siloxane monomer represented by Chemical. Formula 1-1, 31.2 g (0.08 mol) of polyethylene glycol allyl methyl ether represented by Chemical Formula 5 below, 250 g of isopropyl alcohol, and 0.64 ml of a platinum catalyst was placed in a flask equipped with a reflux condenser, and heated under reflux while stirring for 6 hours. The reaction mixture was filtered, then isopropanol was removed under reduced pressure, and the obtained mixture was washed several times with a mixture of acetone and water in a volume ratio of 1:1. A volatile component was further removed under vacuum to obtain a transparent viscous liquid. The obtained amount was 105.2 g and the yield was 72.1%. As a result of the analysis, a compound represented by Chemical Formula 1-2 was synthesized.

(10) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, it was confirmed that OCH.sub.2CH.sub.2 peak was produced at 3.15 to 3.90 ppm. The viscosity was measured with a viscometer to confirm that the viscosity was 321 cP. The weight average molecular weight was confirmed to be 14,972 g/mol by GPC analysis.

(11) ##STR00055##

(12) in Chemical Formula above, l=6, m=140, and n=10.

(13) 2) Preparation of Polymeric Composition

(14) 53.0 g of the siloxane monomer represented by Chemical

(15) Formula 1-2 prepared in 1) above, 42.0 g of N-vinylpyrrolidone (NVP manufactured by Aldrich, V3409) and 4.5 g of 2-hydroxyethyl methacrylate (HEMA manufactured by Aldrich, 128635) as hydrophilic monomers, 0.5 g of ethylene glycol dimethacrylate (EGDMA manufactured by Aldrich, 335681) as a cross-linking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymeric composition.

(16) The above-prepared polymeric 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 C. and polymerized for 1 hour, and the mold was then separated to obtain a lens. The obtained 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.

(17) The releasability and physical properties of the prepared lens were measured and shown in Table 1 below.

EXAMPLE 2

(18) 1) Synthesis of Siloxane Monomer

(19) (1) Synthesis of Siloxane Monomer Having SiH: Synthesis Step 1

(20) A mixture of 145.3 g (0.49 mol) of octamethylcyclotetrasiloxane, 5.1 g (0.021 mol) of 1,3,5,7-tetramethyl-cyclotetrasiloxane, 7.4 g (0.014 mol) of 1,3-bis((acryloxymethyl)phenylethyl)tetramethyldisiloxane, 160 g of chloroform, and 1.5 g of trifluoromethanesulfonic acid was stirred at 25 C. for 24 hours, and then repeatedly washed with purified water until the pH of the mixture became neutral. After the water was separated, chloroform and volatile components were removed under reduced pressure to'obtain a transparent viscous liquid. The obtained amount was 121 g, and the yield was 76.7%.

(21) As a result of the analysis, the compound represented by Chemical Formula 1-3 below was synthesized.

(22) The obtained product was analyzed by 100 MHz hydrogen nuclear magnetic resonance, and as a result, SiCH.sub.3 peak at 0.06 to 0.12 ppm, SiH peak at 4.70 ppm (s, 6H), SiCH.sub.2CH.sub.2Ar peak at 0.55 ppm (t, 4H), SiCH.sub.2CH.sub.2Ar peak at 2.71 ppm (t, 4H), ArH peak at 7.55 ppm (m, 8H), ArCH.sub.2O peak at 4.81 ppm (s, 4H), CHCH.sub.2 peak at 5.60 to 6.15 ppm (dd, 4H), and CHCH.sub.2 peak at 5.87 ppm (dd, 2H) were confirmed. The viscosity was measured with a viscometer to confirm that the viscosity was 111 cP. The weight average molecular weight was confirmed to be 11,270 g/mol by GPC analysis.

(23) ##STR00056##

(24) in Chemical Formula above, l=6, and m=140.

(25) (2) Synthesis of Siloxane Monomer Having PEG Functional Group: Synthesis Step 2

(26) A mixture of 100 g of the above-synthesized siloxane monomer represented by Chemical Formula 1-3, 28.4 g (0.08 mol) of polyethylene glycol allyl methyl ether, 200 g of isopropyl alcohol, and 0.51 ml of a platinum catalyst was placed in a flask equipped with a reflux condenser, and heated under reflux while stirring for 3 hours. The reaction mixture was filtered, then isopropanol was removed under reduced pressure, and the obtained mixture was washed several times with a mixture of acetone and water in a volume ratio of 1:1. A volatile component was further removed under vacuum to obtain a transparent viscous liquid. The obtained amount was 95.2 g and the yield was 80.0%. As a result of the analysis, a compound represented by Chemical Formula 1-4 was synthesized.

(27) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, it was confirmed that OCH.sub.2CH.sub.2 peak was produced at 3.15 to 3.90 ppm. The viscosity was measured with a viscometer to confirm that the viscosity was 308 cP. The weight average molecular weight was confirmed to be 13,408 g/mol by GPC analysis.

(28) ##STR00057##

(29) in Chemical Formula above, l=6, and m=140.

(30) 2) Preparation of Polymeric Composition

(31) 53 g of the siloxane monomer represented by Chemical

(32) Formula 1-4 prepared in 1) above, 42.0 g of N-vinylpyrrolidone (NVP manufactured by Aldrich, V3409) and 4.5 g of 2-hydroxyethyl methacrylate (HEMA manufactured by Aldrich, 128635) as hydrophilic monomers, 0.5 g of ethylene glycol dimethacrylate (EGDMA manufactured by Aldrich, 335681) as a cross-linking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymeric composition.

(33) The above-prepared polymeric 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 C. and polymerized for 1 hour, and the mold was then 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.

(34) The releasability and physical properties of the prepared lens were measured and shown in Table 1 below.

EXAMPLE 3

(35) 1) Synthesis of Siloxane Monomer

(36) A mixture of 145 g (0.49 mol) of octamethylcyclotetrasiloxane, 21.9 g (0.047 mol) of 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane, 7.4 g (0.014 mol) of 1,3-bis((acryloxymethyl)phenylethyl)tetramethyldisiloxane, 180 g of chloroform, and 1.5 g of trifluoromethanesulfonic acid was stirred at 25 C. for 24 hours, and then repeatedly washed with purified water until the pH of the mixture became neutral. After the water was separated, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The obtained amount was 135 g, and the yield was 77.3%.

(37) As a result of the analysis, the compound represented by Chemical Formula 1-5 below was synthesized.

(38) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, SiCH.sub.3 peak at 0.06 to 0.12 ppm, SiCH.sub.2CH.sub.2CF.sub.3 peak at 0.70 ppm (t, 20H), SiCH.sub.2CH.sub.2CF.sub.3 peak at 2.07 ppm (t, 20H), SiCH.sub.2CH.sub.2Ar peak at 0.55 ppm (t, 4H), SiCH.sub.2CH.sub.2Ar peak at 2.71 ppm (t, 4H), ArH peak at 7.55 ppm (m, 8H), ArCH.sub.2O peak at 4.81 ppm (s, 4H), CHCH.sub.2 peak at 5.60 to 6.15 ppm (dd, 4H), and CHCH.sub.2 peak at 5.87 ppm (dd, 2H) were confirmed. The viscosity was measured with a viscometer to confirm that the viscosity was 124 cP. The weight average molecular weight was confirmed to be 12,474 g/mol by GPC analysis.

(39) ##STR00058##

(40) in Chemical Formula above, m=140, and n=10.

(41) 2) Preparation of Polymeric Composition

(42) 42.0 g of the siloxane monomer represented by Chemical

(43) Formula 1-5 prepared in 1) above, 53.0 g of N-vinylpyrrolidone (NVP manufactured by Aldrich, V3409) and 4.5 g of 2-hydroxyethyl methacrylate (HEMA manufactured by Aldrich, 128635) as hydrophilic monomers, 0.5 g of ethylene glycol dimethacrylate (EGDMA manufactured by Aldrich, 335681) as a cross-linking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymeric composition.

(44) The above-prepared polymeric 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 C. and polymerized for 1 hour, and the mold was then 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.

(45) The releasability and physical properties of the prepared lens were measured and shown in Table 1 below.

EXAMPLE 4

(46) 1) Synthesis of Siloxane Monomer

(47) A mixture of 145 g (0.49 mol) of octamethylcyclotetrasiloxane, 21.9 g (0.047 mol) of 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane, 5.1 g (0.021 mol) of 1,3,5,7-tetramethyl-cyclotetrasiloxane, 7.4 g (0.014 mol) of 1,3-bis((acryloxymethyl)phenylethyl)tetramethyldisiloxane, 180 g of chloroform, and 1.50 g of trifluoromethanesulfonic acid was stirred at 25 C. for 24 hours, and then repeatedly washed with purified water until the pH of the mixture became neutral. After the water was separated, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The obtained amount was 131 g (82.3%).

(48) As a result of the analysis, the compound represented by Chemical Formula 1-6 below was synthesized.

(49) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, SiCH.sub.3 peak at 0.06 to 0.12 ppm, SiCH.sub.2CH.sub.2CF.sub.3 peak at 0.70 ppm (t, 20H), SiCH.sub.2CH.sub.2CF.sub.3 peak at 2.07 ppm (t, 20H), SiH peak at 4.70 ppm (s, 6H), SiCH.sub.2CH.sub.2Ar peak at 0.55 ppm (t, 4H), SiCH.sub.2CH.sub.2Ar peak at 2.71 ppm (t, 4H), ArH peak at 7.55 ppm (m, 8H), ArCH.sub.2O peak at 4.81 ppm (s, 4H), CH=CH.sub.2 peak at 5.60 to 6.15 ppm (dd, 4H), and CHCH.sub.2 peak at 5.87 ppm (dd, 2H) were confirmed. The viscosity was measured with a viscometer to confirm that the viscosity was 132 cP. The weight average molecular weight was confirmed to be 12,835 g/mol by GPC analysis.

(50) ##STR00059##

(51) in Chemical Formula above, l=6, m=140, and n=10.

(52) 2) Preparation of Polymeric Composition

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

(54) The above-prepared polymeric 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 C. and polymerized for 1 hour, and the mold was then 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.

(55) The releasability and physical properties of the prepared lens were measured and shown in Table 1 below.

EXAMPLE 5

(56) 1) Synthesis of Siloxane Monomer

(57) A mixture of 145 g (0.49 mol) of octamethylcyclotetrasiloxane, 5.1 g (0.021 mol) of 1,3,5,7-tetramethyl-cyclotetrasiloxane, 7.4 g (0.014 mol) of 1,3-bis((acryloxymethyl)phenylethyl)tetramethyldisiloxane, 160 g of chloroform, and 1.5 g of trifluoromethanesulfonic acid was stirred at 25 C. for 24 hours, and then repeatedly washed with purified water until the pH of the mixture became neutral. After the water was separated, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The obtained amount was 121 g, and the yield was 76.7%.

(58) As a result of the analysis, the compound represented by Chemical Formula 1-7 below was synthesized.

(59) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, SiCH.sub.3 peak at 0.06 to 0.12 ppm, SiH peak at 4.70 ppm (s, 6H), SiCH.sub.2CH.sub.2Ar peak at 0.55 ppm (t, 4H), SiCH.sub.2CH.sub.2Ar peak at 2.71 ppm (t, 4H), ArH peak at 7.55 ppm (m, 8H), AlCH.sub.2O peak at 4.81 ppm (s, 4H), CHCH.sub.2 peak at 5.60 to 6.15 ppm (dd, 4H), and CHCH.sub.2 peak at 5.87 ppm (dd, 2H) were confirmed. The viscosity was measured with a viscometer to confirm that the viscosity was 110 cP. The weight average molecular weight was confirmed to be 11,270 g/mol by GPC analysis.

(60) ##STR00060##

(61) in Chemical Formula above, l=6; and m=140.

(62) 2) Preparation of Polymeric Composition

(63) 30.0 g of the siloxane monomer represented by Chemical Formula 1-7 prepared in 1) above, 65.0 g of N-vinylpyrrolidone (NVP manufactured by Aldrich, V3409) and 4.5 g of 2-hydroxyethyl methacrylate (HEMA manufactured by Aldrich, 128635) as hydrophilic monomers, 0.5 g of ethylene glycol dimethacrylate (EGDMA manufactured by Aldrich, 335681) as a cross-linking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymeric composition.

(64) The above-prepared polymeric 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 C. and polymerized for 1 hour, and the mold was then 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.

(65) The releasability and physical properties of the prepared lens were measured and shown in Table 1 below.

EXAMPLE 6

(66) 1) Synthesis of Siloxane Monomer

(67) A mixture of 74.0 g (0.25 mol) of octamethylcyclotetrasiloxane, 26.3 g (0.050 mol) of 1,3-bis((acryloxymethyl)phenylethyl)tetramethyldisiloxane, 100 g of chloroform, and 0.7 g of trifluoromethanesulfonic acid was stirred at 25 C. for 24 hours, and then repeatedly washed with purified water until the pH of the mixture became neutral. After the water was separated, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The obtained amount was 81.2 g, and the yield was 81.1%.

(68) As a result of the analysis, the compound represented by Chemical Formula 1-8 below was synthesized.

(69) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, SiCH.sub.3 peak at 0.06 to 0.12 ppm, SiCH.sub.2CH.sub.2Ar peak at 0.55 ppm (t, 4H), SiCH.sub.2CH.sub.2Ar peak at 2.71 ppm (t, 4H), ArH peak at 7.55 ppm (m, 8H), ArCH.sub.2O peak at 4.81 ppm (s, 4H), CHCH.sub.2 peak at 5.60 to 6.15 ppm (dd, 4H), and CHCH.sub.2 peak at 5.87 ppm (dd, 2H) were confirmed. The viscosity was measured with a viscometer to confirm that the viscosity was 71 cP. The weight average molecular weight was confirmed to be 2,011 g/mol by GPC analysis.

(70) ##STR00061##

(71) in Chemical Formula above, m=20.

(72) 2) Preparation of Polymeric Composition

(73) 20 g of the siloxane monomer represented by Chemical Formula 1-8 prepared in 1) above, 75.0 g of N-vinylpyrrolidone (NVP manufactured by Aldrich, V3409) and 4.5 g of 2-hydroxyethyl methacrylate (HEMA manufactured by Aldrich, 128635) as hydrophilic monomers, 0.5 g of ethylene glycol dimethacrylate (EGDMA manufactured by Aldrich, 335681) as a cross-linking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymeric composition.

(74) The above-prepared polymeric 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 C. and polymerized for 1 hour, and the mold was then 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.

(75) The releasability and physical properties of the prepared lens were measured and shown in Table 1 below.

EXAMPLE 7

(76) 1) Synthesis of Siloxane Monomer

(77) A mixture of 74.9 g (0.16 mol) of 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane, 25.3 g (0.048 mol) of 1,3-bis((acryloxymethyl)phenylethyl)tetramethyldisiloxane, 100 g of chloroform, and 0.7 g of trifluoromethanesulfonic acid was stirred at 25 C. for 24 hours, and then repeatedly washed with purified water until the pH of the mixture became neutral. After the water was separated, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The obtained amount was 80.5 g, and the yield was 80.3%.

(78) As a result of the analysis, the compound represented by Chemical Formula 1-9 below was synthesized.

(79) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, SiCH.sub.3 peak at 0.06 to 0.12 ppm, SiCH.sub.2CH.sub.2CF.sub.3 peak at 0.70 ppm (t, 20H), SiCH.sub.2CH.sub.2CF.sub.3 peak at 2.07 ppm (t, 20H), SiCH.sub.2CH.sub.2Ar peak at 0.55 ppm (t, 4H), SiCH.sub.2CH.sub.2Ar peak at 2.71 ppm (t, 4H), ArH peak at 7.55 ppm (m, 8H), ArCH.sub.2O peak at 4.81 ppm (s, 4H), CHCH.sub.2 peak at 5.60 to 6.15 ppm (dd, 4H), and CHCH.sub.2 peak at 5.87 ppm (dd, 2H) were confirmed. The viscosity was measured with a viscometer to confirm that the viscosity was 117 cP. The weight average molecular weight was confirmed to be 2,093 g/mol by GPC analysis.

(80) ##STR00062##

(81) in Chemical Formula above, n=10.

(82) 2) Preparation of Polymeric Composition

(83) 15 g of the siloxane monomer represented by Chemical Formula 1-9 prepared in 1) above, 80.0 g of N-vinylpyrrolidone (NVP manufactured by Aldrich, V3409) and 4.5 g of 2-hydroxyethyl methacrylate (HEMA manufactured by Aldrich, 128635) as hydrophilic monomers, 0.5 g of ethylene glycol dimethacrylate (EGDMA manufactured by Aldrich, 335681) as a cross-linking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymeric composition.

(84) The above-prepared polymeric 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 C. and polymerized for 1 hour, and the mold was then 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.

(85) The releasability and physical properties of the prepared lens were measured and shown in Table 1 below.

EXAMPLE 8

(86) 1) Synthesis of Siloxane Monomer

(87) (1) Synthesis of Siloxane Monomer Having SiH: Synthesis Step 1

(88) A mixture of 69.6 g (0.29 mol) of 1,3,5,7-tetramethyl-cyclotetrasiloxane, 30.6 g (0.058 mol) of 1,3-bis((acryloxymethyl)phenylethyl)tetramethyldisiloxane, 100 g of chloroform, and 0.7 g of trifluoromethanesulfonic acid was stirred at 25 C. for 24 hours, and then repeatedly washed with purified water until the pH of the mixture became neutral. After the water was separated, chloroform and volatile components were removed under reduced pressure'to obtain a transparent viscous liquid. The obtained amount was 76.5 g, and the yield was 76.3%.

(89) As a result of the analysis, the compound represented by Chemical Formula 1-10 below was synthesized.

(90) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, SiCH.sub.3 peak at 0.06 to 0.12 ppm, SiH peak at 4.70 ppm (s, 20H), SiCH.sub.2CH.sub.2Ar peak at 0.55 ppm (t, 4H), SiCH.sub.2CH.sub.2Ar peak at 2.71 ppm (t, 4H), ArH peak at 7.55 ppm (m, 8H), ArCH.sub.2O peak at 4.81 ppm (s, 4H), CHCH.sub.2 peak at 5.60 to 6.15 ppm (dd, 4H), and CHCH.sub.2 peak at 5.87 ppm (dd, 2H) were confirmed. The viscosity was measured with a viscometer to confirm that the viscosity was 108 cP. The weight average molecular weight was confirmed to be 1,731 g/mol by GPC analysis.

(91) ##STR00063##

(92) in Chemical Formula above, l=20.

(93) (2) Synthesis of Siloxane Monomer Having PEG Functional Group: Synthesis Step 2

(94) A mixture of 75 g of the above-synthesized siloxane monomer represented by Chemical Formula 1-10, 463 g (1.30 mol) of polyethylene glycol allyl methyl ether, 150 g of isopropyl alcohol, and 0.38 ml of a platinum catalyst was placed in a flask equipped with a reflux condenser, and heated under reflux while stirring for 3 hours. The reaction mixture was filtered, then isopropanol was removed under reduced pressure, and the obtained mixture was washed several times with a mixture of acetone and water in a volume ratio of 1:1. A volatile component was further removed under vacuum to obtain a transparent viscous liquid. The obtained amount was 278 g and the yield was 72.5%. As a result of the analysis, a compound represented by Chemical Formula 1-11 was synthesized.

(95) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, it was confirmed that OCH.sub.2CH.sub.2 peak was produced at 3.15 to 3.90 ppm. The viscosity was measured with a viscometer to confirm that the viscosity was 275 cP. The weight average molecular weight was confirmed to be 8,855 g/mol by GPC analysis.

(96) ##STR00064##

(97) in Chemical Formula above, l=20.

(98) 2) Preparation of Polymeric Composition

(99) 50 g of the siloxane monomer represented by Chemical Formula 1-11 prepared in 1) above, 45.0 g of N-vinylpyrrolidone (NVP manufactured by Aldrich, V3409) and 4.5 g of 2-hydroxyethyl methacrylate (HEMA manufactured by Aldrich, 128635) as hydrophilic monomers, 0.5 g of ethylene glycol dimethacrylate (EGDMA manufactured by Aldrich, 335681) as a cross-linking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymeric composition.

(100) The above-prepared polymeric 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 C. and polymerized for 1 hour, and the mold was then 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.

(101) The releasability and physical properties of the prepared lens were measured and shown in Table 1 below.

EXAMPLE 9

(102) 1) Synthesis of Siloxane Monomer

(103) (1) Synthesis of Siloxane Monomer Having SiH: Synthesis Step 1

(104) A mixture of 84.8 g (0.35 mol) of 1,3,5,7-tetramethyl-cyclotetrasiloxane, 14.9 g(0.028 mol) of 1,3-bis((acryloxymethyl)phenylethyl)tetramethyldisiloxane, 100 g of chloroform, and 0.8 g of trifluoromethanesulfonic acid was stirred at 25 C. for 24 hours, and then repeatedly washed with purified water until the pH of the mixture became neutral. After the water was separated, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The obtained amount was 79.5 g, and the yield was 79.8%.

(105) As a result of the analysis, the compound represented by Chemical Formula 1-12 below was synthesized.

(106) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, SiCH.sub.3 peak at 0.06 to 0.12 ppm, SiH peak at 4.70 ppm (s, 50H), SiCH.sub.2CH.sub.2Ar peak at 0.55 ppm (t, 4H), SiCH.sub.2CH.sub.2Ar peak at 2.71 ppm (t, 4H), ArH peak at 7.55 ppm (m, 8H), ArCH.sub.2O peak at 4.81 ppm (s, 4H), CHCH.sub.2 peak at 5.60 to 6.15 ppm (dd, 4H), and CHCH.sub.2 peak at 5.87 ppm (dd, 2H) were confirmed. The viscosity was measured with a viscometer to confirm that the viscosity was 119 cP. The weight average molecular weight was confirmed to be 3,535 g/mol by GPC analysis.

(107) ##STR00065##

(108) in Chemical Formula above, l=50.

(109) (2) Synthesis of Siloxane Monomer Having PEG Functional Group: Synthesis Step 2

(110) A mixture of 75 g of the above-synthesized siloxane monomer represented by Chemical Formula 1-12, 567 g (1.60 mol) of polyethylene glycol allyl methyl ether, 150 g of isopropyl alcohol, and 0.38 ml of a platinum catalyst was placed in a flask equipped with a reflux condenser, and heated under reflux while stirring for 3 hours. The reaction mixture was filtered, then isopropanol was removed under reduced pressure, and the obtained mixture was washed several times with a mixture of acetone and water in a volume ratio of 1:1. A volatile component was further removed under vacuum to obtain a transparent viscous liquid. The obtained amount was 368 g and the yield was 81.3%. As a result of the analysis, a compound represented by Chemical Formula 1-13 was synthesized.

(111) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, it was confirmed that OCH.sub.2CH.sub.2 peak was produced at 3.15 to 3.90 ppm. The viscosity was measured with a viscometer to confirm that the viscosity was 327 cP. The weight average molecular weight was confirmed to be 21,346 g/mol by GPC analysis.

(112) ##STR00066##

(113) in Chemical Formula above, l=50.

(114) 2) Preparation of Polymeric Composition

(115) 60.0 g of the siloxane monomer represented by Chemical Formula 1-13 prepared in 1) above, 35.0 g of N-vinylpyrrolidone (NVP manufactured by Aldrich, V3409) and 4.5 g of 2-hydroxyethyl methacrylate (HEMA manufactured by Aldrich, 128635) as hydrophilic monomers, 0.5 g of ethylene glycol dimethacrylate (EGDMA manufactured by Aldrich, 335681) as a cross-linking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymeric composition.

(116) The above-prepared polymeric 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 C. and polymerized for 1 hour, and the mold was then 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.

(117) The releasability and physical properties of the prepared lens were measured and shown in Table 1 below.

COMPARATIVE EXAMPLE 1

(118) 1) Synthesis of Siloxane Monomer

(119) (1) Synthesis of Siloxane Monomer Having SiH: Synthesis Step 1

(120) A mixture of 147 g (0.50 mol) of octamethylcyclotetrasiloxane, 22.2 g (0.047 mol) of 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane, 5.1 g (0.021 mol) of 1,3,5,7-tetramethyl-cyclotetrasiloxane, 4.8 g (0.014 mol) of 1,3-bis((methacryloxypropyl)tetramethyldisiloxane) which is a compound represented by Chemical Formula 6 below, 180 g of chloroform, and 1.5 g of trifluoromethanesulfonic acid was stirred at 25 C. for 24 hours, and then repeatedly washed with purified water until the pH of the mixture became neutral. After the water was separated, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The obtained amount was 153 g, and the yield was 85.3%.

(121) As a result of the analysis, the compound represented by Chemical Formula 7-1 below was synthesized.

(122) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, SiCH.sub.3 peak at 0.06 to 0.12 ppm, SiCH.sub.2CH.sub.2CF.sub.3 peak at 0.70 ppm (m, 20H), SiCH.sub.2CH.sub.2CF.sub.3 peak at 2.07 ppm (m, 20H), SiH peak at 4.70 ppm (s, 6H), CHCH.sub.2 peak at 5.606.15 ppm (dd, 4H), CCH.sub.3CH.sub.2 at 1.96 ppm (S, 6H), SiCH.sub.2CH.sub.2CH.sub.2O peak at 0.76 ppm (m, 4H), SiCH.sub.2CH.sub.2CH.sub.2O peak at 1.69 ppm (m, 4H), and SiCH.sub.2CH.sub.2CH.sub.2O peak at 3.94 ppm (m, 4H) were confirmed. The viscosity was measured with a viscometer to confirm that the viscosity was 119 cP. The weight average molecular weight was confirmed to be 12,645 g mol by GPC analysis.

(123) ##STR00067##

(124) in Chemical Formula above, l=6, m=140, and n=10.

(125) (2) Synthesis of Siloxane Monomer Having PEG Functional Group: Synthesis Step 2

(126) A mixture of 125 g of the above-synthesized siloxane monomer represented by Chemical Formula 7-1, 31.7 g (0.089 mol) of polyethylene glycol allyl methyl ether, 250 g of isopropyl alcohol, and 0.64 ml of a platinum catalyst was placed in a flask equipped with a reflux condenser, and heated under reflux while stirring for 3 hours. The reaction mixture was filtered, then isopropanol was removed under reduced pressure, and the obtained mixture was washed several times with a mixture of acetone and water in a volume ratio of 1:1. A volatile component was further removed under vacuum to obtain a transparent viscous liquid. The obtained amount was 114 g and the yield was 78.0%. As a result of the analysis, a compound represented by Chemical Formula 7-2 was synthesized.

(127) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, it was confirmed that OCH.sub.2CH.sub.2 peak was produced at 3.15 to 3.90 ppm. The viscosity was measured with a viscometer to confirm that the viscosity was 295 cP. The weight average molecular weight was confirmed to be 14,782 g/mol by GPC analysis.

(128) ##STR00068##

(129) in Chemical Formula above, l=6, m=140, and n=10.

(130) 2) Preparation of Polymeric Composition

(131) 53 g of the siloxane monomer -represented by Chemical Formula 7-2 prepared in 1) above, 42.0 g of N-vinylpyrrolidone (NVP manufactured by Aldrich, V3409) and 4.5 g of 2-hydroxyethyl methacrylate (HEMA manufactured by Aldrich, 128635) as hydrophilic monomers, 0.5 g of ethylene glycol dimethacrylate (EGDMA manufactured by Aldrich, 335681) as a cross-linking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymeric composition.

(132) The above-prepared polymeric 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 C. and polymerized for 1 hour, and the mold was then 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

(133) 1) Synthesis of Siloxane Monomer

(134) (1) Synthesis of Siloxane Monomer Having SiH: Synthesis Step 1

(135) A mixture of 147 g (0.50 mol) of octamethylcyclotetrasiloxane, 5.1 g (0.021 mol) of 1,3,5,7-tetramethyl-cyclotetrasiloxane, 4.8 g (0.014 mol) of 1,3-bis((methacryloxypropyl)tetramethyldisiloxane, 160 g of chloroform, and 1.5 g of trifluoromethanesulfonic acid was stirred at 25 C. for 24 hours, and then repeatedly washed with purified water until the pH of the mixture became neutral. After the water was separated, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The obtained amount was 135 g, and the yield was 85.9%.

(136) As a result of the analysis, the compound represented by Chemical Formula 8-1 below was synthesized.

(137) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, SiCH.sub.3 peak at 0.06 to 0.12 ppm, SiH peak at 4.70 ppm (s, 6H), CHCH.sub.2 peak at 5.60 to 6.15 ppm (dd, 4H), CCH.sub.3CH.sub.2 peak at 1.96 ppm (S, 6H), SiCH.sub.2CH.sub.2CH.sub.2O peak at 0.76 ppm (m, 4H), SiCH.sub.2CH.sub.2CH.sub.2O peak at 1.69 ppm (m, 4H), and SiCH.sub.2CH.sub.2CH.sub.2O peak at 3.94 ppm (m, 4H) were confirmed. The viscosity was measured with a viscometer to confirm that the viscosity was 104 cP. The weight average molecular weight was confirmed to be 11,080 g/mol by GPC analysis.

(138) ##STR00069##

(139) in Chemical Formula above, l=6 and m=140.

(140) (2) Synthesis of Siloxane Monomer Having PEG Functional Group: Synthesis Step 2

(141) A mixture of 125 g of the above-synthesized siloxane monomer represented by Chemical Formula 8-1, 36.2 g (0.10 mol) of polyethylene glycol allyl methyl ether, 250 g of isopropyl alcohol, and 0.64 ml of a platinum catalyst was placed in a flask equipped with a reflux condenser, and heated under reflux while stirring for 3 hours. The reaction mixture was filtered, then isopropanol was removed under reduced pressure, and the obtained mixture was washed several times with a mixture of acetone and water in a volume ratio of 1:1. A volatile component was further removed under vacuum to obtain a transparent viscous liquid. The obtained amount was 121 g and the yield was 81.1%. As a result of the analysis, a compound represented by Chemical Formula 8-2 was synthesized.

(142) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, it was confirmed that OCH.sub.2CH.sub.2 peak was produced at 3.15 to 3.90 ppm. The viscosity was measured with a viscometer to confirm that the viscosity was 281 cP. The weight average molecular weight was confirmed to be 13,217 g/mol by GPC analysis.

(143) ##STR00070##

(144) in Chemical Formula above, l=6, and m=140.

(145) 2) Preparation of polymeric composition

(146) 53.0 g of the siloxane monomer represented by Chemical

(147) Formula 8-2 prepared in 1) above, 42.0 g of N-vinylpyrrolidone (NVP manufactured by Aldrich, V3409) and 4.5 g of 2-hydroxyethyl methacrylate (HEMA manufactured by Aldrich, 128635) as hydrophilic monomers, 0.5 g of ethylene glycol dimethacrylate (EGDMA manufactured by Aldrich, 335681) as a cross-linking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymeric composition.

(148) The above-prepared polymeric 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 C. and polymerized for 1 hour, and the mold was then 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.

(149) The physical properties of the prepared polymeric composition and the prepared silicone hydrogel contact lens were measured, and the results are shown in Table 1 below.

COMPARATIVE EXAMPLE 3

(150) 1) Synthesis of Siloxane Monomer

(151) A mixture of 147 g (0.50 mol) of octamethylcyclotetrasiloxane, 22.2 g (0.047 mol) of 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane, 4.8 g (0.014 mol) of 1,3-bis(metacryloxympropyl)tetramethyldisiloxane, 180 g of chloroform, and 1.5 g of trifluoromethanesulfonic acid was stirred at 25 C. for 24 hours, and then repeatedly washed with purified water until the pH of the mixture became neutral. After the water was separated, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The obtained amount was 147 g, and the yield was 84.4%.

(152) As a result of the analysis, the compound represented by Chemical Formula 9 below was synthesized.

(153) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, SiCH.sub.3 peak at 0.06 to 0.12 ppm, SiCH.sub.2CH.sub.2CF.sub.3 peak at 0.70 ppm (m, 20H), SiCH.sub.2CH.sub.2CF.sub.3 peak at 2.07 ppm (m, 20H), CHCH.sub.2 peak at 5.60 to 6.15 ppm (dd, 4H), CCH.sub.3CH.sub.2 peak at 1.96 ppm (S, 6H), SiCH.sub.2CH.sub.2CH.sub.2O peak at 0.76 ppm (m, 4H), SiCH.sub.2CH.sub.2CH.sub.2O peak at 1.69 ppm (m, 4H), and SiCH.sub.2CH.sub.2CH.sub.2O peak at 3.94 ppm (m, 4H) were confirmed. The viscosity was measured with a viscometer to confirm that the viscosity was 108 cP. The weight average molecular weight was confirmed to be 12,284 g/mol by GPC analysis.

(154) ##STR00071##

(155) in Chemical Formula above, l=10 and m=140.

(156) 2) Preparation of Polymeric Composition

(157) 42 g of the siloxane monomer represented by Chemical Formula 9 prepared 1) above, 53.0 g of N-vinylpyrrolidone (NVP manufactured by Aldrich, V3409) and 4.5 g of 2-hydroxyethyl methacrylate (HEMA manufactured by Aldrich, 128635) as hydrophilic monomers, 0.5 g of ethylene glycol dimethacrylate (EGDMA manufactured by Aldrich, 335681) as a cross-linking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymeric composition.

(158) The above-prepared polymeric 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 C. and polymerized for 1 hour, and the mold was then 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.

(159) The releasability and physical properties of the prepared lens were measured and shown in Table 1 below.

COMPARATIVE EXAMPLE 4

(160) 1) Synthesis of Siloxane Monomer

(161) A mixture of 147 g (0.07 mol) of octamethylcyclotetrasiloxane, 22.2 g (0.047 mol) of 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane, 5.1 g (0.021 mol) of 1,3,5,7-tetramethyl-cyclotetrasiloxane, 4.8 g (0.014 mol) of 1,3-bis((methacryloxypropyl)tetramethyldisiloxane), 180 g of chloroform, and 1.5 g of trifluoromethanesulfonic acid was stirred at 25 C. for 24, hours, and then repeatedly washed with purified water until the pH of the mixture became neutral. After the water was separated, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The obtained amount was 153 g, and the yield was 85.3%.

(162) As a result of the analysis, the compound represented by Chemical Formula 10 below was synthesized.

(163) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, SiCH.sub.3 peak at 0.06 to 0.12 ppm, SiCH.sub.2CH.sub.2CF.sub.3 peak at 0.70 ppm (m, 20H), SiCH.sub.2CH.sub.2CF.sub.3 peak at 2.07 ppm (m, 20H), SiH peak at 4.70 ppm (s, 6H), CHCH.sub.2 peak at 5.60 to 6.15 ppm (dd, 4H), CCH.sub.3CH.sub.2 at 1.96 ppm (S, 6H), SiCH.sub.2CH.sub.2CH.sub.2O peak at 0.76 ppm (m, .sup.4H), SiCH.sub.2CH.sub.2CH.sub.2O peak at 1.69 ppm (m, 4H), and SiCH.sub.2CH.sub.2CH.sub.2O peak at 3.94 ppm (m, 4H) were confirmed. The viscosity was measured with a viscometer to confirm that the viscosity was 119 cP. The weight average molecular weight was confirmed to be 12,645 g/mol by GPC analysis.

(164) ##STR00072##

(165) in Chemical Formula above, l=6, m=140, and n=10.

(166) 2) Preparation of Polymeric Composition

(167) 30 g of the siloxane monomer represented by Chemical Formula 10 prepared 1) above, 65.0 g of N-vinylpyrrolidone (NVP manufactured by Aldrich, V3409) and 4.5 g of 2-hydroxyethyl methacrylate (HEMA manufactured by Aldrich, 128635) as hydrophilic monomers, 0.5 g of ethylene glycol dimethacrylate (EGDMA manufactured by Aldrich, 335681) as a cross-linking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymeric composition.

(168) The above-prepared polymeric 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 C. and polymerized for 1 hour, and the mold was then 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.

(169) The releasability and physical properties of the prepared lens were measured and shown in Table 1 below.

COMPARATIVE EXAMPLE 5

(170) 1) Synthesis of Siloxane Monomer

(171) A mixture of 147 g (0.50 mol) of octamethylcyclotetrasiloxane, 5.1 g (0.021 mol) of 1,3,5,7-tetramethyl-cyclotetrasiloxane, 4.8 g (0.014 mol) of 1,3-bis((methacryloxypropyl)tetramethyldisiloxane, 160 g of chloroform, and 1.5 g of trifluoromethanesulfonic acid was stirred at 25 C. for 24 hours, and then repeatedly washed with purified water until the pH of the mixture became neutral. After the water was separated, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The obtained amount was 135 g, and the yield was 85.9%.

(172) As a result of the analysis, the compound represented by Chemical Formula 11 below was synthesized.

(173) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, SiCH.sub.3 peak at 0.06 to 0.12 ppm, SiH peak at 4.70 ppm (s, 6H), CHCH.sub.2 peak at 5.60 to 6.15 ppm (dd, 4H), CCH.sub.3CH.sub.2 peak at 1.96 ppm (S, 6H), SiCH.sub.2CH.sub.2CH.sub.2O peak at 0.76 ppm (m, 4H), SiCH.sub.2CH.sub.2CH.sub.2O peak at 1.69 ppm (m, 4H), and SiCH.sub.2CH.sub.2CH.sub.2O peak at 3.94 ppm (m, 4H) were confirmed. The viscosity was measured with a viscometer to confirm that the viscosity was 104 cP. The weight average molecular weight was confirmed to be 11,080 g/mol by GPC analysis.

(174) ##STR00073##

(175) in Chemical Formula above, l=6 and m=140.

(176) 2) Preparation of Polymeric Composition

(177) 30 g of the siloxane monomer represented by Chemical Formula 11 prepared 1) above, 65.0 g of N-vinylpyrrolidone (NVP manufactured by Aldrich, V3409) and 4.5 g of 2-hydroxyethyl methacrylate (HEMA manufactured by Aldrich, 128635) as hydrophilic monomers, 0.5 g of ethylene glycol dimethacrylate (EGDMA manufactured by Aldrich, 335681) as a cross-linking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymeric composition.

(178) The above-prepared polymeric 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 C. and polymerized for 1 hour, and the mold was then 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.

(179) The releasability and physical properties of the prepared lens were measured and shown in Table 1 below.

COMPARATIVE EXAMPLE 6

(180) 1) Synthesis of Siloxane Monomer

(181) A mixture of 0.81 g (0.28 mol) of octamethylcyclotetrasiloxane, 18.6 g (0.055 mol) of 1,3-bis(metacryloxypropyl)tetramethyldisiloxane, 100 g of chloroform, and 0.8 g of trifluoromethanesulfonic acid was stirred at 25 C. for 24 hours, and then repeatedly washed with purified water until the pH of the mixture became neutral. After the water was separated, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The obtained amount was 82.1 g, and the yield was 82.0%.

(182) As a result of the analysis, the compound represented by Chemical Formula 12 below was synthesized.

(183) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, SiCH.sub.3 peak at 0.06 to 0.12 ppm, CHCH.sub.2 peak at 5.60 to 6.15 ppm (dd, 4H), CCH.sub.3CH.sub.2 peak at 1.96 ppm (S, 6H), SiCH.sub.2CH.sub.2CH.sub.2O peak at 0.76 ppm (m, 4H), SiCH.sub.2CH.sub.2CH.sub.2O peak at 1.69 ppm (m, 4H), and SiCH.sub.2CH.sub.2CH.sub.2O peak at 3.94 ppm (m, 4H) were, confirmed. The viscosity was measured with a viscometer to confirm that the viscosity was 70 cP. The weight average molecular weight was confirmed to be 1,821 g/mol by GPC analysis.

(184) ##STR00074##

(185) in Chemical Formula above, m=20.

(186) 2) Preparation of Polymeric Composition

(187) 20 g of the siloxane monomer represented by Chemical Formula 12 prepared 1) above, 75 g of N-vinylpyrrolidone (NVP manufactured by Aldrich, V3409) and 4.5 g of 2-hydroxyethyl methacrylate (HEMA manufactured by Aldrich, 128635) as hydrophilic monomers, 0.5 g of ethylene glycol dimethacrylate (EGDMA manufactured by Aldrich, 335681) as a cross-linking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymeric composition.

(188) The above-prepared polymeric 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 C. and polymerized for 1 hour, and the mold was then 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.

(189) The releasability and physical properties of the prepared lens were measured and shown in Table 1 below.

COMPARATIVE EXAMPLE 7

(190) 1) Synthesis of Siloxane Monomer

(191) A mixture of 82.3 g (0.18 mol) of 1,3,5-trimethyltrifluoropropyl-cyclotrisiloxane, 17.8 g (0.053 mol) of 1,3-bis(metacryloxypropyl)tetramethyldisiloxane, 100 g of chloroform, and 0.8 g of trifluoromethanesulfonic acid was stirred at 25 C. for 24 hours, and then repeatedly washed with purified water until the pH of the mixture became neutral. After the water was separated, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The obtained amount was 81.6 g, and the yield was 81.5%.

(192) As a result of the analysis, the compound represented by Chemical Formula 13 below was synthesized.

(193) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, SiCH.sub.3 peak at 0.06 to 0.12 ppm, SiCH.sub.2CH.sub.2CF.sub.3 peak at 0.70 ppm (m, 20H), SiCH.sub.2CH.sub.2CF.sub.3 peak at 2.07 ppm (m, 20H), CHCH.sub.2 peak at 5.60 to 6.15 ppm (dd, 4H), CCH.sub.3CH.sub.2 peak at 1.96 ppm (S, 6H), SiCH.sub.2CH.sub.2CH.sub.2O peak at 0.76 ppm (m, 4H), SiCH.sub.2CH.sub.2CH.sub.2O peak at 1.69 ppm (m, 4H), and SiCH.sub.2CH.sub.2CH.sub.2O peak at 3.94 ppm (m, 4H) were confirmed. The viscosity was measured with a viscometer to confirm that the viscosity was 109 cP. The weight average molecular weight was confirmed to be 1,903 g/mol measured by GPC analysis.

(194) ##STR00075##

(195) in Chemical Formula above, n=10.

(196) 2) Preparation of Polymeric Composition

(197) 15 g of the siloxane monomer represented by Chemical Formula 13 prepared 1) above, 80.0 g of N-vinylpyrrolidone (NVP manufactured by Aldrich, V3409) and 4.5 g of 2-hydroxyethyl methacrylate (HEMA manufactured by Aldrich, 128635) as hydrophilic monomers, 0.5 g of ethylene glycol dimethacrylate (EGDMA manufactured by Aldrich, 335681) as a cross-linking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymeric composition.

(198) The above-prepared polymeric 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 C. and polymerized for 1 hour, and the mold was then separated to obtain a lens. The obtained lens was immersed in deionized water for 1 hour, arid then subjected to high pressure sterilization in a phosphate buffered saline solution to prepare a silicone hydrogel contact lens.

(199) The releasability and physical properties of the prepared lens were measured and shown in Table 1 below.

COMPARATIVE EXAMPLE 8

(200) 1) Synthesis of Siloxane Monomer

(201) (1) Synthesis of Siloxane Monomer Having SiH: Synthesis Step 1

(202) A mixture of 78.1 g (0.35 mol) of 1,3,5,7-tetramethyl-cyclotetrasiloxane, 22.0 g(0.028 mol) of 1,3-bis(metacryloxypropyl)tetramethyldisiloxane, 100 g of chloroform, and 0.8 g of trifluoromethanesulfonic acid was stirred at 25 C. for 24 hours, and then repeatedly washed with purified water until the pH of the mixture became neutral. After the water was separated, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The obtained amount was 82.3 g, and the yield was 82.2%.

(203) As a result of the analysis, the compound represented by Chemical Formula 14-1 below was synthesized.

(204) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, SiCH.sub.3 peak at 0.06 to 0.12 ppm, SiH peak at 4.70 ppm (s, 20H), CHCH.sub.2 peak at 5.60 to 6.15 ppm (dd, 4H), CCH.sub.3CH.sub.2 peak at 1.96 ppm (S, 6H), SiCH.sub.2CH.sub.2CH.sub.2O peak at 0.76 ppm (m, 4H), SiCH.sub.2CH.sub.2CH.sub.2O peak at 1.69 ppm (m, 4H), and SiCH.sub.2CH.sub.2CH.sub.2O peak at 3.94 ppm (m, 4H) were confirmed. The viscosity was measured with a viscometer to confirm that the viscosity was 103 cP. The weight average molecular weight was confirmed to be 1,541 g/mol measured by GPC analysis.

(205) ##STR00076##

(206) in Chemical Formula above, n=20.

(207) (2) Synthesis of Siloxane Monomer Having PEG Functional Group: Synthesis Step 2

(208) A mixture of 75 g of the above-synthesized siloxane monomer represented by Chemical Formula 14-1, 520 g (1.46 mol) of polyethylene glycol allyl methyl ether, 150 g of isopropyl alcohol, and 0.38 ml of a platinum catalyst was placed in a flask equipped with a reflux condenser, and heated under reflux while stirring for 3 hours. The reaction mixture was filtered, then isopropanol was removed under reduced pressure, and the obtained mixture was washed several times with a mixture of acetone and water in a volume ratio of 1:1. A volatile component was further removed under vacuum to obtain a transparent viscous liquid. The obtained amount was 357 g and the yield was 84.7%. As a result of the analysis, a compound represented by Chemical Formula 14-2 was synthesized.

(209) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, it was confirmed that OCH.sub.2CH.sub.2 peak was produced at 3.15 to 3.90 ppm. The viscosity was measured with a viscometer to confirm that the viscosity was 277 cP. The weight average molecular weight was confirmed to be 8,665 g/mol measured by GPC analysis.

(210) ##STR00077##

(211) in Chemical Formula above, n=6.

(212) 2) Preparation of Polymeric Composition

(213) 50 g of the siloxane monomer represented by Chemical

(214) Formula 14-2 prepared in 1) above, 45.0 g of N-vinylpyrrolidone (NVP manufactured by Aldrich, V3409) and 4.5 g of 2-hydroxyethyl methacrylate (HEMA manufactured by Aldrich, 128635) as hydrophilic monomers, 0.5 g of ethylene glycol dimethacrylate (EGDMA manufactured by Aldrich, 335681) as a cross-linking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymeric composition.

(215) The above-prepared polymeric 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 C. and polymerized for 1 hour, and the mold was then 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.

(216) The releasability and physical properties of the prepared lens were measured and shown in Table 1 below.

COMPARATIVE EXAMPLE 9

(217) 1) Synthesis of Siloxane Monomer

(218) (1) Synthesis of Siloxane Monomer Having SiH: Synthesis Step 1

(219) A mixture of 90.6 g (0.38 mol) of 1,3,5,7-tetramethyl-cyclotetrasiloxane, 10.2 g (0.30 mol) of 1,3-bis(metacryloxypropyl)tetramethyldisiloxane, 100 g of chloroform, and 0.9 g of trifluoromethanesulfonic acid was stirred at 25 C. for 24 hours, and then repeatedly washed with purified water until the pH of the mixture became neutral. After the water was separated, chloroform and volatile components were removed under reduced pressure to obtain a transparent viscous liquid. The obtained amount was 83.5 g, and the yield was 82.9%.

(220) As a result of the analysis, the compound represented by Chemical Formula 15-1 below was synthesized.

(221) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, SiCH.sub.3 peak at 0.06 to 0.12 ppm, SiH peak at 4.70 ppm (s, 50H), CHCH.sub.2 peak at 5.60 to 6.15 ppm (dd, 4H), CCH.sub.3CH.sub.2 peak at 1.96 ppm (S, 6H), SiCH.sub.2CH.sub.2CH.sub.2O peak at 0.76 ppm (m, 4H), SiCH.sub.2CH.sub.2CH.sub.2O peak at 1.69 ppm (m, 4H), and SiCH.sub.2CH.sub.2CH.sub.2O peak at 3.94 ppm (m, 4H) were confirmed. The viscosity was measured with a viscometer to confirm that the viscosity was 121 cP. The weight average molecular weight was confirmed to be 3,345 g/mol measured by GPC analysis.

(222) ##STR00078##

(223) in Chemical Formula above, n=50.

(224) (2) synthesis of Siloxane Monomer Having PEG Functional Group: Synthesis Step 2

(225) A mixture of 75 g of the above-synthesized siloxane monomer represented by Chemical Formula 15-1, 599 g (1.46 mol) of, polyethylene glycol allyl methyl ether, 150 g of isopropyl alcohol, and 0.38 ml of a platinum catalyst was placed in a flask equipped with a reflux condenser, and heated under reflux while stirring for 3 hours. The reaction mixture was filtered, then isopropanol was removed under reduced pressure, and the obtained mixture was washed several times with a mixture of acetone and water in a volume ratio of 1:1. A volatile component was further removed under vacuum to obtain a transparent viscous liquid. The obtained amount was 378 g and the yield was 79.7%. As a result of the analysis, a compound represented by Chemical Formula 15-2 was synthesized.

(226) The obtained product was analyzed by 400 MHz hydrogen nuclear magnetic resonance, and as a result, it was confirmed that OCH.sub.2CH.sub.2 peak was produced at 3.15 to 3.90 ppm. The viscosity was measured with a viscometer to confirm that the viscosity was 340 cP. The weight average molecular weight was confirmed to be 21,156 g/mol measured by GPC analysis.

(227) ##STR00079##

(228) in Chemical Formula above, n=50.

(229) 2) Preparation of Polymeric Composition

(230) 60 g of the siloxane monomer represented by Chemical Formula 15-2 prepared in 1) above, 35.0 g of N-vinylpyrrolidone (NVP manufactured by Aldrich, V3409) and 4.5 g of 2-hydroxyethyl methacrylate (HEMA manufactured by Aldrich, 128635) as hydrophilic monomers, 0.5 g of ethylene glycol dimethacrylate (EGDMA manufactured by Aldrich, 335681) as a cross-linking agent, and 0.05 g of azobisisobutylonitrile (AIBN) as an initiator were mixed to prepare a polymeric composition.

(231) The above-prepared polymeric 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 C. and polymerized for 1 hour, and the mold was then 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.

(232) The releasability and physical properties of the prepared lens were measured and shown in Table 1 below.

(233) TABLE-US-00001 TABLE 1 Oxygen Releasability Water permeability (separation yield) content coefficient Example 1 Excellent (92%) 45% 115 Example 2 Excellent (93%) 49% 108 Example 3 Excellent (95%) 55% 87 Example 4 Excellent (88%) 40% 121 Example 5 Excellent (91%) 57% 78 Example 6 Excellent (89%) 59% 65 Example 7 Excellent (92%) 60% 57 Example 8 Excellent (90%) 42% 97 Example 9 Excellent (89%) 38% 132 Comparative Normal (33%) 47% 105 Example 1 Comparative Normal (31%) 51% 101 Example 2 Comparative Poor (15%) 56% 81 Example 3 Comparative Poor (22%) 43% 115 Example 4 Comparative Poor (29%) 61% 82 Example 5 Comparative Poor (25%) 57% 61 Example 6 Comparative Poor (18%) 58% 59 Example 7 Comparative Normal (35%) 44% 101 Example 8 Comparative Poor (11%) 41% 122 Example 9

(234) As shown in Table 1, it could be appreciated that Examples to 9 according to the present invention had lower adhesion than those of Comparative Examples 1 to 9 to be easily releasable from a mold using a suction of a separator. On the other hand, it could be appreciated that Comparative Examples 1 to 9 had the separation yield of about 10% to 30%, which was difficult to be applied to the process.

(235) Further, as shown in Examples 1 to 3, it could be appreciated that the oxygen permeability coefficient increased as the content of the siloxane monomer of the present invention increased.

(236) Further, in Comparative Examples 1 to 9 in which the siloxane monomer containing no aromatic ring was used, when the lens was forcibly released from the mold, the lens was damaged, and the lens could be separated from the mold without damaging the lens only when applying the conventional method using a solvent.