High-oxygen-permeability silica hydrogel and silica hydrogel contact lens

Abstract

The invention belongs to the technical field of contact lenses, and provides a high-oxygen-permeability silica hydrogel and a silica hydrogel contact lens. The product is prepared from the following raw materials in parts by mass: 20 to 90 parts of organic silicon monomer, 20 to 80 parts of hydrophilic monomer, 0.1 to 5 parts of cross-linking agent, 0.2 to 7 parts of initiator and 20 to 50 parts of solvent. Symmetrical monomethacryloyloxy propyl modified polydimethylsiloxane, methyl-di (trimethylsiloxy)-silyl propyl glyceryl methacrylate and 2-(trimethylsiloxy) ethyl methacrylate are selected as organic silicon monomers together, and the three organic silicon monomers cooperate with one another, so that the viscosity of the organic silicon resin is improved; the oxygen permeability of the lens is improved; and the three organic silicon monomers and the hydrophilic monomer have good solubility. In addition, the sample is soaked in an isopropanol solution, so that the transparency of the lens is improved, and meanwhile, a channel on the lens is opened, so that the oxygen permeation coefficient of the lens is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of contact lenses, and in particular to a highly oxygen permeable silicone hydrogel and a silicone hydrogel contact lens. Background Art

[0002] Corneal contact lenses, also known as "contact lenses", are lenses worn on the cornea of ​​the eye to correct vision. Compared with ordinary glasses, they are beautiful, convenient and comfortable to wear, so they have always been loved by people. Hydrogels have good biocompatibility, excellent hydrophilicity and air permeability, and are therefore widely used in the field of contact lenses. However, the overall oxygen permeability of traditional hydrogels is relatively low. And oxygen permeability is the primary factor that determines the length of time contact lenses are worn. Under normal circumstances, our cornea needs to "breathe". After wearing contact lenses, if the oxygen permeability of the lenses is low, it will cause corneal hypoxia, and long-term corneal hypoxia can easily lead to complications such as chronic corneal edema and corneal neovascularization. Therefore, it is of great significance to provide a contact lens that meets the needs of the contact lens field and has high oxygen permeability. Summary of the invention

[0003] The purpose of the present invention is to overcome the problems existing in the prior art and provide a highly oxygen permeable silicone hydrogel and a silicone hydrogel contact lens.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides a high oxygen permeability silicone hydrogel, comprising the following raw materials in parts by weight:

[0006] 20-90 parts of organosilicon monomer, 20-80 parts of hydrophilic monomer, 0.1-5 parts of crosslinking agent, 0.2-7 parts of initiator and 20-50 parts of solvent;

[0007] The organic silicon monomer comprises symmetrical monomethacryloxypropyl modified polydimethylsiloxane, methyl-bis(trimethylsiloxy)-silylpropyl methacrylate and 2-(trimethylsiloxy)ethyl methacrylate.

[0008] Preferably, the mass ratio of the symmetrical monomethacryloxypropyl modified polydimethylsiloxane, methyl-bis(trimethylsiloxy)-silylpropyl methacrylate and 2-(trimethylsiloxy)ethyl methacrylate is 4-6:1-3:2-4.

[0009] Preferably, the hydrophilic monomer comprises hydroxyethyl methacrylate, N-vinyl pyrrolidone and N,N-dimethylacrylamide;

[0010] The mass ratio of hydroxyethyl methacrylate, N-vinyl pyrrolidone and N,N-dimethylacrylamide is 3-5:2-4:0.5-1.5.

[0011] Preferably, the crosslinking agent includes trimethylolpropane trimethacrylate or trimethylolpropane triacrylate.

[0012] Preferably, the initiator includes azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide or D1173.

[0013] Preferably, the solvent includes one or more of isopropanol, ethanol, n-hexanol and n-butanol.

[0014] The present invention also provides a silicone hydrogel contact lens, which is prepared by using highly oxygen-permeable silicone hydrogel.

[0015] Preferably, the method for preparing the silicone hydrogel contact lens comprises the following steps:

[0016] The raw materials are mixed and injected into a mold to carry out a polymerization reaction. After the polymerization reaction is completed, the obtained sample is immersed in an isopropanol solution and taken out to obtain the silicone hydrogel contact lens.

[0017] Preferably, the mass fraction of the isopropanol solution is 5-20%; and the soaking time is 0.5-2h.

[0018] The beneficial effects of the present invention are:

[0019] The present invention provides a highly oxygen permeable silicone hydrogel, comprising the following raw materials in parts by weight: 20 to 90 parts of silicone monomer, 20 to 80 parts of hydrophilic monomer, 0.1 to 5 parts of crosslinking agent, 0.2 to 7 parts of initiator and 20 to 50 parts of solvent. The present invention selects symmetrical monomethacryloxypropyl modified polydimethylsiloxane, methyl-bis(trimethylsiloxane)-silylpropyl methacrylate and 2-(trimethylsiloxy)ethyl methacrylate as silicone monomers. The three silicone monomers cooperate with each other to improve the oxygen permeability of the lens; and the three silicone monomers have good solubility with the hydrophilic monomer, which further improves the comprehensive performance of the silicone hydrogel. In addition, the present invention also provides a silicone hydrogel contact lens, and the preparation method comprises the following steps: mixing the raw materials, injecting them into a mold, and performing a polymerization reaction. After the polymerization reaction is completed, the obtained sample is immersed in an isopropanol solution, taken out, and a silicone hydrogel contact lens is obtained. The present invention soaks the sample in an isopropanol solution, which can improve the transparency of the lens and open the channels on the lens, thereby improving the oxygen permeability coefficient of the lens. DETAILED DESCRIPTION

[0020] The present invention provides a high oxygen permeability silicone hydrogel, comprising the following raw materials in parts by weight:

[0021] 20-90 parts of organosilicon monomer, 20-80 parts of hydrophilic monomer, 0.1-5 parts of crosslinking agent, 0.2-7 parts of initiator and 20-50 parts of solvent;

[0022] The organic silicon monomer comprises symmetrical monomethacryloxypropyl modified polydimethylsiloxane, methyl-bis(trimethylsiloxy)-silylpropyl methacrylate and 2-(trimethylsiloxy)ethyl methacrylate.

[0023] In the present invention, the mass fraction of the organosilicon monomer is 20 to 90 parts, preferably 40 to 75 parts, more preferably 50 to 70 parts, and even more preferably 60 to 65 parts.

[0024] In the present invention, the mass fraction of the hydrophilic monomer is 20 to 80 parts, preferably 25 to 70 parts, more preferably 30 to 50 parts, and even more preferably 40 to 45 parts.

[0025] In the present invention, the mass fraction of the crosslinking agent is 0.1 to 5 parts, preferably 0.2 to 4 parts, more preferably 0.7 to 3 parts, and even more preferably 1 to 1.5 parts.

[0026] In the present invention, the mass fraction of the initiator is 0.2 to 7 parts, preferably 0.5 to 5 parts, more preferably 1.0 to 2.5 parts, and even more preferably 1.3 to 1.8 parts.

[0027] In the present invention, the mass fraction of the solvent is 20 to 50 parts, preferably 30 to 45 parts, more preferably 35 to 42 parts, and even more preferably 37 to 40 parts.

[0028] In the present invention, the mass ratio of the symmetrical monomethacryloxypropyl modified polydimethylsiloxane, methyl-bis(trimethylsiloxy)-silylpropyl methacrylate and 2-(trimethylsiloxy)ethyl methacrylate is preferably 4-6:1-3:2-4, more preferably 4.5-5.5:1.5-2.5:2.5-3.5, and more preferably 5:2:3.

[0029] In the present invention, the hydrophilic monomer preferably comprises hydroxyethyl methacrylate, N-vinyl pyrrolidone and N,N-dimethylacrylamide; the mass ratio of hydroxyethyl methacrylate, N-vinyl pyrrolidone and N,N-dimethylacrylamide is preferably 3-5:2-4:0.5-1.5, more preferably 3.5-4.5:2.5-3.5:0.7-1.3, and more preferably 4:3:1.

[0030] In the present invention, the crosslinking agent preferably includes trimethylolpropane trimethacrylate or trimethylolpropane triacrylate.

[0031] In the present invention, the initiator preferably includes azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide or D1173.

[0032] In the present invention, the solvent preferably includes one or more of isopropanol, ethanol, n-hexanol and n-butanol.

[0033] The present invention also provides a silicone hydrogel contact lens, which is prepared by using highly oxygen-permeable silicone hydrogel.

[0034] In the present invention, the method for preparing the silicone hydrogel contact lens preferably comprises the following steps:

[0035] The raw materials are mixed and injected into a mold to carry out a polymerization reaction. After the polymerization reaction is completed, the obtained sample is immersed in an isopropanol solution and taken out to obtain the silicone hydrogel contact lens.

[0036] In the present invention, the polymerization reaction is preferably carried out in a photo-induced polymerization reaction or a heat-induced polymerization reaction. When the polymerization reaction is carried out in a photo-induced polymerization reaction, the illumination of the ultraviolet light is preferably 80 to 120 lx, more preferably 90 to 110 lx, and more preferably 100 lx; ​​the polymerization reaction time is preferably 30 to 40 min, more preferably 32 to 38 min, and more preferably 35 min; when the polymerization reaction is carried out in a heat-induced polymerization reaction, the polymerization reaction temperature is preferably 100 to 120°C, more preferably 105 to 115°C, and more preferably 110°C; the polymerization reaction time is preferably 0.5 to 1.5 h, more preferably 0.7 to 1.3 h, and more preferably 1 h.

[0037] In the present invention, after the polymerization reaction is completed, the mold containing the sample is immersed in purified water, and the sample is obtained after demolding; then, the sample is immersed in an isopropanol solution, taken out after the immersion, and immersed in purified water for 20 to 30 minutes, and the soaking process in purified water is repeated 1 to 2 times, and finally taken out, immersed in a sodium chloride solution, and taken out to obtain the silicone hydrogel contact lens.

[0038] In the present invention, the mass fraction of the isopropanol solution is preferably 5-20%, more preferably 8-15%, and more preferably 10-12%; the immersion time in the isopropanol solution is preferably 0.5-2h, more preferably 0.8-1.8h, and more preferably 1.2-1.6h; the mass fraction of the sodium chloride solution is preferably 0.7-1.1%, more preferably 0.8-1.0%, and more preferably 0.9%; the immersion time in the sodium chloride solution is preferably 0.5-2h, more preferably 0.8-1.8h, and more preferably 1.2-1.6h.

[0039] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0040] Example 1

[0041] 32.5 parts of symmetrical monomethacryloxypropyl modified polydimethylsiloxane, 13 parts of methyl-bis(trimethylsiloxy)-silylpropyl methacrylate, 19.5 parts of 2-(trimethylsiloxy)ethyl methacrylate, 20 parts of hydroxyethyl methacrylate, 15 parts of N-vinyl pyrrolidone, 5 parts of N,N-dimethylacrylamide, 1 part of trimethylolpropane trimethacrylate, 1.8 parts of azobisisobutyronitrile and 40 parts of ethanol are mixed and injected into a mold, and a polymerization reaction is carried out at 110° C. The polymerization reaction time is set to 1 hour. After the reaction is completed, the mold containing the sample is immersed in purified water, and the sample is demolded to obtain the sample; then, the sample is immersed in an isopropanol solution with a mass fraction of 8% for 1.6 hours, taken out after the immersion, immersed in purified water for 30 minutes, the immersion process in purified water is repeated once, and finally taken out, immersed in a sodium chloride solution with a mass fraction of 0.9% for 1.2 hours, and taken out to obtain the silicone hydrogel contact lens.

[0042] Example 2

[0043] 30 parts of symmetrical monomethacryloxypropyl modified polydimethylsiloxane, 12.5 parts of methyl-bis(trimethylsiloxy)-silylpropyl methacrylate, 17.5 parts of 2-(trimethylsiloxy)ethyl methacrylate, 25 parts of hydroxyethyl methacrylate, 15 parts of N-vinyl pyrrolidone, 5 parts of N,N-dimethylacrylamide, 1.5 parts of trimethylolpropane triacrylate, 1.3 parts of azobisisoheptonitrile and 37 parts of n-butanol were mixed and injected into a mold and heated for 11 min. The polymerization reaction was carried out at 5°C, and the polymerization reaction time was set to 0.7h. After the reaction was completed, the mold containing the sample was immersed in purified water, and the sample was obtained after demolding; then, the sample was immersed in a 10% by mass isopropanol solution for 1.2h, taken out after the immersion, immersed in purified water for 20min, and the soaking process in purified water was repeated twice, and finally taken out, immersed in a 0.9% by mass sodium chloride solution for 0.8h, and taken out to obtain the silicone hydrogel contact lens.

[0044] Example 3

[0045] 22.5 parts of symmetrical monomethacryloxypropyl modified polydimethylsiloxane, 5 parts of methyl-bis(trimethylsiloxy)-silylpropyl methacrylate, 12.5 parts of 2-(trimethylsiloxy)ethyl methacrylate, 15 parts of hydroxyethyl methacrylate, 10 parts of N-vinyl pyrrolidone, 5 parts of N,N-dimethylacrylamide, 0.7 parts of trimethylolpropane trimethacrylate, 1.0 parts of D1173 and 30 parts of n-hexanol were mixed and injected into a mold and heated at 100 °C. The polymerization reaction was carried out under 1x ultraviolet light, and the polymerization reaction time was set to 35 minutes. After the reaction was completed, the mold containing the sample was immersed in purified water, and the sample was obtained after demolding; then, the sample was immersed in an isopropanol solution with a mass fraction of 12% for 0.8 hours, taken out after the immersion, immersed in purified water for 30 minutes, and the soaking process in purified water was repeated once, and finally taken out, immersed in a sodium chloride solution with a mass fraction of 0.9% for 1 hour, and taken out to obtain the silicone hydrogel contact lens.

[0046] Example 4

[0047] 42 parts of symmetrical monomethacryloxypropyl modified polydimethylsiloxane, 14 parts of methyl-bis(trimethylsiloxy)-silylpropyl methacrylate, 14 parts of 2-(trimethylsiloxy)ethyl methacrylate, 25 parts of hydroxyethyl methacrylate, 20 parts of N-vinyl pyrrolidone, 5 parts of N,N-dimethylacrylamide, 3 parts of trimethylolpropane triacrylate, 2.5 parts of azobisisobutyronitrile and 45 parts of ethanol are mixed and injected into a mold, and a polymerization reaction is carried out at 110° C. The polymerization reaction time is set to 1 hour. After the reaction is completed, the mold containing the sample is immersed in purified water, and the sample is demoulded to obtain the sample; then, the sample is immersed in an isopropanol solution with a mass fraction of 15% for 0.5 hour, taken out after the immersion, immersed in purified water for 20 minutes, the immersion process in purified water is repeated twice, and finally taken out, immersed in a sodium chloride solution with a mass fraction of 0.9% for 1.6 hours, and taken out to obtain the silicone hydrogel contact lens.

[0048] Comparative Example 1

[0049] The other conditions in Example 1 were kept unchanged, methyl-bis(trimethylsiloxy)-silylpropyl methacrylate and 2-(trimethylsiloxy)ethyl methacrylate were omitted, and the weight fraction of the symmetrical monomethacryloxypropyl modified polydimethylsiloxane was changed to 65 parts.

[0050] Comparative Example 2

[0051] The other conditions in Example 1 were kept unchanged, the addition of the symmetrical monomethacryloxypropyl modified polydimethylsiloxane was omitted, and the mass fractions of methyl-bis(trimethylsiloxy)-silylpropyl methacrylate were modified to 26 parts and 2-(trimethylsiloxy)ethyl methacrylate to 39 parts.

[0052] Comparative Example 3

[0053] The other conditions in Example 1 are controlled to remain unchanged, and the mold containing the sample is immersed in purified water. After demolding, the silicone hydrogel contact lens is directly obtained.

[0054] The performance of the silicone hydrogel contact lenses prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were tested respectively, and the performance test results of different silicone hydrogel contact lenses are recorded in Table 1. Among them, the oxygen permeability coefficient is obtained by the coulometric method according to the national standard (GBT11417.3-2012), and the unit is (cm 2 / s)(mLO2 / mL·mmHg); the test formula for water content is: water content = (M2-M1) / M1*100%, M1 is dry weight, M2 is wet weight, the unit is %; the elongation at break is obtained by using an electronic tensile testing machine XLW (PC) and the unit is %; the transmittance is obtained by using an ultraviolet spectrophotometer and the unit is %.

[0055] Table 1 Performance test results of different silicone hydrogel contact lenses

[0056] Case Oxygen permeability Water content Elongation at break Light transmittance Example 1 <![CDATA[263*10 -11 ]]> 61 225 98.5 Example 2 <![CDATA[256*10 -11 ]]> 63 218 99 Example 3 <![CDATA[239*10 -11 ]]> 55 223 98.5 Example 4 <![CDATA[241*10 -11 ]]> 58 215 98 Comparative Example 1 <![CDATA[195*10 -11 ]]> 41 198 96 Comparative Example 2 <![CDATA[162*10 -11 ]]> 45 179 98 Comparative Example 3 <![CDATA[188*10 -11 ]]> 47 203 96

[0057] It can be seen from the above embodiments that the present invention provides a highly oxygen permeable silicone hydrogel, comprising the following raw materials by mass: 20 to 90 parts of silicone monomer, 20 to 80 parts of hydrophilic monomer, 0.1 to 5 parts of crosslinking agent, 0.2 to 7 parts of initiator and 20 to 50 parts of solvent. The present invention selects symmetrical monomethacryloxypropyl modified polydimethylsiloxane, methyl-di(trimethylsiloxy)-silylpropyl methacrylate and 2-(trimethylsiloxy)ethyl methacrylate as silicone monomers. The three silicone monomers cooperate with each other to improve the oxygen permeability of the lens; and the three silicone monomers have good solubility with the hydrophilic monomer, which further improves the comprehensive performance of the silicone hydrogel. In addition, the present invention also provides a silicone hydrogel contact lens, and the preparation method comprises the following steps: mixing the raw materials, injecting them into a mold, and performing a polymerization reaction. After the polymerization reaction is completed, the obtained sample is immersed in an isopropanol solution, taken out, and a silicone hydrogel contact lens is obtained. The present invention soaks the sample in an isopropanol solution, which can improve the transparency of the lens and open the channels on the lens, thereby improving the oxygen permeability coefficient of the lens.

[0058] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A highly oxygen permeable silicone hydrogel, characterized in that: Contains the following raw materials by mass: 20-90 parts of organosilicon monomer, 20-80 parts of hydrophilic monomer, 0.1-5 parts of crosslinking agent, 0.2-7 parts of initiator and 20-50 parts of solvent; The organic silicon monomer comprises symmetrical monomethacryloxypropyl modified polydimethylsiloxane, methyl-bis(trimethylsiloxy)-silylpropyl methacrylate and 2-(trimethylsiloxy)ethyl methacrylate.

2. The highly oxygen permeable silicone hydrogel according to claim 1, characterized in that: The mass ratio of the symmetrical monomethacryloxypropyl modified polydimethylsiloxane, methyl-bis(trimethylsiloxy)-silylpropyl methacrylate and 2-(trimethylsiloxy)ethyl methacrylate is 4-6:1-3:2-4.

3. The highly oxygen permeable silicone hydrogel according to claim 1 or 2, characterized in that: The hydrophilic monomers include hydroxyethyl methacrylate, N-vinyl pyrrolidone and N,N-dimethylacrylamide; The mass ratio of hydroxyethyl methacrylate, N-vinyl pyrrolidone and N,N-dimethylacrylamide is 3-5:2-4:0.5-1.

5.

4. The highly oxygen permeable silicone hydrogel according to claim 3, characterized in that: The crosslinking agent includes trimethylolpropane trimethacrylate or trimethylolpropane triacrylate.

5. The highly oxygen permeable silicone hydrogel according to claim 4, characterized in that: The initiator includes azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide or D1173.

6. The highly oxygen permeable silicone hydrogel according to claim 5, characterized in that: The solvent includes one or more of isopropanol, ethanol, n-hexanol and n-butanol.

7. A silicone hydrogel contact lens, characterized in that: The silicone hydrogel contact lens is prepared by using the high oxygen permeability silicone hydrogel according to any one of claims 1 to 6.

8. The silicone hydrogel contact lens according to claim 7, wherein: The method for preparing the silicone hydrogel contact lens comprises the following steps: The raw materials are mixed and injected into a mold to carry out a polymerization reaction. After the polymerization reaction is completed, the obtained sample is immersed in an isopropanol solution and taken out to obtain the silicone hydrogel contact lens.

9. The silicone hydrogel contact lens according to claim 8, wherein: The mass fraction of the isopropanol solution is 5-20%; the soaking time is 0.5-2h.