Preparation method of recessive glasses and recessive glasses

Abstract

The invention discloses a preparation method of a pair of hidden glasses and the pair of hidden glasses. The preparation method of the recessive glasses comprises the following steps: directly mixing and stirring an organic silicon monomer, an amide monomer, a cross-linking agent, a photoinitiator and a thermal initiator, dropwise adding the mixed raw materials into a lens mold, carrying out a thermocuring reaction, and then carrying out a photocuring reaction to prepare the recessive glasses. According to the preparation method, only one-step mixing is needed, the operation is simple, the advantages of photo-thermal curing are integrated, and the production efficiency is improved; the lens prepared by the method has high oxygen permeability and surface wettability.

Description

Technical Field

[0001] The invention belongs to the field of material preparation, and in particular relates to a method for preparing a contact lens and the contact lens. Background Art

[0002] Contact lenses, also called contact lenses or contact glasses, are lenses worn on the cornea of ​​the eyeball to correct vision or protect the eyes. Soft contact lenses are popular among consumers because of their comfort, adaptability, and convenience.

[0003] Traditional hydrogel soft corneal contact lenses are mainly made of polyhydroxyethyl methacrylate materials, but because the oxygen permeability of this material is weak, it is easy to cause long-term corneal hypoxia and epithelial edema during wearing, especially when worn incorrectly such as when sleeping, and finally cause shedding, and even edema and infection accompanied by inflammation. Silicone hydrogel materials can greatly improve the oxygen permeability coefficient of corneal contact lenses because they contain dimethylsiloxane structures, but the hydrophobicity of dimethylsiloxane itself will lead to poor wettability of the lens, and the lens has poor toughness, which affects the wearing comfort and safety of the lens. In the prior art, the improvement of the wettability of the lens is mainly focused on surface modification, adding internal wetting agents, improving the process, etc. For example, CN116940639A proposes to coat the surface of contact lenses with collagen-containing biomaterials as hydrophilic polymers to improve the physical and chemical properties of the lenses, such as bioaffinity, tensile strength and wettability. CN106939066A polymerizes the non-silicon-containing monomers first, and then polymerizes the polymers and silicon-containing monomers in a second step to prepare products with wettability and anti-oil sedimentation properties. However, the preparation process of this method is relatively cumbersome. Therefore, there is an urgent need for a method that can improve the lens preparation efficiency and improve the wettability of the lens. Summary of the invention

[0004] Purpose of the invention: The technical problem to be solved by the present invention is to provide a method for preparing contact lenses.

[0005] Another technical problem to be solved by the present invention is to provide contact lenses prepared by the preparation method.

[0006] Technical solution: The present invention provides a method for preparing contact lenses, comprising the following steps: directly mixing and stirring an organosilicon monomer, an amide monomer, a crosslinking agent, a photoinitiator and a thermal initiator, dripping the mixed raw materials drop by drop into a lens mold, first performing a thermal curing reaction, and then performing a photocuring reaction to prepare the contact lenses. Among them, the organosilicon monomer comprises 20 to 60 parts, the amide monomer comprises 40 to 75 parts, the crosslinking agent comprises 0.1 to 5 parts, the thermal initiator comprises 0.1 to 5 parts, and the photoinitiator comprises 0.1 to 5 parts.

[0007] The heat curing reaction conditions are as follows: the heat curing temperature is 30°C to 90°C, and the heat curing time is 10min to 24h. Preferably, the heat curing time is 10min to 12h. More preferably, the heat curing time is 10min to 3h.

[0008] The light curing reaction condition is a light intensity of 0.1 mW / cm 2 -50mW / cm 2 , curing time 10s~60min.

[0009] The organosilicon monomer contains at least one olefinic unsaturated reactive group and has a dimethylsiloxane structure, wherein the olefinic unsaturated reactive group includes acrylate, vinyl ester or methacrylate. Preferably, if the organosilicon monomer has only one olefinic unsaturated reactive group, the relative average molecular mass is less than 3000; if there are two olefinic reactive groups, the relative average molecular mass is greater than 1000 and less than 20000; preferably, the amide monomer includes one or more of N,N-dimethylacrylamide, N-vinyl, N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylformamide or 2-hydroxyethylacrylamide.

[0010] Wherein, the cross-linking agent includes one or more of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, allyl methacrylate, ethylene glycol diallyl ether, triethylene glycol diallyl ether, tetraethylene glycol diallyl ether, 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,1-trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetra(acrylate), tetraethylene glycol diacrylate, ethylenediacrylamide, 1,4-bis(acrylamide)butene or poly(ethylene glycol) di(acrylate).

[0011] The thermal initiator includes one or more of azobisisobutyronitrile, azobisisoheptanenitrile (ABVN), 2,2′-azobis(2,4-dimethylvaleronitrile, benzoyl peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate or bis(2-phenylethoxy) peroxydicarbonate.

[0012] Wherein, the photoinitiator includes one or more of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, di(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenylphosphine oxide, di(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methyl benzoate, camphorquinone or ethyl 4-(N,N-dimethylamino)benzoate.

[0013] The present invention also includes contact lenses prepared by the method.

[0014] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: the preparation method of the contact lens of the present invention requires only one step of mixing of raw materials, is simple to operate, combines the advantages of light and heat curing, and improves production efficiency; the lenses prepared by the method have higher oxygen permeability and surface wettability. DETAILED DESCRIPTION

[0016] The compounds used in the embodiments of the present invention include: M1: 3-methacryloyloxy-2-hydroxyoxypolyethylene glycol ether propyl terminated polydimethylsiloxane, the structural formula of which is as follows:

[0017]

[0018] Tris: Methacryloyloxypropyl tris(trimethylsiloxy)silane, the structural formula is as follows:

[0019]

[0020] MCS-M11: Symmetrical monomethacryloxypropyl modified polydimethylsiloxane, the structural formula is as follows:

[0021] Example 1

[0022] According to Table 1, M1, Tris, VMA, PEGDMA (200), and ABVN were directly mixed and stirred for 8 h. The mixed raw materials were dripped into the lens mold drop by drop, and cured in an oven at 30 °C for 15 h. 2 After curing for 5 minutes, the lens was taken out, soaked in ethanol, transferred to pure water, and finally placed in standard saline for storage.

[0023] Example 2

[0024] According to Table 1, M1, Tris, VMA, PEGDMA (200), and ABVN were directly mixed and stirred for 8 h. The mixed raw materials were dripped into the lens mold drop by drop, and cured in an oven at 40 °C for 7.5 h. 2 After curing for 20 minutes, the lens was taken out, soaked in ethanol, transferred to pure water, and finally placed in standard saline for storage.

[0025] Example 3

[0026] According to Table 1, M1, Tris, VMA, PEGDMA (200), ABVN, and tert-amyl alcohol were directly mixed and stirred for 8 h. The mixed raw materials were dripped into the lens mold drop by drop, and cured in an oven at 50 °C for 7.5 h. 2 After curing for 30 minutes, the lens was taken out, soaked in ethanol, transferred to pure water, and finally stored in standard saline.

[0027] Example 4

[0028] According to Table 1, M1, MCS-M11, VMA, PEGDMA (200), and ABVN were directly mixed and stirred for 8 h. The mixed raw materials were dripped into the lens mold drop by drop, and cured in an oven at 30 °C for 15 h. 2 After curing for 5 minutes, the lens was taken out, soaked in ethanol, transferred to pure water, and finally placed in standard saline for storage.

[0029] Example 5

[0030] According to Table 1, M1, MCS-M11, VMA, PEGDMA (200), ABVN, and tert-amyl alcohol were directly mixed and stirred for 8 h. The mixed raw materials were dripped into the lens mold drop by drop, and cured in an oven at 40 °C for 7.5 h. 2 After curing for 20 minutes, the lens was taken out, soaked in ethanol, transferred to pure water, and finally placed in standard saline for storage.

[0031] Example 6

[0032] According to Table 1, M1, MCS-M11, VMA, PEGDMA (200), ABVN, and tert-amyl alcohol were directly mixed and stirred for 8 h. The mixed raw materials were dripped into the lens mold drop by drop, and cured in an oven at 50 °C for 7.5 h. 2 After curing for 30 minutes, the lens was taken out, soaked in ethanol, transferred to pure water, and finally stored in standard saline.

[0033] Comparative Example 1

[0034] According to Table 1, M1, Tris, VMA, PEGDMA (200), and ABVN were directly mixed and stirred for 8 h. The mixed raw materials were dripped into the lens mold drop by drop, and cured in an oven at 50°C for 7.5 h. The lens was taken out, soaked in ethanol, transferred to pure water, and finally placed in standard saline for storage.

[0035] Comparative Example 2

[0036] According to Table 1, M1, Tris, VMA, PEGDMA (200), and ABVN were directly mixed and stirred for 8 h. The mixed raw materials were dripped into the lens mold drop by drop. The mixture was illuminated under a 365 nm fluorescent light source with a wavelength of 5 mW / cm 2 After curing for 5 minutes, the lens was taken out, soaked in ethanol, transferred to pure water, and finally placed in standard saline for storage.

[0037] Comparative Example 3

[0038] According to Table 1, M1, Tris, VMA, PEGDMA (200), and ABVN were directly mixed and stirred for 8 h. The mixed raw materials were dripped into the lens mold drop by drop. The mixture was illuminated under a 365 nm fluorescent light source with a wavelength of 5 mW / cm 2 Curing was performed for 5 minutes, and then cured in an oven at 50°C for 7.5 hours. The lenses were taken out, soaked in ethanol, transferred to pure water, and finally stored in standard saline.

[0039] The silicone hydrogel material was tested according to the oxygen permeability polarography test method in 4.4.3 of GB11417.7-2012;

[0040] The silicone hydrogel material was tested according to the water content test method in 4.4.6 of GB11417.7-2012;

[0041] The silicone hydrogel material was tested according to the light transmittance test method in 4.4.6 of GB11417.5-2012.

[0042] Table 1 Reaction composition, reaction conditions and test results of Examples 1 to 3 and Comparative Examples 1 to 3

[0043]

[0044]

[0045] The contact angle and transmittance of the lens materials prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were tested. The results are shown in Table 1. As can be seen from Table 1, the contact angle of the lens using the photothermal curing process is significantly lower than that of the lens using only photocuring, while the lens using only thermal curing cannot be cured, and the lenses prepared using the preparation methods of Examples 1 to 6 all have high transmittance and high oxygen permeability.

Claims

1. A method for preparing contact lenses, characterized in that: The method comprises the following steps: directly mixing and stirring an organic silicon monomer, an amide monomer, a crosslinking agent, a photoinitiator and a thermal initiator, dripping the mixed raw materials drop by drop into a lens mold, first performing a thermal curing reaction, and then performing a photocuring reaction to obtain the preparation.

2. The preparation method according to claim 1, characterized in that: The organic silicon monomer comprises 20 to 60 parts, the amide monomer comprises 40 to 75 parts, the cross-linking agent comprises 0.1 to 5 parts, the thermal initiator comprises 0.1 to 5 parts, and the photoinitiator comprises 0.1 to 5 parts.

3. The preparation method according to claim 1, characterized in that: The heat curing reaction conditions are as follows: the heat curing temperature is 30°C to 90°C, and the heat curing time is 10min to 24h. Preferably, the heat curing time is 10min to 12h. More preferably, the heat curing time is 10min to 3h.

4. The preparation method according to claim 1, characterized in that: The photocuring reaction conditions are light intensity 0.1 mW / cm 2 -50mW / cm 2 , curing time 10s~60min.

5. The preparation method according to claim 1, characterized in that: The organosilicon monomer contains at least one olefinic unsaturated reactive group and has a dimethylsiloxane structure, wherein the olefinic unsaturated reactive group includes acrylate, vinyl ester or methacrylate. Preferably, if the organosilicon monomer has only one olefinic unsaturated reactive group, the relative average molecular mass is less than 3000; if there are two olefinic reactive groups, the relative average molecular mass is greater than 1000 and less than 20000; preferably, the amide monomer includes one or more of N,N-dimethylacrylamide, N-vinyl, N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylformamide or 2-hydroxyethylacrylamide.

6. The preparation method according to claim 1, characterized in that: The cross-linking agent includes one or more of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, allyl methacrylate, ethylene glycol diallyl ether, triethylene glycol diallyl ether, tetraethylene glycol diallyl ether, 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,1-trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetra(acrylate), tetraethylene glycol diacrylate, ethylenediacrylamide, 1,4-bis(acrylamide)butene or poly(ethylene glycol) di(acrylate).

7. The preparation method according to claim 1, characterized in that: The thermal initiator includes one or more of azobisisobutyronitrile, azobisisoheptanenitrile, 2,2'-azobis(2,4-dimethylvaleronitrile, benzoyl peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate or bis(2-phenylethoxy) peroxydicarbonate.

8. The preparation method according to claim 1, characterized in that: The photoinitiator includes one or more of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, di(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenylphosphine oxide, di(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methyl benzoate, camphorquinone or ethyl 4-(N,N-dimethylamino)benzoate.

9. Contact lenses prepared by the method according to any one of claims 1 to 8.

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