Anti-blue-light hydrogel as well as preparation method and application thereof
By preparing anti-blue light hydrogels containing silicone monomers and p-aminoazobenzene monomers, the problem that existing corneal contact lenses cannot effectively shield blue light is solved, and the efficient blue light shielding and oxygen permeability are improved.
Patent Information
- Application Number
- CN202510428440.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-07
- Publication Date
- 2025-08-08
AI Technical Summary
Existing corneal contact lenses cannot effectively shield blue light, and existing anti-blue light materials have problems such as decreased light transmittance, easy agglomeration of nanoparticles, easy migration and precipitation of dyes, or high costs.
Using a combination of siloxane monomer, p-aminoazobenzene monomer, hydrophilic monomer, crosslinking agent and initiator, an anti-blue light hydrogel is prepared through polymerization and crosslinking reaction to form a core-shell structure hydrogel to improve the blue light shielding effect.
It achieves efficient blue light shielding, improves the oxygen permeability coefficient of corneal contact lenses, and meets biosafety requirements.
Smart Images
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of medical materials, and in particular to a blue light blocking hydrogel and a preparation method and application thereof. Background Art
[0002] With the development of electronic products such as mobile phones and computers, people spend more and more time using them. To increase contrast, the LED light sources in display screens add large doses of blue light. Long-term exposure to this excessive, high-energy light can damage the organic molecular structure of eye cells, causing damage, most commonly macular degeneration.
[0003] Contact lenses, also known as contact lenses, are lenses worn on the cornea to correct vision or protect the eyes. They can significantly improve vision for patients with refractive errors such as myopia, hyperopia, and astigmatism. However, current contact lenses fail to block blue light. Existing methods for preparing blue light-blocking materials include: inorganic nanoparticle doping, which involves dispersing cerium oxide or zinc oxide in a hydrogel. However, this method only blocks 40-50% of blue light, and the nanoparticles easily aggregate, resulting in reduced transmittance; organic dye blending, such as the copolymerization of lutein esters with poly(hydroxyethyl methacrylate), which blocks approximately 55% of blue light, but the dyes are prone to migration and precipitation, raising concerns about their safety with long-term use; and surface coating, which involves applying a blue light-reflecting film to the lens surface. However, this film easily wears off and is expensive, making it difficult to apply to flexible contact lenses. Therefore, developing a blue light-blocking hydrogel and its preparation method for use in the production of blue light-blocking contact lenses is of great significance. Summary of the Invention
[0004] The purpose of the present invention is to provide a blue light blocking hydrogel and its preparation method and application, so as to solve the problem of poor blue light blocking effect of corneal contact lenses in the prior art.
[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:
[0006] The present invention provides a blue light blocking hydrogel, which is prepared from the following raw materials in parts by weight: 30 to 50 parts of a siloxane monomer, 5 to 15 parts of a p-aminoazobenzene monomer, 10 to 60 parts of a hydrophilic monomer, 0.1 to 1 part of a cross-linking agent, 0.3 to 1.5 parts of an initiator, and 30 to 60 parts of a solvent; the siloxane monomer comprises mercaptosiloxane, acryloxysiloxane, and vinylsiloxane.
[0007] Preferably, the preparation method of the p-aminoazobenzene monomer is: reacting p-aminoazobenzene and isocyanoethyl methacrylate as raw materials to obtain the p-aminoazobenzene monomer.
[0008] Preferably, the mass ratio of p-aminoazobenzene to isocyanoethyl methacrylate is 1:1.0-1.5; the reaction temperature is 20-30° C., and the reaction time is 4-8 hours.
[0009] Preferably, the hydrophilic monomer comprises one or more of N,N-dimethylacrylamide, 2-hydroxyethyl methacrylate, N-vinyl pyrrolidone and methacrylic acid.
[0010] Preferably, the crosslinking agent comprises one or more of ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, divinylbenzene, 1,3,5-triallyl cyanurate and triethylene glycol divinyl ether; the initiator is azobisisobutyronitrile or benzoyl peroxide; and the solvent is n-butanol or n-hexanol.
[0011] The present invention also provides a method for preparing the above-mentioned blue light blocking hydrogel, comprising the following steps:
[0012] 1) mixing a siloxane monomer, a p-aminoazobenzene monomer, an initiator, and a solvent and performing a polymerization reaction to obtain a first product;
[0013] 2) Adding a hydrophilic monomer and a cross-linking agent to the first product for cross-linking polymerization to obtain a blue light blocking hydrogel.
[0014] Preferably, in step 1), the polymerization reaction is carried out at room temperature, and the polymerization reaction time is 10 to 16 hours.
[0015] Preferably, in step 2), the temperature of the cross-linking polymerization is 40 to 50° C., and the time of the cross-linking polymerization is 4 to 6 hours.
[0016] The present invention also provides a use of the above-mentioned blue light blocking hydrogel in the preparation of corneal contact lenses.
[0017] Beneficial effects of the present invention:
[0018] The invention adds p-aminoazobenzene monomer to prepare hydrogel, and can obtain corneal contact lens that blocks blue light.
[0019] The siloxane monomers of the present invention comprise mercaptosiloxane, acryloxysiloxane and vinylsiloxane. Polymerization of the three siloxanes can improve the oxygen permeability coefficient of corneal contact lenses.
[0020] The present invention first polymerizes siloxane monomers and p-aminoazobenzene monomers, and then adds hydrophilic monomers and crosslinking agents for crosslinking polymerization to form a hydrogel similar to a core-shell structure. The hydrophilic monomer wraps the azobenzene structure, so that the corneal contact lens meets the cytotoxicity requirements. DETAILED DESCRIPTION
[0021] The present invention provides a blue light blocking hydrogel, which is prepared from the following raw materials in parts by weight: 30 to 50 parts of a siloxane monomer, 5 to 15 parts of a p-aminoazobenzene monomer, 10 to 60 parts of a hydrophilic monomer, 0.1 to 1 part of a cross-linking agent, 0.3 to 1.5 parts of an initiator, and 30 to 60 parts of a solvent; the siloxane monomer comprises mercaptosiloxane, acryloxysiloxane, and vinylsiloxane.
[0022] In the present invention, the mercaptosiloxane is selected from KH580 or KH590; the acryloxysiloxane is selected from KH570, KH571, KH670; and the vinylsiloxane is selected from KH151 or KH171.
[0023] In the present invention, the mass ratio of the mercaptosiloxane, acryloxysiloxane and vinylsiloxane is 1:2 to 3:1, preferably 1:2:1.
[0024] In the present invention, the preparation method of the p-aminoazobenzene monomer is as follows: p-aminoazobenzene and isocyanoethyl methacrylate are reacted as raw materials to prepare the p-aminoazobenzene monomer.
[0025] In the present invention, the mass ratio of p-aminoazobenzene to isocyanoethyl methacrylate is 1:1.0-1.5, preferably 1:1.2-1.4, more preferably 1:1.3; the reaction temperature is 20-30°C, and the reaction time is 4-8h, preferably 5-7h, more preferably 6h.
[0026] In the present invention, the amount of the hydrophilic monomer added is preferably 20 to 60 parts, more preferably 40 to 60 parts.
[0027] In the present invention, the hydrophilic monomer comprises one or more of N,N-dimethylacrylamide, 2-hydroxyethyl methacrylate, N-vinyl pyrrolidone and methacrylic acid.
[0028] In the present invention, the crosslinking agent comprises one or more of ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, divinylbenzene, 1,3,5-triallyl cyanurate and triethylene glycol divinyl ether; the initiator is azobisisobutyronitrile or benzoyl peroxide; and the solvent is n-butanol or n-hexanol.
[0029] The present invention also provides a method for preparing the above-mentioned blue light blocking hydrogel, comprising the following steps:
[0030] 1) mixing a siloxane monomer, a p-aminoazobenzene monomer, an initiator, and a solvent and performing a polymerization reaction to obtain a first product;
[0031] 2) Adding a hydrophilic monomer and a cross-linking agent to the first product for cross-linking polymerization to obtain a blue light blocking hydrogel.
[0032] In the present invention, in step 1), the polymerization reaction is carried out at room temperature, and the polymerization reaction time is 10 to 16 hours, preferably 10 hours, 12 hours, 14 hours, or 16 hours.
[0033] In the present invention, in step 2), the temperature of the cross-linking polymerization is 40 to 50° C., preferably 45° C., and the time of the cross-linking polymerization is 4 to 6 hours, preferably 5 hours.
[0034] The present invention also provides a use of the above-mentioned blue light blocking hydrogel in the preparation of corneal contact lenses.
[0035] The technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.
[0036] Example 1
[0037] 5 g of p-aminoazobenzene and 50 mL of N,N-dimethylformamide were mixed evenly, and then 6.5 g of isocyanoethyl methacrylate was added. The mixture was stirred and reacted at room temperature for 6 hours to obtain p-aminoazobenzene monomer.
[0038] Prepare the raw materials according to the following weight parts: 40 parts of siloxane monomer (including 10 parts of KH580, 20 parts of KH570, and 10 parts of KH151), 5 parts of the above-prepared p-aminoazobenzene monomer, 60 parts of 2-hydroxyethyl methacrylate, 1 part of ethylene glycol dimethacrylate, 0.5 parts of azobisisobutyronitrile, and 60 parts of n-hexanol.
[0039] The blue light protection hydrogel was prepared using the raw materials prepared above: KH580, KH570 and KH151 were mixed with n-hexanol, and then p-aminoazobenzene monomer was added and stirred evenly, and finally azobisisobutyronitrile was added and continued to be stirred. The polymerization reaction was carried out for 16 hours to obtain the first product; 2-hydroxyethyl methacrylate and ethylene glycol dimethacrylate were added to the first product, stirred evenly, and then transferred to a mold, cross-linked and polymerized at a temperature of 45°C for 5 hours, and finally demolded, cleaned, swollen, and balanced to obtain a blue light protection corneal contact lens.
[0040] Example 2
[0041] 5 g of p-aminoazobenzene and 50 mL of N,N-dimethylformamide were mixed evenly, and then 6.5 g of isocyanoethyl methacrylate was added. The mixture was stirred and reacted at room temperature for 6 hours to obtain p-aminoazobenzene monomer.
[0042] Prepare the raw materials according to the following weight parts: 50 parts of siloxane monomer (including 10 parts of KH580, 30 parts of KH570, and 10 parts of KH151), 10 parts of the above-prepared p-aminoazobenzene monomer, 50 parts of 2-hydroxyethyl methacrylate, 0.8 parts of ethylene glycol dimethacrylate, 1 part of azobisisobutyronitrile, and 60 parts of n-hexanol.
[0043] The blue light protection hydrogel was prepared using the raw materials prepared above: KH580, KH570 and KH151 were mixed with n-hexanol, and then p-aminoazobenzene monomer was added and stirred evenly, and finally azobisisobutyronitrile was added and continued to be stirred. The polymerization reaction was carried out for 16 hours to obtain the first product; 2-hydroxyethyl methacrylate and ethylene glycol dimethacrylate were added to the first product, stirred evenly, and then transferred to a mold, cross-linked and polymerized at a temperature of 45°C for 5 hours, and finally demolded, cleaned, swollen, and balanced to obtain a blue light protection corneal contact lens.
[0044] Example 3
[0045] 5 g of p-aminoazobenzene and 50 mL of N,N-dimethylformamide were mixed evenly, and then 6.5 g of isocyanoethyl methacrylate was added. The mixture was stirred and reacted at room temperature for 6 hours to obtain p-aminoazobenzene monomer.
[0046] Prepare the raw materials according to the following weight parts: 30 parts of siloxane monomer (including 6 parts of KH580, 18 parts of KH570, and 6 parts of KH151), 15 parts of the above-prepared p-aminoazobenzene monomer, 40 parts of 2-hydroxyethyl methacrylate, 0.5 parts of ethylene glycol dimethacrylate, 1.5 parts of azobisisobutyronitrile, and 60 parts of n-hexanol.
[0047] The blue light protection hydrogel was prepared using the raw materials prepared above: KH580, KH570 and KH151 were mixed with n-hexanol, and then p-aminoazobenzene monomer was added and stirred evenly, and finally azobisisobutyronitrile was added and continued to be stirred. The polymerization reaction was carried out for 16 hours to obtain the first product; 2-hydroxyethyl methacrylate and ethylene glycol dimethacrylate were added to the first product, stirred evenly, and then transferred to a mold, cross-linked and polymerized at a temperature of 45°C for 5 hours, and finally demolded, cleaned, swollen, and balanced to obtain a blue light protection corneal contact lens.
[0048] Comparative Example 1
[0049] The difference from Example 1 is that no p-aminoazobenzene monomer is added. Other conditions are the same to prepare a corneal contact lens.
[0050] Comparative Example 2
[0051] The difference from Example 1 is that the added amount of p-aminoazobenzene monomer is 4 parts, and other conditions are the same.
[0052] Comparative Example 3
[0053] 5 g of p-aminoazobenzene and 50 mL of N,N-dimethylformamide were mixed evenly, and then 6.5 g of isocyanoethyl methacrylate was added. The mixture was stirred and reacted at room temperature for 6 hours to obtain p-aminoazobenzene monomer.
[0054] Prepare the raw materials according to the following weight parts: 40 parts of siloxane monomer (including 10 parts of KH580, 20 parts of KH570, and 10 parts of KH151), 5 parts of the above-prepared p-aminoazobenzene monomer, 60 parts of 2-hydroxyethyl methacrylate, 1 part of ethylene glycol dimethacrylate, 0.5 parts of azobisisobutyronitrile, and 60 parts of n-hexanol.
[0055] The blue light blocking hydrogel was prepared using the raw materials prepared above: KH580, KH570 and KH151 were mixed with n-hexanol, and then p-aminoazobenzene monomer, azobisisobutyronitrile, 2-hydroxyethyl methacrylate and ethylene glycol dimethacrylate were added, stirred evenly, transferred to a mold, cross-linked and polymerized at 45°C for 5 hours, and finally demolded, cleaned, swollen and balanced to obtain a blue light blocking corneal contact lens.
[0056] Comparative Example 4
[0057] The difference from Example 1 is that all the siloxane monomers are KH570, and no KH580 and KH151 are added. Other conditions are the same.
[0058] Performance testing:
[0059] (1) Optical Properties: The blue light transmittance of the contact lenses was tested using a UV-Vis spectrophotometer. The contact lens samples of Examples 1 to 3 and Comparative Examples 1 to 4 were placed in a PBS solution and soaked for 24 hours. The lenses were then attached to the surface of a cuvette containing PBS solution. The PBS solution was used as a reference solution. The transmittance of the samples was tested in the visible light range of 380 to 460 nm, with a spectral scan width of 1 nm. The average transmittance was used to represent the absorption effect. The lower the transmittance, the better the absorption effect. At least three samples of each material were tested.
[0060] (2) Oxygen permeability test: Test in accordance with GB 11417.7-2012.
[0061] The test results are shown in Table 1:
[0062] Table 1 Test results of Examples 1 to 3 and Comparative Examples 1 to 4
[0063]
[0064]
[0065] As can be seen from Table 1, adding an appropriate amount of p-aminoazobenzene monomer can reduce the transmittance of blue light. Using a composite siloxane monomer can significantly increase the oxygen permeability of corneal contact lenses.
[0066] 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 principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.
Claims
1. A blue light blocking hydrogel, characterized in that: The invention is prepared from the following raw materials in parts by weight: 30 to 50 parts of siloxane monomer, 5 to 15 parts of p-aminoazobenzene monomer, 10 to 60 parts of hydrophilic monomer, 0.1 to 1 part of cross-linking agent, 0.3 to 1.5 parts of initiator, and 30 to 60 parts of solvent; the siloxane monomer comprises mercaptosiloxane, acryloxysiloxane, and vinylsiloxane.
2. The blue light blocking hydrogel according to claim 1, characterized in that: The preparation method of the p-aminoazobenzene monomer comprises the following steps: taking p-aminoazobenzene and isocyanoethyl methacrylate as raw materials for reaction to prepare the p-aminoazobenzene monomer.
3. The blue light blocking hydrogel according to claim 2, characterized in that: The mass ratio of p-aminoazobenzene to isocyanoethyl methacrylate is 1:1.0-1.5; the reaction temperature is 20-30° C., and the reaction time is 4-8 hours.
4. The blue light blocking hydrogel according to any one of claims 1 to 3, characterized in that: The hydrophilic monomer comprises one or more of N,N-dimethylacrylamide, 2-hydroxyethyl methacrylate, N-vinyl pyrrolidone and methacrylic acid.
5. The blue light blocking hydrogel according to claim 4, characterized in that: The crosslinking agent comprises one or more of ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, divinylbenzene, 1,3,5-triallyl cyanurate and triethylene glycol divinyl ether; the initiator is azobisisobutyronitrile or benzoyl peroxide; and the solvent is n-butanol or n-hexanol.
6. The method for preparing the blue light blocking hydrogel according to any one of claims 1 to 5, characterized in that: The steps include: 1) mixing a siloxane monomer, a p-aminoazobenzene monomer, an initiator, and a solvent and performing a polymerization reaction to obtain a first product; 2) Adding a hydrophilic monomer and a cross-linking agent to the first product for cross-linking polymerization to obtain a blue light blocking hydrogel.
7. The method for preparing the blue light blocking hydrogel according to claim 6, wherein: In the step 1), the polymerization reaction is carried out at room temperature, and the polymerization reaction time is 10 to 16 hours.
8. The method for preparing the blue light blocking hydrogel according to claim 6 or 7, characterized in that: In the step 2), the temperature of the cross-linking polymerization is 40 to 50° C., and the time of the cross-linking polymerization is 4 to 6 hours.
9. Use of the blue light blocking hydrogel according to any one of claims 1 to 5 in the preparation of corneal contact lenses.