Silicone hydrogel for contact lenses and preparation method thereof

Abstract

The invention provides silicone hydrogel for contact lenses and a preparation method of the silicone hydrogel, and belongs to the technical field of silicone hydrogel. The silicon hydrogel for the contact lenses, prepared by the invention, is prepared from the following raw materials in parts by weight: 10 to 30 parts of silicon-based monomers, 20 to 40 parts of amino modified polydimethylsiloxane, 15 to 50 parts of hydroxyethyl methylacrylate, 10 to 50 parts of N, N-dimethylacrylamide, 0.1 to 5 parts of a cross-linking agent, 0.1 to 5 parts of an initiator and 20 to 30 parts of a solvent. The silicone hydrogel provided by the invention has high oxygen permeability, durability and comfort, and can effectively reduce adhesion of lipid and microorganisms, so that the problem of eye inflammation is solved, and the long-term stability and wearing comfort of contact lenses are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of silicone hydrogels, and in particular to a silicone hydrogel for contact lenses and a preparation method thereof. Background Art

[0002] Silicone hydrogel is a kind of organic silicon polymer material, which is hydrophilic and is currently the most promising corneal contact lens material. Silicone hydrogel contains silicon-oxygen bond groups, which can increase oxygen permeability by attaching to each other. Silicone hydrogel lenses are deeply loved by consumers because of their high oxygen permeability and can reduce corneal hypoxia.

[0003] Oxygen permeability is the primary factor that determines the length of time it can be worn. If the oxygen permeability of the lens is low, it will lead to corneal hypoxia, and long-term corneal hypoxia can easily lead to complications such as chronic corneal edema and corneal neovascularization. In addition, the water content of the lens will also affect the characteristics of the lens. The higher the water content, the better the oxygen permeability, the softer the lens, but it is also easier to deform and break, the lens is more likely to lose water, and the durability is poor; conversely, the lower the water content, the better the lens formability, the smaller the degree of deformation, and it is less likely to dehydrate than a lens with a high water content, but it is easy to affect the wearing comfort. For example, Chinese patent CN102964532A discloses the use of a special amphiphilic organosiloxane monomer, and the oxygen permeability coefficient Dk of the material prepared by combining the amphiphilic organosiloxane monomer with a hydrophilic monomer is 35 to 40 Barrer. However, the use of the above-mentioned silicone water material still has the problem of low oxygen permeability and easy to cause eye inflammation.

[0004] In addition, Chinese patent CN112159505A discloses that the silicone hydrogel prepared by mixing silicon-containing monomers, hydrophilic monomers, crosslinking agents, initiators and organic solvents has the characteristics of medium water content and high oxygen permeability coefficient. The oxygen permeability coefficient of the lens is above 80, and the highest can reach 88, which meets people's requirements for contact lens comfort and oxygen permeability. Although this silicone hydrogel has a high oxygen permeability coefficient, it is easy to precipitate oil and protein, which increases the difficulty of cleaning, thereby affecting the long-term stability and wearing comfort of contact lenses.

[0005] Therefore, it is of great significance to provide a silicone hydrogel that has high oxygen permeability, durability, and comfort and can effectively reduce the attachment of lipids and microorganisms. Summary of the invention

[0006] The object of the present invention is to provide a silicone hydrogel for contact lenses and a preparation method thereof, so as to solve the problem in the prior art that it is difficult to balance high oxygen permeability, durability and comfort, and it is easy to precipitate oil and protein.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0008] The present invention provides a silicone hydrogel for contact lenses, which is prepared from the following raw materials in parts by weight:

[0009]

[0010] Furthermore, the silicon-based monomer is a mixture of 3-(methacryloyloxy)propyltri(trimethylsiloxane)silane and N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane.

[0011] Furthermore, the mass ratio of the 3-(isomethacryloyloxy)propyltri(trimethylsiloxane)silane to N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane is 1-3:1-3.

[0012] Furthermore, the cross-linking agent includes at least two of ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate and 1,3,5-triallyl cyanurate.

[0013] Furthermore, the initiator includes azobisisobutyronitrile and / or benzoyl peroxide.

[0014] Furthermore, the solvent includes n-butanol and / or n-hexanol.

[0015] The present invention also provides a method for preparing the silicone hydrogel for contact lenses, comprising the following steps: mixing a silicon-based monomer, amino-modified polydimethylsiloxane, hydroxyethyl methacrylate, N,N-dimethylacrylamide, a crosslinking agent, an initiator and a solvent, injecting the mixture into a contact lens mold, and performing a polymerization reaction by thermal initiation to obtain the silicone hydrogel for contact lenses.

[0016] Furthermore, the mixing is performed during stirring, the stirring speed is 100 to 800 rpm, and the stirring time is 3 to 12 hours.

[0017] Furthermore, the polymerization reaction temperature is 60-120° C., and the polymerization reaction time is 8-15 hours.

[0018] Beneficial effects of the present invention:

[0019] (1) The present invention uses hydroxyethyl methacrylate and N,N-dimethylacrylamide with reactive double bonds. The hydroxyethyl side chain of hydroxyethyl methacrylate can provide additional reaction sites, while the double bond of N,N-dimethylacrylamide provides the basis for polymerization. Crosslinking is achieved through the synergistic effect of the two monomers. In addition, the two monomers can further enhance the crosslinking effect with silicon-based monomers and crosslinking agents, thereby obtaining a silicone hydrogel with specific physical and chemical properties.

[0020] (2) The present invention can not only increase the water content and air permeability of contact lenses, but also maintain the softness and comfort of contact lenses through the synergistic effect of hydroxyethyl methacrylate and amino-modified polydimethylsiloxane in a specific ratio, thereby reducing the side effects of contact lenses and maintaining eye health;

[0021] (3) The silicone hydrogel prepared by the present invention has high oxygen permeability, durability and comfort, and can effectively reduce the attachment of lipids and microorganisms. DETAILED DESCRIPTION

[0022] The present invention provides a silicone hydrogel for contact lenses, which is prepared from the following raw materials in parts by weight:

[0023]

[0024] In the present invention, the content of the silicon-based monomer is preferably 12 to 28 parts by weight, and more preferably 15 to 25 parts by weight.

[0025] In the present invention, the silicon-based monomer is a mixture of 3-(methacryloyloxy)propyltri(trimethylsiloxane)silane and N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane.

[0026] In the present invention, the mass ratio of 3-(methacryloyloxy)propyltri(trimethylsiloxane)silane to N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane is 1-3:1-3, preferably 1.2-2.8:1.2-2.8, and more preferably 1.5-2.5:1.5-2.5.

[0027] In the present invention, 3-(isomethacryloyloxy)propyltri(trimethylsiloxane)silane and N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane are used as silicon-based monomers to participate in the polymerization reaction to obtain a cross-linked network structure, which not only improves the mechanical strength of the contact lens, but also has good optical properties and biocompatibility.

[0028] In the present invention, the content of the amino-modified polydimethylsiloxane is preferably 22 to 38 parts by weight, and more preferably 25 to 35 parts by weight.

[0029] In the present invention, the amino-modified polydimethylsiloxane is used to improve the wearing comfort and surface properties of contact lenses.

[0030] In the present invention, the content of hydroxyethyl methacrylate is preferably 18 to 45 parts by weight, and more preferably 20 to 40 parts by weight.

[0031] In the present invention, the hydroxyethyl methacrylate can adjust the hydrophilicity and softness of the polymer, and help to improve the comfort and water retention performance of the contact lens.

[0032] In the present invention, the content of the N,N-dimethylacrylamide is preferably 15 to 45 parts by weight, and more preferably 20 to 40 parts by weight.

[0033] In the present invention, the N,N-dimethylacrylamide can adjust the chemical and physical properties of the polymer, especially its solubility and processing properties.

[0034] In the present invention, the content of the cross-linking agent is preferably 0.3 to 4.8 parts by weight, and more preferably 0.5 to 4.5 parts by weight.

[0035] In the present invention, the cross-linking agent includes at least two of ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate and 1,3,5-triallyl cyanurate, preferably at least two of ethylene glycol dimethacrylate, ethylene glycol dimethacrylate and 1,3,5-triallyl cyanurate, and more preferably a mixture of ethylene glycol dimethacrylate and ethylene glycol dimethacrylate or a mixture of ethylene glycol dimethacrylate and 1,3,5-triallyl cyanurate.

[0036] In the present invention, the cross-linking agent is used to form a network structure during the polymerization process, enhance the strength and stability of the polymer, and prevent the lens from deforming or breaking.

[0037] In the present invention, the content of the initiator is preferably 0.3 to 4.8 parts by weight, and more preferably 0.5 to 4.5 parts by weight.

[0038] In the present invention, the initiator comprises azobisisobutyronitrile and / or benzoyl peroxide, preferably benzoyl peroxide.

[0039] In the present invention, the initiator generates free radicals by decomposition to initiate chain polymerization between monomer molecules.

[0040] In the present invention, the content of the solvent is preferably 22 to 28 parts by weight, and more preferably 24 to 26 parts by weight.

[0041] In the present invention, the solvent includes n-butanol and / or n-hexanol, preferably n-butanol.

[0042] The present invention also provides a method for preparing silicone hydrogel for contact lenses, comprising the following steps: mixing a silicon-based monomer, amino-modified polydimethylsiloxane, hydroxyethyl methacrylate, N,N-dimethylacrylamide, a crosslinking agent, an initiator and a solvent, and then injecting the mixture into a contact lens mold, and performing a polymerization reaction by thermal initiation to obtain the silicone hydrogel for contact lenses.

[0043] In the present invention, the mixing is carried out under stirring at a speed of 100 to 800 rpm, preferably 150 to 750 rpm, more preferably 200 to 700 rpm; the stirring time is 3 to 12 h, preferably 4 to 11 h, more preferably 5 to 10 h.

[0044] In the present invention, the polymerization reaction temperature is 60 to 120° C., preferably 65 to 115° C., and more preferably 70 to 110° C.; the polymerization reaction time is 8 to 15 h, preferably 9 to 14 h, and more preferably 10 to 12 h.

[0045] 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.

[0046] The amino-modified polydimethylsiloxane used in the present invention is produced by Zhangjiagang Guotai Huarong Chemical New Materials Co., Ltd.

[0047] Example 1

[0048] 10 parts of 3-(isomethacryloyloxy)propyltri(trimethylsiloxane)silane, 5 parts of N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, 30 parts of amino-modified polydimethylsiloxane, 30 parts of hydroxyethyl methacrylate, 25 parts of N,N-dimethylacrylamide, 1.5 parts of ethylene glycol dimethacrylate, 1.5 parts of ethylene glycol dimethacrylate, 2 parts of benzoyl peroxide and 25 parts of n-butanol were mixed at a rotation speed of 600 rpm for 7 hours, then injected into a contact lens mold, and polymerized at 100°C using thermal initiation for 10 hours. After the reaction, a silicone hydrogel for contact lenses was obtained.

[0049] Example 2

[0050] 10 parts of 3-(isomethacryloyloxy)propyltri(trimethylsiloxane)silane, 5 parts of N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, 30 parts of amino-modified polydimethylsiloxane, 30 parts of hydroxyethyl methacrylate, 25 parts of N,N-dimethylacrylamide, 1.5 parts of ethylene glycol dimethacrylate, 1.5 parts of 1,3,5-triallylcyanurate, 2 parts of benzoyl peroxide and 25 parts of n-butanol were mixed at a rotation speed of 600 rpm for 7 hours, then injected into a contact lens mold, and polymerized at 100°C using thermal initiation for 10 hours. After the reaction, a silicone hydrogel for contact lenses was obtained.

[0051] Example 3

[0052] 15 parts of 3-(isomethacryloyloxy)propyltri(trimethylsiloxane)silane, 6 parts of N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, 25 parts of amino-modified polydimethylsiloxane, 30 parts of hydroxyethyl methacrylate, 30 parts of N,N-dimethylacrylamide, 1.2 parts of ethylene glycol dimethacrylate, 1.8 parts of ethylene glycol dimethacrylate, 3 parts of benzoyl peroxide and 30 parts of n-butanol were mixed at a rotation speed of 600 rpm for 7 hours, then injected into a contact lens mold, and polymerized at 100°C using thermal initiation for 10 hours. After the reaction, a silicone hydrogel for contact lenses was obtained.

[0053] Example 4

[0054] Compared with Example 1, the difference is that in Example 4, the polymerization reaction is carried out at 120° C. and the polymerization reaction time is 9 hours.

[0055] Example 5

[0056] Compared with Example 1, the difference is that in Example 5, the polymerization reaction is carried out at 70° C. and the polymerization reaction time is 12 hours.

[0057] Comparative Example 1

[0058] Compared with Example 1, the difference is that the crosslinking agent in Comparative Example 1 is 3 parts of ethylene glycol dimethacrylate.

[0059] Comparative Example 2

[0060] Compared with Example 1, the difference is that the silicon-based monomer in Comparative Example 2 is 15 parts of 3-(methacryloyloxy)propyltri(trimethylsiloxane)silane.

[0061] Comparative Example 3

[0062] Compared with Example 1, the difference is that the hydroxyethyl methacrylate in Example 1 is replaced by N-vinyl pyrrolidone.

[0063] Comparative Example 4

[0064] Compared with Example 1, the difference is that Comparative Example 4 does not add amino-modified polydimethylsiloxane.

[0065] Comparative Example 5

[0066] Compared with Example 1, the difference is that in Comparative Example 5, 20 parts of 3-(isomethacryloyloxy)propyl tris(trimethylsiloxane) silane, 15 parts of N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyl triethoxysilane, 10 parts of amino-modified polydimethylsiloxane, 10 parts of hydroxyethyl methacrylate, 25 parts of N,N-dimethylacrylamide, 3 parts of ethylene glycol dimethacrylate, 2.5 parts of ethylene glycol dimethacrylate, 3 parts of benzoyl peroxide and 30 parts of n-butanol are added.

[0067] Comparative Example 6

[0068] Compared with Example 1, the difference is that the polymerization temperature in Comparative Example 6 is 130°C.

[0069] The properties of the silicone hydrogel lenses for contact lenses prepared in Examples 1 to 5 and Comparative Examples 1 to 6 were tested. The test results are shown in Table 1.

[0070] Table 1 Performance test results of silicone hydrogels prepared in Examples 1 to 5 and Comparative Examples 1 to 6

[0071]

[0072] It can be seen from the above embodiments that the present invention provides a silicone hydrogel for contact lenses and a preparation method thereof. The silicone hydrogel of the present invention is prepared from the following raw materials in parts by weight: 10 to 30 parts of silicon-based monomers, 20 to 40 parts of amino-modified polydimethylsiloxane, 15 to 50 parts of hydroxyethyl methacrylate, 10 to 50 parts of N,N-dimethylacrylamide, 0.1 to 5 parts of cross-linking agents, 0.1 to 5 parts of initiators, and 20 to 30 parts of solvents. The silicone hydrogel provided by the present invention has high oxygen permeability, durability and comfort, can effectively reduce lipid and microbial attachment, thereby solving the problem of eye inflammation and improving the long-term stability and wearing comfort of contact lenses.

[0073] 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 silicone hydrogel for contact lenses, characterized in that: Prepared from the following raw materials in parts by weight:

2. The silicone hydrogel for contact lenses according to claim 1, characterized in that: The silicon-based monomer is a mixture of 3-(isomethacryloyloxy)propyltri(trimethylsiloxane)silane and N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane.

3. The silicone hydrogel for contact lenses according to claim 2, characterized in that: The mass ratio of the 3-(isomethacryloyloxy)propyl tris(trimethylsiloxane)silane to N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyl triethoxysilane is 1-3:1-3.

4. The silicone hydrogel for contact lenses according to any one of claims 1 to 3, characterized in that: The crosslinking agent includes at least two of ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate and triallyl cyanurate.

5. The silicone hydrogel for contact lenses according to claim 4, characterized in that: The initiator includes azobisisobutyronitrile and / or benzoyl peroxide.

6. The silicone hydrogel for contact lenses according to claim 1 or 5, characterized in that: The solvent includes n-butanol and / or n-hexanol.

7. A method for preparing a silicone hydrogel for contact lenses according to any one of claims 1 to 6, characterized in that: The following steps are involved: Silicone-based monomers, amino-modified polydimethylsiloxane, hydroxyethyl methacrylate, N,N-dimethylacrylamide, a crosslinking agent, an initiator and a solvent are mixed and then injected into a contact lens mold, and a polymerization reaction is carried out by thermal initiation to obtain a silicone hydrogel for contact lenses.

8. The method for preparing silicone hydrogel for contact lenses according to claim 7, characterized in that: The mixing is carried out during stirring at a speed of 100 to 800 rpm for a time of 3 to 12 hours.

9. The method for preparing silicone hydrogel for contact lenses according to claim 8, characterized in that: The polymerization reaction temperature is 60-120° C., and the polymerization reaction time is 8-15 hours.

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