Anti-blue light corneal contact lens for controlling myopia

Abstract

The invention belongs to the technical field of contact lenses. The invention relates to an anti-blue-light corneal contact lens for controlling myopia, which is prepared from the following components in parts by weight: 10-40 parts of organic silicon resin, 10-30 parts of silicon monomer, 30-80 parts of water-soluble monomer, 1.0-1.5 parts of anti-blue-light monomer, 0.5-3.0 parts of antibacterial monomer and 0.5-2.0 parts of photoinitiator, wherein the total weight part of the organic silicon resin, the silicon monomer and the water-soluble monomer is 100 parts. The anti-blue-light corneal contact lens for controlling myopia is obtained through formula optimization design and UV curing of self-made anti-blue-light monomers and antibacterial monomers. According to the anti-blue-light corneal contact lens for controlling myopia, the problem that an existing anti-blue-light corneal contact lens is serious in yellowing or poor in antibacterial property, and consequently inflammation hazards are caused is effectively solved.

Description

Technical Field

[0001] The invention relates to a blue light protection corneal contact lens for controlling myopia and belongs to the technical field of contact lenses. Background Art

[0002] With the rapid development and popularization of electronic products, myopia is becoming younger and younger. Myopia is the most common eye disease among adolescents and children in most parts of the world. The progression of myopia will increase the risk of related eye diseases such as glaucoma and retinal degeneration. The main visual angle signal of corneal contact lenses in the prior art for myopia control is generally to change the defocus amount and defocus amount distribution on the lens, such as designing a honeycomb structure, so as to achieve myopia control, that is, to adjust the optical focus through physical structure design to control myopia.

[0003] Corneal contact lenses, also known as "contact lenses", are lenses that are directly attached to the tear layer on the surface of the cornea. They change the refractive power of the eye to achieve the purpose of treating certain eye diseases. Traditional corneal contact lenses for controlling myopia are divided into hard and soft types. Currently, soft corneal contact lenses are mainly available on the market, and soft corneal contact lenses are mainly divided into hydrophilic ones with hydroxyethyl methacrylate as the main material and non-hydrophilic corneal contact lenses with polysiloxane as the main material.

[0004] Hydrophilic corneal contact lenses have high water absorption and become soft and highly water-containing after hydration, which greatly improves the comfort of wearing. However, their oxygen permeability is still low, and corneal hypoxic edema and other lesions often occur after long-term wearing. The flexibility and loose structure of the long siloxane chain of non-hydrophilic corneal contact lenses can directly transmit oxygen in the air to the eyeball, improving oxygen permeability. However, this type of material is highly hydrophobic and easily absorbs protein in tears, resulting in poor comfort. Therefore, the combination of the two types of contact lenses has become the mainstream of development.

[0005] In addition, with the popularity of electronic products such as LCD TVs, tablets and smart phones, the problem of blue light hazards has gradually attracted people's attention. It is generally believed that short-wave blue light (381-460nm) is the main cause of health hazards. Excessive short-wave blue light may cause cataracts and even macular degeneration. Blue light will hinder sleep and seriously endanger our health. Traditional corneal contact lenses for controlling myopia have no anti-blue light effect, and the commonly used anti-blue light means are to add dyes with certain colors, mainly yellow. This method can solve the problem of blue light protection to a certain extent, but at the same time there are the following problems: for example, due to the migration and precipitation of small molecules, it is easy to cause discoloration, which makes the wearer's eyes allergic; for example, the lenses turn yellow, which is difficult for consumers to accept.

[0006] At the same time, the lenses are exposed to a large number of bacteria on the hands every day, which has a significant adverse effect on eye hygiene. Although the care solution has a bactericidal and disinfecting function, it is taken directly by hand when put on and put on, which can easily cause inflammation; and it is also in contact with the outside world during normal wearing, so it is contaminated with bacteria, posing a hygiene risk.

[0007] Therefore, it is necessary to design a new type of corneal contact lens for controlling myopia, which has blue light protection and antibacterial functions and is comfortable to wear so as to achieve the purpose of long-term use. Summary of the invention

[0008] The purpose of the present invention is to provide a blue light-blocking contact lens for controlling myopia and a preparation method thereof, in view of the problems that the blue light-blocking contact lens for controlling myopia in the prior art has serious yellowing or poor antibacterial properties, thereby causing inflammatory hazards. The present invention prepares a blue light-blocking monomer and an antibacterial monomer light-converting agent by molecular design and through formula design. While overcoming the above problems, it also has excellent difficult migration and precipitation properties and has broad application potential. The technical solution adopted by the present invention to solve its technical problems is:

[0009] The present invention provides a method for preparing a blue light blocking monomer, comprising the following steps:

[0010] S11, performing a nucleophilic addition reaction on the blue light blocking substance and the electrophilic reagent containing an acryloyloxy group to obtain a blue light blocking monomer.

[0011] Furthermore, the blue light blocking substance is azobenzene or benzotriazole.

[0012] The present invention also provides a blue light protection monomer, which is prepared by the above-mentioned preparation method.

[0013] Another object of the present invention is to provide a method for preparing an antibacterial monomer, comprising the following steps:

[0014] S21, conducting a coordination reaction between a copper salt and an amino acid under acidic conditions to obtain an intermediate product;

[0015] S22, coupling reaction of the intermediate product with an acryloyloxy derivative to obtain an antibacterial monomer.

[0016] Furthermore, the molar ratio of the copper salt to the amino acid is 1.0:2.0-4.0.

[0017] Furthermore, the acryloxy derivative contains another functional group that can react with a carboxyl group or an amino group.

[0018] The present invention also provides an antibacterial monomer prepared by the above-mentioned preparation method.

[0019] Another object of the present invention is to provide a blue light blocking corneal contact lens for controlling myopia, comprising the following raw materials in parts by weight:

[0020] 10-40 parts of silicone resin;

[0021] 10-30 parts of silicon monomer;

[0022] 30-80 parts of water-soluble monomer;

[0023] 1.0-1.5 parts of anti-blue light monomer;

[0024] Antibacterial monomer 0.5-3.0 parts;

[0025] Photoinitiator 0.5-2.0 parts;

[0026] The total weight of the organic silicon resin, the silicon monomer and the water-soluble monomer is 100 parts.

[0027] Furthermore, the organic silicone resin is an acryloxy-terminated structure.

[0028] Another object of the present invention is to provide a method for preparing a blue light blocking corneal contact lens for controlling myopia, comprising the following steps:

[0029] S31, mixing, i.e.

[0030] Adding raw materials into a mixer according to the formula ratio, mixing and stirring to obtain mixed raw materials;

[0031] S32, solidification, i.e.

[0032] Placing the mixed raw materials in S31 into a mold, curing, and demoulding; and

[0033] S33, washing, swelling, equilibrium, i.e.

[0034] After soaking in an organic solvent, deionized water and physiological saline, the blue light blocking corneal contact lens for controlling myopia is obtained.

[0035] Beneficial effects of the present invention:

[0036] (1) The present invention provides a blue light blocking corneal contact lens for controlling myopia, wherein the formula system contains a self-made blue light blocking monomer, which is a substance containing an acryloyloxy structure. First, the azobenzene or benzotriazole structure has an excellent blue light absorption effect, especially a high absorption rate for short-wave blue light; second, the azobenzene or benzotriazole structure has the advantages of a wide range of selection and strong operability; third, the acryloyloxy structure can be bonded to the system, without the risk of precipitation, and is safe and reliable.

[0037] (2) The present invention provides a blue light-blocking corneal contact lens for controlling myopia. The formula system contains a homemade antibacterial monomer, which is a complex with copper ions as the center and amino acids as ligands, and is terminated with an acryloyloxy group. First, copper ions are inorganic antibacterial agents with excellent broad-spectrum antibacterial properties; second, amino acids are used as ligands. On the one hand, amino acids are excellent organic antibacterial agents, and on the other hand, they can provide anchor points for the next reaction; third, the acryloyloxy structure allows the monomer to be bonded to the system without the risk of precipitation, extending the use time; and it is a multifunctional structure with the advantage of a cross-linking agent to improve performance; fourth, copper ions usually show a blue phase, which can effectively eliminate the yellowing phenomenon caused by the blue light-blocking monomer. In addition, the color development of copper ions is designable, and different hues can be selected according to user preferences for customization.

[0038] (3) The present invention provides a blue light blocking corneal contact lens for controlling myopia. In the formula system, silicone resin, silicone monomer and water-soluble monomer are used in combination. The silicone resin is in a loose state and has excellent oxygen permeability; the water-soluble monomer has excellent water solubility; the three are compounded to have excellent compatibility, moderate hardness and softness, hydrophilic swelling and softening, and eliminate foreign body sensation; at the same time, it also has excellent oxygen permeability and water permeability, is comfortable to wear, and has great practical significance. DETAILED DESCRIPTION

[0039] The present invention is described in detail below with reference to the examples. However, it should be understood that the following examples are only illustrative of the embodiments of the present invention, and are not intended to limit the scope of the present invention.

[0040] The purpose of the present invention is to develop a blue light-proof corneal contact lens for controlling myopia to meet the application requirements of existing corneal contact lenses. The idea of ​​realization is: first, a reactive blue light-proof monomer is made to solve the problem of blue light protection and non-migration; then, the yellowing problem caused by the blue light-proof monomer is eliminated. Considering that blue is the complementary color of yellow, adding an appropriate amount of blue can eliminate yellow. In combination with copper (II) ions, blue is presented in most cases, and copper ions have excellent antibacterial effects at the same time, which can achieve the purpose of antibacterial and covering yellow at the same time. In addition, copper ions are introduced in the form of amino acid complexes, which have synergistic antibacterial effects while adjusting the color development reaction of copper complexes, and technical customization can be achieved for consumers who need personalized colors. The theoretical basis for realization is: for the preparation of reactive blue light-proof monomers, blue light-proof substances and electrophilic addition reactions containing acryloyloxy structures are used for preparation; for the preparation of antibacterial monomers, firstly, the coordination reaction of copper ions and amino acids is carried out, and then the generated structure containing pendant aminocarboxyl groups and the structure containing acryloyloxy groups are prepared by coupling reaction. The above self-made monomers are formulated with silicone resin, silicon monomer, and water-soluble monomers, and UV curing is performed to obtain the target product, i.e., a blue light-blocking corneal contact lens for controlling myopia. The embodiments of the present invention are as follows:

[0041] An embodiment of the present invention provides a method for preparing a blue light blocking monomer, comprising the following steps:

[0042] S11, protecting from light, adding the blue light blocking substance and the electrophilic reagent containing acryloyloxy group to N,N-dimethylformamide, reacting at 0-30° C. for 6-12 hours to obtain the blue light blocking monomer.

[0043] The blue light protection substance and the electrophilic reagent containing an acryloyl group are added in a molar ratio of active hydrogen to the electrophilic reagent of 1:1.

[0044] The blue light blocking substance is azobenzene or benzotriazole and can undergo nucleophilic addition reaction, so it also contains active hydrogen structures such as -OH or -NH2;

[0045] The azobenzene may be aminoazobenzene or hydroxyazobenzene;

[0046] The aminoazobenzene may be 4-aminoazobenzene, p-diaminoazobenzene, N,N-dimethyl-4,4'-azodiphenylamine or 4-amino-3'-methylazobenzene, etc.; and 4-aminoazobenzene is preferred.

[0047] The hydroxyazobenzene may be p-hydroxyazobenzene, 4,4'-dihydroxyazobenzene, 3,3'-dihydroxyazobenzene, or Disperse Orange B.

[0048] The benzotriazoles may be aminobenzotriazoles or hydroxybenzotriazoles;

[0049] The aminobenzotriazoles may be 2-phenyl-2H-benzotriazole-5-ylamine, 1-methyl-1H-1,2,3-benzotriazole-5-amine, 1-aminobenzotriazole, 4-aminobenzotriazole, etc.; and preferably 2-phenyl-2H-benzotriazole-5-ylamine.

[0050] The hydroxybenzotriazoles may be 4-hydroxybenzotriazole, (1H-benzo[D][1,2,3]triazol-5-yl)methanol, and the like.

[0051] The electrophilic reagent containing acryloyloxy group is acryloyl chloride or isocyanoethyl methacrylate, etc.

[0052] The preparation method of the anti-blue light monomer described in the present invention adopts a nucleophilic addition reaction, in which the active hydrogen such as hydroxyl or amino group in the anti-blue light substance reacts with the acyl chloride or isocyanate in the electrophilic reagent; in the embodiment of the present invention, the reaction efficiency is considered from multiple factors such as reaction conditions, controllability, and later impurity removal, and the amino structure is preferably reacted with isocyanoethyl methacrylate for nucleophilic addition reaction.

[0053] The present invention also provides a method for preparing an antibacterial monomer, comprising the following steps:

[0054] S21, adding copper salt to deionized water, heating to 40-60°C, adding amino acid, adjusting pH to 4.0-6.0, controlling the pH value to be constant, and continuing stirring for 0.5-2.0h; cooling to room temperature, distilling under reduced pressure, taking the concentrate and vacuum drying it at 40°C for 12h to obtain an intermediate product;

[0055] The molar ratio of the copper salt to the amino acid is 1.0:2.0-4.0;

[0056] The amount of the copper salt and deionized water is 1g:10mL;

[0057] The copper salt may be copper chloride, copper sulfate or copper nitrate, etc.; and, in the following embodiments of the present invention, the copper salt is copper chloride;

[0058] The amino acid may be an acidic amino acid, a neutral amino acid or a basic amino acid;

[0059] The acidic amino acid may be aspartic acid, glutamic acid, etc.; and glutamic acid is preferred;

[0060] The neutral amino acid may be glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, tryptophan, etc.; and preferably glycine;

[0061] The basic amino acid may be arginine, lysine, histidine, etc., and arginine is preferred.

[0062] The selection of acidic, neutral and alkaline amino acids is related to the coordination number of copper ions, and the complexes formed by different amino acids and copper ions have different colors, which can be customized according to needs.

[0063] S22, protect from light, add the intermediate product, acryloyloxy derivative, inhibitor and tetrabutylammonium bromide into tetrahydrofuran, heat and reflux for 18-24 hours; cool to room temperature, distill under reduced pressure, take the concentrate and place it under vacuum at 40°C for 12 hours to obtain an antibacterial monomer.

[0064] The acryloyloxy derivative contains another functional group that can react with a carboxyl group or an amino group, and mainly reacts with a carboxyl group. Therefore, the acryloyloxy derivative is glycidyl methacrylate or (glycidyloxy)ethyl methacrylate, etc., and glycidyl methacrylate is preferred.

[0065] The intermediate product and the acryloyloxy derivative are added in a molar ratio of aminocarboxyl group to epoxy group of 1:1;

[0066] The usage ratio of the acryloyloxy derivative, tetrabutylammonium bromide and tetrahydrofuran is 0.1 mol: 0.02 mol: 100 mL;

[0067] The amount of the polymerization inhibitor is 0.2 wt % of the acryloyloxy derivative; and the polymerization inhibitor in the following examples of the present invention is p-hydroxyanisole.

[0068] The embodiment of the present invention further provides a blue light blocking corneal contact lens for controlling myopia, comprising the following raw materials in parts by weight:

[0069] 10-40 parts of silicone resin;

[0070] 10-30 parts of silicon monomer;

[0071] 30-80 parts of water-soluble monomer;

[0072] 1.0-1.5 parts of anti-blue light monomer;

[0073] Antibacterial monomer 0.5-3.0 parts;

[0074] Photoinitiator 0.5-2.0 parts;

[0075] The total weight of the organic silicone resin, the silicon monomer and the water-soluble monomer is 100 parts.

[0076] The organic silicone resin is an acryloxy-terminated structure; and the preparation method of the organic silicone resin is as follows:

[0077] Add hydroxyl-terminated polydimethylsiloxane, isocyanoethyl methacrylate, dibutyltin dilaurate and p-hydroxyanisole to N,N-dimethylformamide, and react at 80°C until the isocyanate peak monitored by infrared disappears; cool to room temperature, distill under reduced pressure, concentrate in vacuo, add methanol to produce a precipitate, filter, take the insoluble matter, and dry in vacuo at 40°C for 12 hours to obtain the silicone resin.

[0078] The hydroxyl-terminated polydimethylsiloxane and isocyanoethyl methacrylate are added in a molar ratio of hydroxyl to isocyanate of 1:1;

[0079] The dosage ratio of the hydroxyl-terminated polydimethylsiloxane and N,N-dimethylformamide is 1 g:10 mL;

[0080] The amount of dibutyltin dilaurate is 0.5wt% of the mass of isocyanoethyl methacrylate;

[0081] The dosage of the p-hydroxyanisole is 0.2 wt % of the mass of isocyanoethyl methacrylate.

[0082] The hydroxyl-terminated polydimethylsiloxane was purchased from Anhui Mingyi Silicon Industry Co., Ltd., model MY1203.

[0083] The silicon monomer may be mercaptosiloxane, acryloxysiloxane or vinylsiloxane;

[0084] The mercaptosiloxane may be KH580 or KH590, etc., and preferably KH580;

[0085] The acryloxysiloxane may be KH570, KH571, KH670 or GX572, etc., and preferably KH570;

[0086] The vinyl siloxane may be KH151, KH171 or KH172, etc., and preferably KH151.

[0087] The water-soluble monomer is (meth)acrylic acid, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate.

[0088] The photoinitiator is a commonly used photoinitiator, which may be photoinitiator 1173, photoinitiator 184, photoinitiator 2959, photoinitiator 369 or photoinitiator TPO, etc.; and the photoinitiator described in the following embodiments of the present invention is photoinitiator 1173.

[0089] The embodiment of the present invention also provides a method for preparing a blue light blocking corneal contact lens for controlling myopia, comprising the following steps:

[0090] S31, mixing, i.e.

[0091] Adding raw materials into a mixer according to the formula ratio, mixing and stirring to obtain mixed raw materials;

[0092] S32, solidification, i.e.

[0093] The mixed raw materials in S31 are placed in a mold, solidified, and demoulded;

[0094] The curing process is: under UV wavelength of 275-398nm, the light intensity is 4-30mW / cm 2 , radiation duration 0.5-4.0h;

[0095] S33, washing, swelling, equilibrium, i.e.

[0096] After soaking in organic solvent ethanol for 2 hours, deionized water for 3 hours, and physiological saline for 2 hours, the blue light blocking corneal contact lens for controlling myopia is obtained.

[0097] In order to further understand the present invention, a blue light blocking corneal contact lens for controlling myopia provided by the present invention is described in detail below in conjunction with specific embodiments. The protection scope of the present invention is not limited by the following embodiments.

[0098] Example 1

[0099] A method for preparing a blue light protection monomer comprises the following steps:

[0100] S11, protected from light, add 4-aminoazobenzene and isocyanoethyl methacrylate to N,N-dimethylformamide, react at 30°C for 6h to obtain a blue light blocking monomer.

[0101] The 4-aminoazobenzene and isocyanoethyl methacrylate are added in a molar ratio of amino group to isocyanate of 1:1.

[0102] Its infrared data are as follows: 3315cm -1 :-NH- exists; 1735cm -1 、1687cm -1 :-C=O exists; 1659cm -1 :-N=N- exists; 1597cm -1 、1402cm -1 : benzene ring exists; 1604cm -1 、811cm -1 :-C=C- exists; 2250cm -1 :-NCO does not exist.

[0103] A method for preparing an antibacterial monomer comprises the following steps:

[0104] S21, adding copper salt to deionized water, heating to 50°C, adding arginine, adjusting the pH to 5.0, controlling the pH value to be constant, and continuing stirring for 1.0h; cooling to room temperature, distilling under reduced pressure, taking the concentrate and placing it under vacuum at 40°C for 12h to obtain an intermediate product;

[0105] The molar ratio of the copper salt to arginine is 1.0:2.0;

[0106] The amount of the copper salt and deionized water is 1g:10mL.

[0107] Its infrared data is as follows: 3426cm -1 :-OH exists; 1760cm -1 :-C=O (carboxyl) exists; 3314cm -1 :-NH- exists; 3288cm -1 :-NH- coordination exists; 418cm -1 : Cu-N coordination exists.

[0108] S22, protect from light, add the intermediate product, glycidyl methacrylate, inhibitor and tetrabutylammonium bromide into tetrahydrofuran, heat and reflux for 20 hours; cool to room temperature, distill under reduced pressure, take the concentrate and place it under vacuum drying at 40°C for 12 hours to obtain the antibacterial monomer.

[0109] The intermediate product and glycidyl methacrylate are added in a molar ratio of aminocarboxyl group to epoxy group of 1:1;

[0110] The usage ratio of glycidyl methacrylate, tetrabutylammonium bromide and tetrahydrofuran is 0.1 mol: 0.02 mol: 100 mL;

[0111] The dosage of the polymerization inhibitor is 0.2 wt % of glycidyl methacrylate.

[0112] Its infrared data is as follows: 3423cm -1 :-OH exists; 1735cm -1 :-C=O (ester group) exists; 3314cm -1 :-NH- exists; 3288cm -1 :-NH- coordination exists; 1604cm -1 、811cm -1 :-C=C- exists; 418cm -1 :Cu-N coordination exists; 1760cm -1 :-C=O (carboxyl) does not exist; 1265cm -1 、938cm -1 、801cm -1 : Epoxy group does not exist.

[0113] A blue light blocking corneal contact lens for controlling myopia, comprising the following raw materials in parts by weight:

[0114] 25 parts of silicone resin;

[0115] Silicon monomer KH570 20 parts;

[0116] 45 parts of hydroxyethyl methacrylate;

[0117] 10 parts of methacrylic acid;

[0118] 1.2 parts of anti-blue light monomer;

[0119] 2.0 parts of antibacterial monomer;

[0120] Photoinitiator 1.0 part

[0121] A method for preparing a blue light blocking corneal contact lens for controlling myopia comprises the following steps:

[0122] S31, mixing, i.e.

[0123] Adding raw materials into a mixer according to the formula ratio, mixing and stirring to obtain mixed raw materials;

[0124] S32, solidification, i.e.

[0125] The mixed raw materials in S31 are placed in a mold, solidified, and demoulded;

[0126] The curing process is: at a UV wavelength of 365nm, the light intensity is 20mW / cm 2 , radiation duration 1.0h;

[0127] S33, washing, swelling, equilibrium, i.e.

[0128] After soaking in organic solvent ethanol for 2 hours, deionized water for 3 hours, and physiological saline for 2 hours, the blue light blocking corneal contact lens for controlling myopia is obtained.

[0129] Example 2

[0130] The rest is the same as in Example 1, except that:

[0131] A method for preparing a blue light protection monomer comprises the following steps:

[0132] S11, protected from light, add 2-phenyl-2H-benzotriazole-5-ylamine and isocyanoethyl methacrylate to N,N-dimethylformamide, and react at 0°C for 12h to obtain a blue light blocking monomer.

[0133] The 2-phenyl-2H-benzotriazole-5-ylamine and isocyanoethyl methacrylate are added in a molar ratio of amino group to isocyanate of 1:1.

[0134] Its infrared data are as follows: 3315cm -1 :-NH- exists; 1735cm -1 、1687cm -1 :-C=O exists; 1647cm -1 :-C=N- exists; 1595cm -1 、1401cm -1 : benzene ring exists; 1604cm -1 、811cm -1 :-C=C- exists; 2250cm -1 :-NCO does not exist.

[0135] A method for preparing an antibacterial monomer comprises the following steps:

[0136] S21, adding copper salt to deionized water, heating to 60°C, adding arginine, adjusting the pH to 4.0, controlling the pH value to be constant, and continuing stirring for 0.5h; cooling to room temperature, distilling under reduced pressure, taking the concentrate and placing it under vacuum at 40°C for 12h to obtain an intermediate product;

[0137] The molar ratio of the copper salt to arginine is 1.0:2.0;

[0138] The amount of the copper salt and deionized water is 1g:10mL.

[0139] Its infrared data is as follows: 3426cm -1 :-OH exists; 1760cm -1 :-C=O (carboxyl) exists; 3314cm -1 :-NH- exists; 3288cm -1 :-NH- coordination exists; 418cm -1 : Cu-N coordination exists.

[0140] S22, protect from light, add the intermediate product, glycidyl methacrylate, inhibitor and tetrabutylammonium bromide into tetrahydrofuran, heat and reflux for 20 hours; cool to room temperature, distill under reduced pressure, take the concentrate and place it under vacuum drying at 40°C for 12 hours to obtain the antibacterial monomer.

[0141] The intermediate product and glycidyl methacrylate are added in a molar ratio of aminocarboxyl group to epoxy group of 1:1;

[0142] The usage ratio of glycidyl methacrylate, tetrabutylammonium bromide and tetrahydrofuran is 0.1 mol: 0.02 mol: 100 mL;

[0143] The dosage of the polymerization inhibitor is 0.2 wt % of glycidyl methacrylate.

[0144] Its infrared data is as follows: 3423cm -1 :-OH exists; 1735cm -1 :-C=O (ester group) exists; 3314cm -1 :-NH- exists; 3288cm -1 :-NH- coordination exists; 1604cm -1 、811cm -1 :-C=C- exists; 418cm -1 :Cu-N coordination exists; 1760cm -1 :-C=O (carboxyl) does not exist; 1265cm -1 、938cm -1 、801cm -1 : Epoxy group does not exist.

[0145] Example 3

[0146] The rest is the same as in Example 1, except that:

[0147] A method for preparing a blue light protection monomer comprises the following steps:

[0148] S11, protected from light, add 2-phenyl-2H-benzotriazole-5-ylamine and isocyanoethyl methacrylate to N,N-dimethylformamide, and react at 20°C for 10 hours to obtain a blue light blocking monomer.

[0149] The 2-phenyl-2H-benzotriazole-5-ylamine and isocyanoethyl methacrylate are added in a molar ratio of amino group to isocyanate of 1:1.

[0150] Its infrared data are as follows: 3315cm -1 :-NH- exists; 1735cm -1 、1687cm -1 :-C=O exists; 1647cm -1 :-C=N- exists; 1595cm -1 、1401cm -1 : benzene ring exists; 1604cm -1 、811cm -1 :-C=C- exists; 2250cm -1 :-NCO does not exist.

[0151] A method for preparing an antibacterial monomer comprises the following steps:

[0152] S21, adding copper salt to deionized water, heating to 40°C, adding arginine, adjusting the pH to 6.0, controlling the pH value to be constant, and continuing stirring for 2.0 hours; cooling to room temperature, distilling under reduced pressure, taking the concentrate and placing it under vacuum at 40°C for 12 hours to obtain an intermediate product;

[0153] The molar ratio of the copper salt to arginine is 1.0:2.0;

[0154] The amount of the copper salt and deionized water is 1g:10mL.

[0155] Its infrared data is as follows: 3426cm -1 :-OH exists; 1760cm -1 :-C=O (carboxyl) exists; 3314cm -1 :-NH- exists; 3288cm -1 :-NH- coordination exists; 418cm -1 : Cu-N coordination exists.

[0156] S22, protect from light, add the intermediate product, glycidyl methacrylate, inhibitor and tetrabutylammonium bromide into tetrahydrofuran, heat and reflux for 20 hours; cool to room temperature, distill under reduced pressure, take the concentrate and place it under vacuum drying at 40°C for 12 hours to obtain the antibacterial monomer.

[0157] The intermediate product and glycidyl methacrylate are added in a molar ratio of aminocarboxyl group to epoxy group of 1:1;

[0158] The usage ratio of glycidyl methacrylate, tetrabutylammonium bromide and tetrahydrofuran is 0.1 mol: 0.02 mol: 100 mL;

[0159] The dosage of the polymerization inhibitor is 0.2 wt % of glycidyl methacrylate.

[0160] Its infrared data is as follows: 3423cm -1 :-OH exists; 1735cm -1 :-C=O (ester group) exists; 3314cm -1 :-NH- exists; 3288cm -1 :-NH- coordination exists; 1604cm -1 、811cm -1 :-C=C- exists; 418cm -1 : Cu-N coordination exists; 1760cm -1 :-C=O (carboxyl) does not exist; 1265cm -1 、938cm -1 、801cm -1 : Epoxy group does not exist.

[0161] Example 4

[0162] The rest is the same as in Example 1, except that:

[0163] A method for preparing an antibacterial monomer comprises the following steps:

[0164] S21, adding copper salt to deionized water, heating to 50°C, adding glycine, adjusting the pH to 5.0, controlling the pH value to be constant, and continuing stirring for 1.0h; cooling to room temperature, distilling under reduced pressure, taking the concentrate and placing it under vacuum at 40°C for 12h to obtain an intermediate product;

[0165] The molar ratio of the copper salt to glycine is 1.0:4.0;

[0166] The amount of the copper salt and deionized water is 1g:10mL.

[0167] Its infrared data is as follows: 3426cm -1 :-OH exists; 1760cm -1 :-C=O (carboxyl) exists; 3288cm -1 :-NH- coordination exists; 418cm -1 : Cu-N coordination exists.

[0168] S22, protect from light, add the intermediate product, glycidyl methacrylate, inhibitor and tetrabutylammonium bromide into tetrahydrofuran, heat and reflux for 18 hours; cool to room temperature, distill under reduced pressure, take the concentrate and place it under vacuum at 40°C for 12 hours to obtain an antibacterial monomer.

[0169] The intermediate product and glycidyl methacrylate are added in a molar ratio of carboxyl group to epoxy group of 1:1;

[0170] The usage ratio of glycidyl methacrylate, tetrabutylammonium bromide and tetrahydrofuran is 0.1 mol: 0.02 mol: 100 mL;

[0171] The dosage of the polymerization inhibitor is 0.2 wt % of glycidyl methacrylate.

[0172] Its infrared data is as follows: 3423cm -1 :-OH exists; 1735cm -1 :-C=O (ester group) exists; 3288cm -1 :-NH- coordination exists; 1604cm -1 、811cm -1 :-C=C- exists; 418cm -1 :Cu-N coordination exists; 1760cm -1 :-C=O (carboxyl) does not exist; 1265cm-1 、938cm -1 、801cm -1 : Epoxy group does not exist.

[0173] Example 5

[0174] The rest is the same as in Example 1, except that:

[0175] S21, adding copper salt to deionized water, heating to 50°C, adding glutamic acid, adjusting the pH to 5.0, controlling the pH value to be constant, and continuing stirring for 1.0h; cooling to room temperature, distilling under reduced pressure, taking the concentrate and placing it under vacuum at 40°C for 12h to obtain an intermediate product;

[0176] The molar ratio of the copper salt to glutamic acid is 1.0:4.0;

[0177] The amount of the copper salt and deionized water is 1g:10mL.

[0178] Its infrared data is as follows: 3426cm -1 :-OH exists; 1760cm -1 :-C=O (carboxyl) exists; 3288cm -1 :-NH- coordination exists; 418cm -1 : Cu-N coordination exists.

[0179] S22, protect from light, add the intermediate product, glycidyl methacrylate, inhibitor and tetrabutylammonium bromide into tetrahydrofuran, heat and reflux for 24 hours; cool to room temperature, distill under reduced pressure, take the concentrate and place it under vacuum at 40°C for 12 hours to obtain an antibacterial monomer.

[0180] The intermediate product and glycidyl methacrylate are added in a molar ratio of carboxyl group to epoxy group of 1:1;

[0181] The usage ratio of glycidyl methacrylate, tetrabutylammonium bromide and tetrahydrofuran is 0.1 mol: 0.02 mol: 100 mL;

[0182] The dosage of the polymerization inhibitor is 0.2 wt % of glycidyl methacrylate.

[0183] Its infrared data is as follows: 3423cm -1 :-OH exists; 1735cm -1 :-C=O (ester group) exists; 3288cm -1 :-NH- coordination exists; 1604cm -1 、811cm -1 :-C=C- exists; 418cm -1 :Cu-N coordination exists; 1760cm-1 :-C=O (carboxyl) does not exist; 1265cm -1 、938cm -1 、801cm -1 : Epoxy group does not exist.

[0184] Example 6

[0185] The rest is the same as in Example 1, except that:

[0186] The silicon monomer KH570 was replaced by KH580.

[0187] Example 7

[0188] The rest is the same as in Example 1, except that:

[0189] The silicon monomer KH570 was replaced by KH151.

[0190] Example 8

[0191] The rest is the same as in Example 1, except that:

[0192] A blue light blocking corneal contact lens for controlling myopia, comprising the following raw materials in parts by weight:

[0193] 10 parts of silicone resin;

[0194] Silicon monomer KH570 30 parts;

[0195] 45 parts of hydroxyethyl methacrylate;

[0196] Methacrylic acid 15 parts;

[0197] 1.2 parts of anti-blue light monomer;

[0198] 2.0 parts of antibacterial monomer;

[0199] 1.5 parts of photoinitiator.

[0200] A method for preparing a blue light blocking corneal contact lens for controlling myopia comprises the following steps:

[0201] S31, mixing, i.e.

[0202] Adding raw materials into a mixer according to the formula ratio, mixing and stirring to obtain mixed raw materials;

[0203] S32, solidification, i.e.

[0204] The mixed raw materials in S31 are placed in a mold, solidified, and demoulded;

[0205] The curing process is: at a UV wavelength of 275nm, the light intensity is 30mW / cm 2, radiation duration 3.0h;

[0206] S33, washing, swelling, equilibrium, i.e.

[0207] After soaking in organic solvent ethanol for 2 hours, deionized water for 3 hours, and physiological saline for 2 hours, the blue light blocking corneal contact lens for controlling myopia is obtained.

[0208] Example 9

[0209] The rest is the same as in Example 1, except that:

[0210] A blue light blocking corneal contact lens for controlling myopia, comprising the following raw materials in parts by weight:

[0211] 40 parts of silicone resin;

[0212] Silicon monomer KH570 10 parts;

[0213] 50 parts of hydroxyethyl methacrylate;

[0214] 1.2 parts of anti-blue light monomer;

[0215] 2.0 parts of antibacterial monomer;

[0216] Photoinitiator 1.0 part

[0217] A method for preparing a blue light blocking corneal contact lens for controlling myopia comprises the following steps:

[0218] S31, mixing, i.e.

[0219] Adding raw materials into a mixer according to the formula ratio, mixing and stirring to obtain mixed raw materials;

[0220] S32, solidification, i.e.

[0221] The mixed raw materials in S31 are placed in a mold, solidified, and demoulded;

[0222] The curing process is: at a UV wavelength of 398nm, the light intensity is 5mW / cm 2 , radiation duration 2.0h;

[0223] S33, washing, swelling, equilibrium, i.e.

[0224] After soaking in organic solvent ethanol for 2 hours, deionized water for 3 hours, and physiological saline for 2 hours, the blue light blocking corneal contact lens for controlling myopia is obtained.

[0225] Example 10

[0226] The rest is the same as in Example 1, except that:

[0227] A blue light blocking corneal contact lens for controlling myopia, comprising the following raw materials in parts by weight:

[0228] 10 parts of silicone resin;

[0229] Silicon monomer KH570 10 parts;

[0230] 60 parts of hydroxyethyl methacrylate;

[0231] 20 parts of methacrylic acid;

[0232] 1.2 parts of anti-blue light monomer;

[0233] 2.0 parts of antibacterial monomer;

[0234] 2.0 parts of photoinitiator.

[0235] A method for preparing a blue light blocking corneal contact lens for controlling myopia comprises the following steps:

[0236] S31, mixing, i.e.

[0237] Adding raw materials into a mixer according to the formula ratio, mixing and stirring to obtain mixed raw materials;

[0238] S32, solidification, i.e.

[0239] The mixed raw materials in S31 are placed in a mold, solidified, and demoulded;

[0240] The curing process is: at a UV wavelength of 365nm, the light intensity is 4mW / cm 2 , radiation duration 4.0h;

[0241] S33, washing, swelling, equilibrium, i.e.

[0242] After soaking in organic solvent ethanol for 2 hours, deionized water for 3 hours, and physiological saline for 2 hours, the blue light blocking corneal contact lens for controlling myopia is obtained.

[0243] Embodiment 11

[0244] The rest is the same as in Example 1, except that:

[0245] A blue light blocking corneal contact lens for controlling myopia, comprising the following raw materials in parts by weight:

[0246] 40 parts of silicone resin;

[0247] Silicon monomer KH570 30 parts;

[0248] 20 parts of hydroxyethyl methacrylate;

[0249] 10 parts of 4-hydroxybutyl acrylate;

[0250] 10 parts of methacrylic acid;

[0251] 1.2 parts of anti-blue light monomer;

[0252] 2.0 parts of antibacterial monomer;

[0253] 0.5 parts of photoinitiator.

[0254] A method for preparing a blue light blocking corneal contact lens for controlling myopia comprises the following steps:

[0255] S31, mixing, i.e.

[0256] Adding raw materials into a mixer according to the formula ratio, mixing and stirring to obtain mixed raw materials;

[0257] S32, solidification, i.e.

[0258] The mixed raw materials in S31 are placed in a mold, solidified, and demoulded;

[0259] The curing process is: at a UV wavelength of 365nm, the light intensity is 30mW / cm 2 , radiation duration 0.5h;

[0260] S33, washing, swelling, equilibrium, i.e.

[0261] After soaking in organic solvent ethanol for 2 hours, deionized water for 3 hours, and physiological saline for 2 hours, the blue light blocking corneal contact lens for controlling myopia is obtained.

[0262] Example 12

[0263] The rest is the same as in Example 1, except that:

[0264] A blue light blocking corneal contact lens for controlling myopia, comprising the following raw materials in parts by weight:

[0265] 25 parts of silicone resin;

[0266] Silicon monomer KH570 20 parts;

[0267] 45 parts of hydroxyethyl methacrylate;

[0268] 10 parts of methacrylic acid;

[0269] 1.0 part of anti-blue light monomer;

[0270] 0.5 parts of antibacterial monomer;

[0271] Photoinitiator 1.0 part

[0272] Example 13

[0273] The rest is the same as in Example 1, except that:

[0274] A blue light blocking corneal contact lens for controlling myopia, comprising the following raw materials in parts by weight:

[0275] 25 parts of silicone resin;

[0276] Silicon monomer KH570 20 parts;

[0277] 45 parts of hydroxyethyl methacrylate;

[0278] 10 parts of methacrylic acid;

[0279] 1.5 parts of anti-blue light monomer;

[0280] 3.0 parts of antibacterial monomer;

[0281] Photoinitiator 1.0 part

[0282] The following comparative examples of anti-blue light corneal contact lenses for controlling myopia are compared with Example 1:

[0283] Comparative Example 1

[0284] The rest is the same as in Example 1, except that:

[0285] A blue light blocking corneal contact lens for controlling myopia, wherein no blue light blocking monomer or antibacterial monomer is added to the formula raw materials.

[0286] Comparative Example 2

[0287] The rest is the same as in Example 1, except that:

[0288] A blue light blocking corneal contact lens for controlling myopia, wherein no blue light blocking monomer is added to the formula raw materials.

[0289] Comparative Example 3

[0290] The rest is the same as in Example 1, except that:

[0291] The blue light blocking monomer is replaced with 4-aminoazobenzene.

[0292] Comparative Example 4

[0293] The rest is the same as in Example 1, except that:

[0294] A blue light blocking corneal contact lens for controlling myopia, wherein no antibacterial monomer is added to the formula raw materials.

[0295] Comparative Example 5

[0296] The rest is the same as in Example 1, except that:

[0297] The copper salt is replaced by a zinc salt of the same anion.

[0298] Comparative Example 6

[0299] The rest is the same as in Example 1, except that:

[0300] The copper salt is replaced by a ferrous salt of the same anion.

[0301] Comparative Example 7

[0302] The rest is the same as in Example 1, except that:

[0303] The arginine was replaced with terephthalic acid.

[0304] Comparative Example 8

[0305] The rest is the same as in Example 1, except that:

[0306] The antibacterial monomer is replaced by the intermediate product in Example 1.

[0307] Comparative Example 9

[0308] The rest is the same as in Example 1, except that:

[0309] A blue light blocking corneal contact lens for controlling myopia, comprising the following raw materials in parts by weight:

[0310] 82 parts of hydroxyethyl methacrylate;

[0311] Methacrylic acid 18 parts;

[0312] 1.2 parts of anti-blue light monomer;

[0313] 2.0 parts of antibacterial monomer;

[0314] Photoinitiator 1.0 part

[0315] Comparative Example 10

[0316] The rest is the same as in Example 1, except that:

[0317] A blue light blocking corneal contact lens for controlling myopia, comprising the following raw materials in parts by weight:

[0318] 45 parts of silicone resin;

[0319] 45 parts of hydroxyethyl methacrylate;

[0320] 10 parts of methacrylic acid;

[0321] 1.2 parts of anti-blue light monomer;

[0322] 2.0 parts of antibacterial monomer;

[0323] Photoinitiator 1.0 part

[0324] The physical properties of the blue light blocking corneal contact lenses for controlling myopia prepared in Examples 1-13 of the present invention and Comparative Examples 1-10 were measured respectively, and the results are shown in Table 1.

[0325] Table 1 Physical test performance of each embodiment

[0326]

[0327] First, it can be concluded from Examples 1-13 in Table 1 that the blue light blocking corneal contact lens for controlling myopia of the present invention has excellent blue light absorption effect and excellent antibacterial performance; it also has high oxygen permeability, low elastic coefficient, and excellent comfort.

[0328] Second, it can be observed from Example 1 and Comparative Examples 1-3 that the blue light blocking corneal contact lens for controlling myopia in the present invention uses a homemade blue light blocking monomer, has excellent blue light absorption effect, and does not have the risk of precipitation.

[0329] Third, it can be observed from Example 1 and Comparative Examples 1 and 4-8 that the blue light blocking corneal contact lenses for controlling myopia in the present invention use homemade antibacterial monomers, have excellent yellow light compensation properties, and can effectively improve the appearance acceptance. At the same time, copper ions are combined with amino acids to have synergistic antibacterial properties and are difficult to precipitate.

[0330] Fourth, it can be observed from Example 1 and Comparative Examples 9-10 that the blue light blocking corneal contact lens for controlling myopia in the present invention uses a compound of silicone resin, silicone monomer and water-soluble monomer, has excellent oxygen permeability, water content and elastic coefficient, and can effectively improve wearing comfort.

[0331] In summary, the blue light blocking corneal contact lens for controlling myopia of the present invention uses homemade blue light blocking monomers and antibacterial monomers, and is formulated with a compound of silicone resin, silicon monomer, and water-soluble monomer. It has excellent blue light absorption, antibacterial properties, and a good experience of comfort.

[0332] The test method is as follows:

[0333] (1) Blue light transmittance: The scanning range is 380-455nm, and the scanning interval is 1nm. The method of expressing UV-visible light absorption: The absorption effect is expressed by the average transmittance value. The lower the transmittance, the better the absorption effect.

[0334] (2) Antibacterial activity: The test was conducted in accordance with the method described in GB / T 21866-2008. The bacterial species was Escherichia coli.

[0335] (3) Oxygen permeability: tested according to the method described in GB 11417.3-2012.

[0336] (4) Moisture content: The moisture content is measured by weighing method, the weight of the slide is Q1, the weight of the lens and the slide is Q2, and after drying in a 50°C oven for 19 hours, the gross weight is G3. Moisture content = (Q2-G3) / (Q2-Q1).

[0337] (5) Elastic modulus: tested according to the method described in ISO 18369.

[0338] (6) Lens discoloration: Soak the lens in ethanol for 2 hours and then take it out. Use a cotton swab to scrape the lens surface 40 times. Finally, visually observe whether there is color on the surface of the cotton swab to determine whether the lens has discolored. ◎ indicates that the lens has not discolored, and X indicates that the lens has discolored.

[0339] (7) Color rendering: Observe the color of the lens visually.

[0340] Based on the above ideal embodiments of the present invention, the relevant staff can make various changes and modifications without departing from the technical concept of the present invention through the above description. The technical scope of the present invention is not limited to the contents of the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. A method for preparing a blue light blocking monomer, characterized in that: The following steps are involved: S11, performing a nucleophilic addition reaction on the blue light blocking substance and the electrophilic reagent containing an acryloyloxy group to obtain a blue light blocking monomer.

2. The preparation method according to claim 1, characterized in that: The blue light protection substance is azobenzene or benzotriazole.

3. A blue light protection monomer, characterized in that: Prepared by the preparation method according to claim 1 or 2.

4. A method for preparing an antibacterial monomer, characterized in that: The following steps are involved: S21, conducting a coordination reaction between a copper salt and an amino acid under acidic conditions to obtain an intermediate product; S22, coupling reaction of the intermediate product with an acryloyloxy derivative to obtain an antibacterial monomer.

5. The preparation method according to claim 4, characterized in that: The molar ratio of the copper salt to the amino acid is 1.0:2.0-4.

0.

6. The preparation method according to claim 4, characterized in that: The acryloxy derivative contains another functional group that can react with a carboxyl group or an amino group.

7. An antibacterial monomer, characterized in that: Prepared by the preparation method according to any one of claims 4 to 6.

8. A blue light blocking corneal contact lens for controlling myopia, characterized in that: The invention comprises the following raw materials in parts by weight: 10-40 parts of silicone resin; 10-30 parts of silicon monomer; 30-80 parts of water-soluble monomer; 1.0-1.5 parts of anti-blue light monomer; Antibacterial monomer 0.5-3.0 parts; Photoinitiator 0.5-2.0 parts; The total weight of the organic silicone resin, the silicon monomer and the water-soluble monomer is 100 parts.

9. The blue light blocking corneal contact lens for controlling myopia according to claim 8, characterized in that: The organic silicon resin is an acryloxy-terminated structure.

10. A method for preparing a blue light blocking corneal contact lens for controlling myopia, characterized in that: The steps include: S31, mixing, i.e. Adding raw materials into a mixer according to the formula ratio, mixing and stirring to obtain mixed raw materials; S32, solidification, i.e. The mixed raw materials in S31 are placed in a mold, solidified, and demoulded; as well as S33, washing, swelling, equilibrium, i.e. After soaking in an organic solvent, deionized water and physiological saline, the blue light blocking corneal contact lens for controlling myopia is obtained.

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