A soft, hydrophilic contact lens and a method of making the same

Abstract

The application relates to the technical field of optical materials, and discloses a soft hydrophilic contact lens and a preparation method thereof. The soft hydrophilic contact lens comprises a hydrogel matrix layer, an antibacterial layer coated on the surface of the hydrogel matrix layer, and a nanometer siloxane composite layer coated on the surface of the antibacterial layer. The raw material of the hydrogel matrix layer comprises a hydrogel monomer, a linear polypeptide and a photoinitiator; the antibacterial layer is composed of a quaternary ammonium salt monomer; the nanometer siloxane composite layer is formed by covalent crosslinking and compounding of nanometer siloxane, the particle size of the nanometer siloxane is 20-50 nm, the nanometer siloxane is selected from at least one of dimethyl siloxy cage polysilsesquioxane, glycidyl ether oxygen propyl cage polysilsesquioxane and octavinyl cage polysilsesquioxane; and the temperature of covalent crosslinking is 43-50 DEG C. The preparation method is simple and efficient, and the prepared soft hydrophilic contact lens has good moisture retention, antibacterial property, wear resistance and water content.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of optical materials, in particular to a soft hydrophilic contact lens and a preparation method thereof. BACKGROUND

[0002] Soft hydrophilic contact lenses bring users clearer vision and more comfortable wearing experience, meet the needs of different groups for eye health and visual improvement, and play an indispensable role in modern ophthalmology. With the increasing attention to eye health and changes in lifestyle, the performance and functional requirements of soft hydrophilic contact lenses are becoming higher and higher, which promotes the continuous improvement of the technology in this field.

[0003] In the prior art, in order to meet the basic performance requirements of soft hydrophilic contact lenses, various means are often used. On the one hand, soft contact lens materials are mainly based on hydrogel polymers, and their moisturizing mechanism relies on physical cross-linking between polymer chains and water absorption performance. On the other hand, existing attempts also include increasing the content of moisturizing agents and performing surface antibacterial treatment. By increasing the content of moisturizing agents, the moisturizing capacity of the lens is improved, and by surface antibacterial treatment, the reproduction of bacteria on the lens surface is inhibited.

[0004] However, the moisturizing mechanism of traditional lens materials based on physical cross-linking between polymer chains and water absorption performance lacks dynamic water management ability, and it is difficult to effectively lock tears, resulting in too fast evaporation of tears and aggravation of dry eye feeling of the wearer. The method of increasing the content of moisturizing agents will sacrifice the oxygen permeability and clarity of the lens. The surface antibacterial treatment has limited effect due to the poor adhesion of the coating, and the functional coating on the surface of the lens, such as the antibacterial layer, is easily detached by daily friction and cleaning, which not only reduces the service life of the lens, but also increases the risk of eye infection. SUMMARY

[0005] In order to at least overcome one of the problems existing in the prior art, one of the purposes of the present application is to provide a soft hydrophilic contact lens, which comprises a hydrogel matrix layer, an antibacterial layer coated on the surface of the hydrogel matrix layer, and a nanosiloxane composite layer coated on the surface of the antibacterial layer. The combination of the hydrogel matrix layer, the antibacterial layer and the nanosiloxane composite layer makes the lens have good moisturizing property, antibacterial property and wear resistance, and the bonding force between the layers is good and not easy to fall off, which meets the more comfortable and healthy wearing experience of the user. The second purpose of the present application is to provide a preparation method of the soft hydrophilic contact lens.

[0006] To this end, the present application adopts the following technical solutions:

[0007] The first aspect of the present application provides a soft hydrophilic contact lens, comprising a hydrogel matrix layer, an antibacterial layer coated on the surface of the hydrogel matrix layer, and a nanosiloxane composite layer coated on the surface of the antibacterial layer; the raw material of the hydrogel matrix layer comprises a hydrogel monomer, a linear polypeptide and a photoinitiator; the antibacterial layer is composed of a quaternary ammonium salt monomer; the nanosiloxane composite layer is formed by covalent cross-linking of nanosiloxane, the particle size of the nanosiloxane is 20-50 nm, and the nanosiloxane is selected from at least one of dimethyl siloxy cage polysilsesquioxane, glycidyl ether oxygen propyl cage polysilsesquioxane and octavinyl cage polysilsesquioxane; the temperature of the covalent cross-linking is 43-50°C.

[0008] In the sandwich structure of the soft hydrophilic contact lens "matrix layer-antibacterial layer-protection layer" of the present application, the linear polypeptide in the hydrogel matrix layer can mimic the function of natural water channel protein to form an efficient water molecule transmission channel in the matrix, thereby realizing dynamic management of tears and significantly improving the moisturizing performance of the lens to relieve eye dryness; the antibacterial layer composed of a quaternary ammonium salt monomer is constructed on the surface of the matrix, and the positive charge characteristics of the quaternary ammonium salt group can effectively adsorb and destroy the negatively charged bacterial cell membrane, thereby endowing the lens surface with persistent antibacterial ability and reducing the risk of eye infection; the nanosiloxane composite layer as the outermost layer forms a stable network structure by covalent cross-linking, effectively disperses external mechanical stress, enhances the anti-friction and anti-wear ability of the lens surface, thereby prolonging the overall service life of the lens and its functional coating, and also preventing the antibacterial layer from falling off in daily friction and cleaning. This structural design enables the three major functions of moisturizing, antibacterial and durability to be distributed in different layers, each performing its own function and protecting each other, thereby realizing the synergy and long-acting of the lens functions.

[0009] Preferably, the particle size of the nanosiloxane is 20-50 nm, and the nanosiloxane is selected from at least one of dimethyl siloxy cage polysilsesquioxane and octavinyl cage polysilsesquioxane. Further preferably, the particle size of the nanosiloxane is 30-50 nm, and the nanosiloxane is selected from at least one of dimethyl siloxy cage polysilsesquioxane and octavinyl cage polysilsesquioxane.

[0010] The nanosiloxane with a particle size of 20-50 nm is much smaller than the wavelength of visible light, which can effectively avoid adverse effects on the transparency of the lens and ensure visual clarity; the nanosiloxane with this size has a large specific surface area, which can better fill the surface of the antibacterial layer to form a compact composite structure, disperse stress and improve the wear resistance of the lens. At the same time, the surface of the nanosiloxane has multiple reactive functional groups such as glycidyl ether oxygen groups and vinyl groups, which can efficiently covalently cross-link with the matrix or itself to form a dense and strong three-dimensional network, greatly improving the mechanical strength, hardness and durability of the composite layer.

[0011] Preferably, the weight ratio of the hydrogel monomer, the linear polypeptide, and the photoinitiator is (93-98):(2-5):(0.1-0.3). Further preferably, the weight ratio of the hydrogel monomer, the linear polypeptide, and the photoinitiator is (95-98):(2-5):(0.1-0.3). Still further preferably, the weight ratio of the hydrogel monomer, the linear polypeptide, and the photoinitiator is (95-98):(3-5):(0.1-0.3).

[0012] Preferably, the hydrogel monomer is at least one of hydroxyethyl methacrylate, 2-methacryloyloxyethyl phosphorylcholine, N-hydroxymethyl acrylamide, and hydroxypropyl acrylate. Further preferably, the hydrogel monomer is at least one of hydroxyethyl methacrylate, 2-methacryloyloxyethyl phosphorylcholine, and N-hydroxymethyl acrylamide. Still further preferably, the hydrogel monomer is at least one of hydroxyethyl methacrylate and 2-methacryloyloxyethyl phosphorylcholine.

[0013] Preferably, the linear polypeptide has a molecular weight of 1000-2000 Da. Further preferably, the linear polypeptide has a molecular weight of 1200-2000 Da. Still further preferably, the linear polypeptide has a molecular weight of 1500-2000 Da.

[0014] Preferably, the photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, and 2,2-diethoxyacetophenone. Further preferably, the photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, and 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide.

[0015] In the raw material components of the hydrogel matrix layer, the hydrogel monomer has excellent hydrophilicity and biocompatibility, and plays a basic role of hydrogel matrix and mechanical skeleton, so that the lens has basic characteristics of high water content and good oxygen permeability; the linear polypeptide with a molecular weight of 1000-2000 Da has a long molecular chain, forms an effective water channel structure, improves the moisturizing property of the lens, and avoids destroying the uniformity, transparency, and mechanical strength of the hydrogel network due to excessive biological macromolecules; and the photoinitiator absorbs light energy to generate free radicals, so that the polymerization reaction proceeds fully and efficiently, thereby forming a hydrogel matrix with complete structure and stable performance, and avoiding performance defects caused by excessive residual monomers or insufficient polymerization degree.

[0016] Preferably, the quaternary ammonium salt monomer is selected from at least one of methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyldimethylbenzylammonium chloride, and 2-methacryloyloxyethyltributylammonium chloride. More preferably, the quaternary ammonium salt monomer is selected from at least one of methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, and methacryloyloxyethyldimethylbenzylammonium chloride. Even more preferably, the quaternary ammonium salt monomer is selected from at least one of methacryloyloxyethyltrimethylammonium chloride and acryloyloxyethyltrimethylammonium chloride.

[0017] In the above technical solution, the quaternary ammonium salt monomers have antibacterial activity. Quaternary ammonium salt monomers such as methacryloyloxyethyltrimethylammonium chloride have polymerizable olefin bonds at their ends, which allows them to be firmly anchored to the lens surface through chemical bonding when forming an antibacterial layer through plasma polymerization, thereby achieving a long-lasting antibacterial effect.

[0018] Preferably, the weight ratio of the hydrogel monomer to the quaternary ammonium salt monomer is (93~98):(1~3). More preferably, the weight ratio of the hydrogel monomer to the quaternary ammonium salt monomer is (95~98):(1~3). Even more preferably, the weight ratio of the hydrogel monomer to the quaternary ammonium salt monomer is (95~98):(1.5~3).

[0019] A second aspect of the present invention provides a method for preparing a soft hydrophilic contact lens according to the first aspect of the present invention, comprising the following steps:

[0020] S1. Preparation of hydrogel matrix layer: Mix hydrogel monomers, linear peptides and photoinitiators, and carry out polymerization reaction to obtain hydrogel matrix layer;

[0021] S2. Formation of antibacterial layer: The hydrogel matrix layer obtained in step S1 is subjected to plasma polymerization with quaternary ammonium salt monomer to form an antibacterial layer on the surface of the hydrogel matrix layer.

[0022] S3. Forming a nano-siloxane composite layer: The matrix with the antibacterial layer obtained in step S2 is immersed in a dispersion of nano-siloxane and covalently crosslinked at 43~50℃ for 1~2 hours to form a nano-siloxane composite layer. After rinsing and drying, the soft hydrophilic contact lens is obtained.

[0023] Preferably, in step S1, the polymerization reaction is carried out under an inert gas atmosphere, and the wavelength of the light used in the polymerization reaction is 250~420nm, and the light intensity is 16~20mW / cm². 2 The reaction time is 25-35 minutes. More preferably, in step S1, the inert gas used in the polymerization reaction is selected from nitrogen or argon, and the wavelength of the light used in the polymerization reaction is 365-400 nm, with a light intensity of 18-20 mW / cm².2 The time is 28-35 minutes.

[0024] Preferably, in step S2, the plasma polymerization is performed using a plasma polymerization device, and the plasma polymerization is carried out at a vacuum degree of 60-80 Pa, a power of 50-180 W, and a temperature of 60-75°C for 4-8 minutes. More preferably, in step S2, the plasma polymerization is performed using a plasma polymerization device, and the plasma polymerization is carried out at a vacuum degree of 60-75 Pa, a power of 70-180 W, and a temperature of 60-70°C for 4-8 minutes. Even more preferably, in step S2, the plasma polymerization is performed using a plasma polymerization device, and the plasma polymerization is carried out at a vacuum degree of 60-75 Pa, a power of 90-180 W, and a temperature of 60-70°C for 4-8 minutes.

[0025] Before plasma polymerization in step S2, the hydrogel matrix layer obtained in step S1 needs to be plasma cleaned and activated. Specifically, the hydrogel matrix layer is placed in a plasma polymerization device, a vacuum of 10~50 Pa is drawn, oxygen or argon is introduced, and then the plasma power supply is turned on and treated at a power of 50~150 W for 1~5 min.

[0026] Preferably, in step S3, the dispersion of nano-siloxane is a nano-siloxane ethanol solution with a mass concentration of 1%~3%, wherein the volume ratio of ethanol to water in the ethanol solution is 1:(1~2), the crosslinking temperature is 43~50℃, and the crosslinking time is 1~2h. More preferably, in step S3, the dispersion of nano-siloxane is a nano-siloxane ethanol solution with a mass concentration of 1%~3%, wherein the volume ratio of ethanol to water in the ethanol solution is 1:(1~2), the crosslinking temperature is 45~50℃, and the crosslinking time is 1.5~2h.

[0027] The preparation method mainly involves steps such as preparing a hydrogel matrix layer, forming an antibacterial layer, and forming a nano-siloxane composite layer to obtain the soft hydrophilic contact lens. In step S1, under inert gas protection, heating causes the photoinitiator to decompose and generate free radicals, which initiate the polymerization reaction between hydrogel monomers and linear peptides to form a three-dimensional cross-linked network hydrogel matrix layer. In step S2, a vacuum of 60-80 Pa and a temperature of 60-70 °C ensure uniform dispersion of quaternary ammonium salt monomer vapor and full contact with the surface of the hydrogel matrix. A power of 50-180 W allows for sufficient ionization of the quaternary ammonium salt monomers, generating quaternary ammonium salt free radicals. These free radicals collide and undergo addition polymerization to form quaternary ammonium salt monomer chains, which are then covalently fixed to the surface of the hydrogel matrix layer to form an antibacterial layer, ensuring that the antibacterial layer is not easily detached. Due to the positive charge of the quaternary ammonium salt groups in the antibacterial layer, it can effectively adsorb and destroy the negatively charged bacterial cell membranes, thereby endowing the lens surface with long-lasting antibacterial ability. In step S3, the dispersion of nano-siloxane is a nano-siloxane ethanol solution with a mass concentration of 1% to 3%. At this concentration, the nano-siloxane can be effectively dispersed and is not prone to aggregation, ensuring the formation of a uniform composite layer during subsequent crosslinking. A crosslinking temperature of 43 to 50°C and a crosslinking time of 1 to 2 hours allow for sufficient covalent crosslinking between the nano-siloxane and the antibacterial layer, enhancing the stability and abrasion resistance of the composite layer and improving the overall quality of the lens. The soft hydrophilic contact lens preparation method of this application is highly reliable. Through plasma polymerization and covalent crosslinking, it ensures a tight bond between the layers, resulting in soft hydrophilic contact lenses with long-lasting moisturizing, antibacterial, and durable properties.

[0028] Compared with the prior art, the present invention has at least the following beneficial effects:

[0029] 1) The soft hydrophilic contact lens of this application includes a hydrogel matrix layer, an antibacterial layer coated on the surface of the hydrogel matrix layer, and a nano-siloxane composite layer coated on the surface of the antibacterial layer; wherein, the raw materials of the hydrogel matrix layer include hydrogel monomers, linear peptides and photoinitiators; the antibacterial layer is composed of quaternary ammonium salt monomers; the nano-siloxane composite layer is formed by covalent cross-linking of nano-siloxanes. Through the reasonable configuration and tight bonding of the components between the layers, the soft hydrophilic contact lens has good moisturizing properties, antibacterial properties and abrasion resistance, with a water content in the range of 50.5%~58%, an antibacterial rate of >99.2%, abrasion resistance (haze increase value ΔH) <0.37, high light transmittance, high tensile strength, and good bonding between the layers, making it not easy to fall off, thus meeting the user's more comfortable and healthy wearing experience.

[0030] 2) The method for preparing the soft hydrophilic contact lens of this application involves steps such as preparing a hydrogel matrix layer, forming an antibacterial layer, and forming a nano-siloxane composite layer to obtain the soft hydrophilic contact lens. This preparation method is simple, reliable, and helps to form a soft hydrophilic contact lens with long-lasting moisturizing, antibacterial, and durable properties. Detailed Implementation

[0031] The present invention will be further described in detail below through specific embodiments, comparative examples and tables, but is not limited to all the discussions and data.

[0032] In the raw material components of the soft hydrophilic contact lens, the linear polypeptide with a molecular weight of 1619.61 Da was purchased from Zhengtai Biochemical Technology (Nanjing) Co., Ltd., model number Pam3CSK4; the linear polypeptide with a molecular weight of 1871 Da was purchased from Shanghai Jinpan Biotechnology Co., Ltd., model number Anantin (linear sequence). Dimethylsiloxy cage-like polysilsesquioxane was purchased from Guangzhou Tinci Advanced Materials Co., Ltd., model number TSR-145, with a particle size of 30 nm; octavinyl cage-like polysilsesquioxane was purchased from Nanjing Xianfeng Nanomaterials Technology Co., Ltd., model number XF-OVS-01, with a particle size of 25~40 nm. The dimethylsiloxy cage-like polysilsesquioxane in Comparative Example 2 was purchased from Guangzhou Tinci Advanced Materials Co., Ltd., model number TSR-148, with a particle size of 70 nm.

[0033] It is particularly important to emphasize that, unless otherwise specified, the raw materials, reagents or devices used in this invention can be obtained from conventional commercial sources.

[0034] Examples of soft hydrophilic contact lenses:

[0035] A soft, hydrophilic contact lens is prepared by the following steps:

[0036] S1. Preparation of the hydrogel matrix layer: Mix 93-98g of hydrogel monomer, 2-5g of linear polypeptide with a molecular weight of 1000-2000 Da and 0.1-0.3g of photoinitiator evenly, inject the mixture into a contact lens mold, and place it in a reaction apparatus protected by an inert gas. The reaction is carried out at a light wavelength of 250-420nm and a light intensity of 16-20mW / cm². 2 Under the conditions, the polymerization reaction was carried out for 25-35 minutes, and the material was demolded to obtain the hydrogel matrix layer.

[0037] S2. Forming an antibacterial layer: The hydrogel matrix layer obtained in step S1 is placed in a plasma polymerization device, evacuated to 10~50Pa, and oxygen or argon is introduced. Then, the plasma power supply is turned on, and plasma cleaning and activation are performed at a power of 50~150 W for 1~5 minutes. Then, 1~3g of quaternary ammonium salt monomer is also placed in the plasma polymerization device, evacuated to 60~80Pa, the temperature is set to 60~75℃, the power is set to 50~180W, and plasma polymerization is performed for 4~8 minutes. The power supply is turned off, argon is introduced to atmospheric pressure, and then the substrate with an antibacterial layer on the surface is obtained.

[0038] S3. Forming a nano-siloxane composite layer: The substrate with the antibacterial layer obtained in step S2 is immersed in an ethanol solution of nano-siloxane with a mass concentration of 1%~3% (the volume ratio of ethanol to water in the ethanol solution is 1:(1~2)), and a cross-linking reaction is carried out at 43~50℃ for 1~2h to form a nano-siloxane composite layer. The substrate is then rinsed with deionized water and dried at 40~50℃ for 1.5~2h to obtain the soft hydrophilic contact lens.

[0039] Regarding step S1, in some specific embodiments, the hydrogel monomer may be selected from at least one of hydroxyethyl methacrylate, 2-methacryloyloxyethyl phosphocholine, N-hydroxymethylacrylamide, and hydroxypropyl acrylate; the molecular weight of the linear polypeptide may be 1000 Da, 1200 Da, 1500 Da, 1800 Da, or 2000 Da; and the photoinitiator may be selected from at least one of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and 2,2-diethoxyacetophenone. The amount of hydrogel monomer can be 93g, 94g, 96g, or 98g; the amount of linear polypeptide can be 2g, 3g, 4g, or 5g; the amount of photoinitiator can be 0.1g, 0.2g, or 0.3g; the inert gas introduced into the polymerization reaction can be selected from nitrogen or argon; the wavelength of light used in the polymerization reaction can be 250nm, 315nm, 365nm, 400nm, or 420nm; and the light intensity can be 16mW / cm². 2 18mW / cm 2 19mW / cm 2 Or 20mW / cm 2 The time can be 25 minutes, 28 minutes, 30 minutes or 35 minutes.

[0040] Regarding step S2, in some specific embodiments, the vacuum for plasma cleaning and activation can be 10 Pa, 20 Pa, 30 Pa, or 50 Pa, the power can be 50 W, 80 W, 100 W, 120 W, or 150 W, and the processing time can be 1 min, 2 min, 4 min, or 5 min; the vacuum for plasma polymerization can be 60 Pa, 65 Pa, 70 Pa, or 80 Pa, the temperature can be 60℃, 65℃, 68℃, 72℃, or 75℃, the power can be 50 W, 100 W, 120 W, 160 W, or 180 W, and the time can be 4 min, 5 min, 6 min, or 8 min; the quaternary ammonium salt monomer can be selected from at least one of methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyldimethylbenzylammonium chloride, and 2-methacryloyloxyethyltributylammonium chloride, and the amount of quaternary ammonium salt monomer can be 1 g, 2 g, or 3 g.

[0041] Regarding step S3, in some specific embodiments, the particle size of the nano-siloxane can be 20nm, 30nm, 40nm, or 50nm, and the nano-siloxane can be selected from at least one of dimethylsiloxy cage-like polysilsesquioxane, glycidyl etheroxypropyl cage-like polysilsesquioxane, and octavinyl cage-like polysilsesquioxane. The mass concentration of the ethanol solution of the nano-siloxane can be 1%, 1.5%, 2%, 2.8%, or 3%. The crosslinking reaction temperature can be 43℃, 45℃, 48℃, or 50℃, and the crosslinking reaction time can be 1h, 1.2, 1.5h, or 2h. The drying temperature can be 40℃, 45℃, 46℃, or 50℃, and the drying time can be 1.5h, 1.6h, 1.7h, 1.8h, or 2h. Example 1

[0042] A soft, hydrophilic contact lens is prepared by the following steps:

[0043] S1. Preparation of the hydrogel matrix layer: 93g of hydroxyethyl methacrylate, 2.5g of a linear polypeptide with a molecular weight of 1619.61 Da, and 0.2g of 1-hydroxycyclohexylphenyl ketone were mixed evenly and injected into a contact lens mold. The mold was then placed in a sealable UV curing chamber filled with nitrogen gas at a wavelength of 365nm and a light intensity of 18mW / cm². 2 Under the conditions, the polymerization reaction was carried out for 30 minutes, and the material was demolded to obtain the hydrogel matrix layer.

[0044] S2. Forming an antibacterial layer: The hydrogel matrix layer obtained in step S1 is placed in a radio frequency glow discharge plasma device, evacuated to 20 Pa, and argon gas is introduced. Then, the plasma power supply is turned on, and plasma cleaning and activation are performed at 80 W for 5 min. 3g of methacryloyloxyethyltrimethylammonium chloride is also placed in the device, evacuated to 65 Pa, the temperature is set to 60℃, the power is 100W, and plasma polymerization is performed for 8 min. The power supply is turned off, argon gas is introduced to atmospheric pressure, and the substrate with an antibacterial layer on the surface is obtained.

[0045] S3. Forming a nano-siloxane composite layer: The substrate with the antibacterial layer obtained in step S2 is immersed in an ethanol solution of dimethylsiloxy cage-like polysilsesquioxane with a mass concentration of 2% (the volume ratio of ethanol to water in the ethanol solution is 1:2), and a crosslinking reaction is carried out at 48°C for 1.5 h to form a nano-siloxane composite layer. The substrate is then rinsed with deionized water and dried at 45°C for 1.5 h to obtain the soft hydrophilic contact lens. Example 2

[0046] The preparation method of a soft hydrophilic contact lens and the amount of each raw material are the same as in Example 1, except that the molecular weight of the linear polypeptide in step S1 in Example 2 is 1871 Da. Example 3

[0047] A method for preparing a soft hydrophilic contact lens and the amount of each raw material are the same as in Example 1, except that in Example 3, the dimethylsiloxy cage polysilsesquioxane in step S3 is replaced with octavinyl cage polysilsesquioxane. Example 4

[0048] The preparation method of a soft hydrophilic contact lens and the amount of each raw material are the same as in Example 1, except that the crosslinking temperature in step S3 of Example 4 is changed to 43°C. Example 5

[0049] The preparation method of a soft hydrophilic contact lens and the amount of each raw material are the same as in Example 1, except that the crosslinking temperature in step S3 of Example 5 is changed to 50°C.

[0050] Comparative Example 1:

[0051] A method for preparing a soft hydrophilic contact lens and the amount of each raw material are the same as in Example 1, except that the linear polypeptide in step S1 of Comparative Example 1 is replaced by an equal amount of hydroxyethyl methacrylate, that is, the amount of hydroxyethyl methacrylate in step S1 is 95.5g.

[0052] Comparative Example 2:

[0053] The preparation method of a soft hydrophilic contact lens and the amount of each raw material are the same as in Example 1, except that the particle size of the dimethylsiloxy cage-like polysilsesquioxane in step S3 of Comparative Example 2 is 70 nm.

[0054] Comparative Example 3:

[0055] The preparation method of a soft hydrophilic contact lens and the amount of each raw material are the same as in Example 1, except that the crosslinking temperature of step S3 in Comparative Example 3 is changed to 35°C.

[0056] Material performance testing:

[0057] The soft hydrophilic contact lenses obtained in Examples 1-5 and Comparative Examples 1-3 were subjected to various performance tests, and the test methods are as follows:

[0058] 1. Moisture content: Soak the lens in physiological saline (0.9% sodium chloride aqueous solution by mass) for 24 hours, remove it, blot the surface moisture with filter paper, and weigh it (wet weight m1). Then dry it at 40℃ for 24 hours, cool it to room temperature, and weigh it (dry weight m2). Calculate the moisture content using the following formula: Moisture content (%) = (m1-m2) / m1×100%.

[0059] 2. Antibacterial rate: Cut the lens into 1cm×1cm samples, sterilize, and then soak in 2mL of solution with a concentration of 1×10⁻⁶. 6 In a CFU / mL suspension of Staphylococcus aureus (ATCC 29213), after incubation at 37℃ for 24 h, the suspension was serially diluted and plated for counting. The colony count of the sample group was recorded as C. At the same time, a blank control group without lenses was set up. After incubation, the colony count of the blank control group was recorded as C0. The antibacterial rate was calculated according to the following formula: Antibacterial rate (%) = (C0-C) / C0×100%, and the average value of the three groups of data was taken.

[0060] 3. Abrasion resistance: Using the Taibo abrasion tester, equipped with a CS-10 grinding wheel, with a load of 500g, and 100 cycles, the haze of the lens before and after wear is measured using a haze meter. The increase in haze is calculated according to the following formula: Haze increase (ΔH) = H2 (haze after wear) - H1 (haze before wear). The smaller the increase in haze, the better the abrasion resistance.

[0061] 4. Transmittance: Using a UV-Vis spectrophotometer, simulate visible light at a wavelength of 550nm, with air as a blank control. Fix the lens on a quartz cuvette holder and test the transmittance (%) at 550nm. Test each sample 3 times and take the average value.

[0062] 5. Tensile strength: Cut the lens into dumbbell-shaped strips with a length of 10mm and a width of 2mm, and test them using a universal tensile testing machine at a tensile speed of 10mm / min.

[0063] 6. Bond strength: Tested according to ASTM D3359 standard, and rated from 0 (no detachment) to 5 (severe detachment).

[0064] The test performance of the soft hydrophilic contact lenses of Examples 1-5 and Comparative Examples 1-3 is shown in Table 1 below:

[0065]

[0066] The soft hydrophilic contact lenses in Examples 1-5, through the rational configuration and tight bonding of components in each layer, are made by setting a hydrogel matrix layer, an antibacterial layer covering the surface of the hydrogel matrix layer, and a nano-siloxane composite layer covering the surface of the antibacterial layer. This results in soft hydrophilic contact lenses with good moisturizing, antibacterial, and abrasion resistance. The water content is in the range of 50.5% to 58%, the antibacterial rate is >99.2%, the abrasion resistance (haze increase value ΔH) is <0.37, the light transmittance is high, the tensile strength is high, and the bonding force between each layer is good, making them less prone to falling off, thus providing users with a more comfortable and healthy wearing experience.

[0067] Compared with Example 1, Comparative Example 1 was prepared in the same way and with the same amount of raw materials. The difference was that the linear polypeptide in step S1 of Comparative Example 1 was replaced with an equal amount of hydroxyethyl methacrylate. The results showed that the water content of the soft hydrophilic contact lens of Comparative Example 1 decreased to 42.1%. This may be because the linear polypeptide in Comparative Example 1 was replaced with hydroxyethyl methacrylate, and the lens relied solely on the water absorption of the hydrogel monomer itself. The lack of linear polypeptide to build water molecule transport channels led to a significant decrease in the moisturizing performance of the lens.

[0068] Compared with Example 1, Comparative Example 2 was prepared in the same way and with the same amount of raw materials. The difference was that the particle size of the dimethylsiloxy cage-like polysilsesquioxane in step S3 of Comparative Example 2 was 70 nm. The results showed that the wear resistance and bonding strength of the soft hydrophilic contact lens of Comparative Example 2 decreased significantly. This may be because the 70 nm nano-siloxane particles in Comparative Example 2 were too large and were prone to agglomeration, resulting in an uneven formation process of the nano-siloxane composite layer and a decrease in the bonding strength with the antibacterial layer.

[0069] Compared with Example 1, Comparative Example 3 was prepared in the same way and with the same amount of raw materials. The difference was that the crosslinking temperature of step S3 in Comparative Example 3 was changed to 35°C. The results showed that the wear resistance and bonding strength of the soft hydrophilic contact lens of Comparative Example 3 decreased significantly, especially the bonding strength dropped to level 3. This may be because the crosslinking temperature of step S3 in Comparative Example 3 was too low, resulting in insufficient bonding strength. This made the structure of the formed nano-siloxane composite layer too loose, thereby reducing its wear resistance and making it easy to peel off due to insufficient bonding strength.

[0070] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. Any obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A soft hydrophilic contact lens, characterized in that, It includes a hydrogel matrix layer, an antibacterial layer coated on the surface of the hydrogel matrix layer, and a nano-siloxane composite layer coated on the surface of the antibacterial layer; The raw materials for the hydrogel matrix layer include hydrogel monomers, linear peptides, and photoinitiators; The antibacterial layer is composed of quaternary ammonium salt monomers; The nano-siloxane composite layer is formed by covalent cross-linking of nano-siloxanes. The nano-siloxanes have a particle size of 20-50 nm and are selected from at least one of dimethylsiloxy cage polysilsesquioxane, glycidyl etheroxypropyl cage polysilsesquioxane, and octavinyl cage polysilsesquioxane. The temperature for covalent crosslinking is 43~50℃; The method for preparing the soft hydrophilic contact lens includes the following steps: S1. Preparation of hydrogel matrix layer: Mix hydrogel monomers, linear peptides and photoinitiators, and carry out polymerization reaction to obtain hydrogel matrix layer; S2. Formation of antibacterial layer: The hydrogel matrix layer obtained in step S1 is subjected to plasma polymerization with quaternary ammonium salt monomer to form an antibacterial layer on the surface of the hydrogel matrix layer. S3. Forming a nano-siloxane composite layer: The matrix with the antibacterial layer obtained in step S2 is immersed in a dispersion of nano-siloxane and covalently crosslinked at 43~50℃ for 1~2 hours to form a nano-siloxane composite layer. After rinsing and drying, the soft hydrophilic contact lens is obtained.

2. The soft hydrophilic contact lens according to claim 1, characterized in that, The weight ratio of the hydrogel monomer, linear polypeptide, and photoinitiator is (93~98):(2~5):(0.1~0.3).

3. The soft hydrophilic contact lens according to claim 1, characterized in that, The hydrogel monomer is selected from at least one of hydroxyethyl methacrylate, 2-methacryloyloxyethyl phosphocholine, N-hydroxymethylacrylamide, and hydroxypropyl acrylate.

4. The soft hydrophilic contact lens according to claim 1, characterized in that, The linear polypeptide has a molecular weight of 1000~2000 Da; And / or, the photoinitiator is selected from at least one of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and 2,2-diethoxyacetophenone.

5. The soft hydrophilic contact lens according to claim 1, characterized in that, The quaternary ammonium salt monomer is selected from at least one of methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyldimethylbenzylammonium chloride, and 2-methacryloyloxyethyltributylammonium chloride.

6. The soft hydrophilic contact lens according to claim 1, characterized in that, The weight ratio of the hydrogel monomer to the quaternary ammonium salt monomer is (93~98):(1~3).

7. The soft hydrophilic contact lens according to claim 1, characterized in that, In step S1, the polymerization reaction is carried out under the protection of an inert gas, the wavelength of the light in the polymerization reaction is 250~420nm, the light intensity is 16~20mW / cm2, and the time is 25~35min.

8. The soft hydrophilic contact lens according to claim 1, characterized in that, In step S2, the plasma polymerization is carried out at a vacuum of 60~80Pa, a power of 50~180W, and a temperature of 60~75℃ for 4~8 minutes.

9. The soft hydrophilic contact lens according to claim 1, characterized in that, In step S3, the dispersion of nano-siloxane is a nano-siloxane ethanol solution with a mass concentration of 1% to 3%.

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