Medical optical material and preparation method and application thereof
By employing continuous liquid surface photopolymerization technology with a 405nm light source and O2/TEMPO dual inhibitors, combined with secondary UV irradiation and post-thermal curing, the problems of ghosting and yellowing during the preparation of orthokeratology lenses have been solved, achieving a medical optical material with high transmittance and biocompatibility.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- 南通诺瞳奕目医疗科技有限公司
- Filing Date
- 2025-12-22
- Publication Date
- 2026-04-14
AI Technical Summary
Existing orthokeratology lenses suffer from defects such as ghosting and yellowing during the manufacturing process, making it difficult to achieve both high surface quality and batch consistency, which limits their application in medical optical materials.
Using a continuous liquid surface photocuring technology based on a 405nm light source, combined with O2/TEMPO dual inhibitors, medical optical materials are prepared through a process of continuous liquid surface photocuring, secondary UV irradiation, and thermal post-curing. This establishes a steep polymerization threshold and a stable inhibition layer, significantly reducing ghosting and window sticking, and improving transmittance and biocompatibility.
A corneal reshaping lens with a smooth surface, high dimensional consistency, and good biocompatibility was prepared, solving the problems of ghosting and yellowing in the traditional layered photopolymerization process, and meeting the requirements of high transmittance and oxygen permeability.
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Figure CN121343070B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of optical material manufacturing technology, specifically a medical optical material, its preparation method, and its application. Background Technology
[0002] Currently, orthokeratology lenses (or "OK lenses") are a type of medical device with a special reverse geometry design, ultra-high oxygen permeability, and the ability to temporarily reshape the cornea. They are commonly used as an effective optical method for treating refractive errors and controlling myopia progression. Due to their reverse geometry design—flat in the center and steep at the periphery—they can change the curvature of the corneal surface to correct refractive errors and improve vision. Orthokeratology lenses have attracted considerable attention in the field of optical components.
[0003] Typically, in actual product manufacturing, orthokeratology lenses mostly require the use of layered photopolymerization technology. This involves using ultraviolet lasers or electron beams to trigger the polymerization reaction of liquid resin, achieving multi-layer stacking to achieve a deep curing effect. This results in the formation of a three-dimensional solid through layer-by-layer stacking, in order to meet the requirements of a reverse geometry design with a flat center and steep edges.
[0004] However, the existing technical solutions mentioned above have the following drawbacks: Traditional layered photopolymerization often results in problems such as ghosting and yellowing in the fabrication of orthokeratology lenses, making it difficult to simultaneously achieve high surface quality and batch consistency, thus limiting their application in medical optical materials. Therefore, developing a direct molding process for orthokeratology lenses to solve defects such as ghosting and yellowing, and to obtain orthokeratology lenses that meet the requirements of high transmittance and biocompatibility, is a pressing technical challenge in this field. Summary of the Invention
[0005] The purpose of this invention is to provide a medical optical material to solve the problem mentioned in the background art that most existing orthokeratology lenses adopt traditional layered light curing processes, which result in defects such as ghosting and yellowing.
[0006] To achieve the above objectives, the embodiments of the present invention provide the following technical solutions:
[0007] A medical optical material comprises the following raw materials: photosensitive resin, crosslinking agent, photoinitiator, inhibitor, and ultraviolet blocking monomer; wherein the photosensitive resin comprises a silica-containing oxygen-permeable monomer and a hydrophilic monomer, and the dissolved oxygen of the photosensitive resin is not greater than 10 mg / L.
[0008] Preferably, the inhibitor is selected from any one of tetramethylpiperidine oxide, triphenyl phosphite, phenolic derivatives, or quinone compounds.
[0009] More preferably, the medical optical material is prepared by pretreatment of photosensitive resin, crosslinking agent, photoinitiator, inhibitor, and ultraviolet blocking monomer, followed by continuous liquid surface photocuring and post-treatment.
[0010] Another objective of this invention is to provide a method for preparing a medical optical material, the method specifically comprising the following steps:
[0011] 1) Weigh out the photosensitive resin, crosslinking agent, photoinitiator, inhibitor, and ultraviolet blocking monomer according to the proportion for pretreatment, then perform continuous liquid surface photocuring, and clean to obtain the pre-dried material.
[0012] 2) The pre-dried material obtained in step 1) is post-processed to obtain the medical optical material; wherein the post-processing includes secondary UV irradiation and thermal curing.
[0013] Another objective of this invention is to provide a medical optical material prepared using the above-described preparation method.
[0014] Another objective of this invention is to provide the application of the above-mentioned medical optical material in the preparation of vision correction medical devices or corneal reshaping medical devices.
[0015] Compared with the prior art, the beneficial effects of the embodiments of the present invention are:
[0016] The medical optical material provided in this invention utilizes photosensitive resin, crosslinking agent, photoinitiator, inhibitor, and UV-blocking monomers in a rational manner. Simultaneously, it employs continuous liquid surface photocuring technology based on a 405nm light source. Through O2 / TEMPO dual inhibition, a steep polymerization threshold and stable inhibition layer are achieved, significantly reducing ghosting and window adhesion. Combined with secondary UV irradiation and post-curing under nitrogen atmosphere, deep crosslinking is completed, suppressing yellowing and haze. Compared to traditional layered photocuring technology, it has a smoother surface, reduced polishing requirements, and improved dimensional and surface consistency, meeting medical biocompatibility requirements. This solves the problem of existing orthokeratology lenses, which mostly use traditional layered photocuring processes and are prone to defects such as ghosting and yellowing. Furthermore, the preparation method of the medical optical material provided in this invention is simple and can be used to prepare orthokeratology lenses and other optical components with high optical quality, high oxygen permeability, and biocompatibility, showing broad market prospects. Attached Figure Description
[0017] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention.
[0018] Figure 1The dose-curing depth working curve and Dc / Esat fitting diagram of the medical optical material provided in an embodiment of the present invention during the preparation process.
[0019] Figure 2 The figure shows the effect of DO and TEMPO on the thickness of the inhibition layer and the edge MTF during the preparation process of the medical optical material provided in an embodiment of the present invention.
[0020] Figure 3 The graph shows the relationship between the post-curing thermal range and the yellowness index / conversion rate during the preparation process of the medical optical material provided in an embodiment of the present invention.
[0021] Figure 4 The surface morphology of a medical optical material provided in an embodiment of the present invention is shown in the atomic force microscopy (AFM) / white light interference result image. Detailed Implementation
[0022] To make the technical problems, technical solutions, and beneficial effects of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the following embodiments will help those skilled in the art to further understand the embodiments of this invention, but do not limit the embodiments of this invention in any way. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the embodiments of this invention. These all fall within the protection scope of the embodiments of this invention.
[0023] The specific implementation of the present invention will be described in detail below with reference to specific embodiments.
[0024] First, it's important to clarify that orthokeratology lenses (OK lenses), as a corrective tool worn overnight to reshape the cornea and control myopia progression, involve multidisciplinary technologies in their design and manufacturing. Typically, orthokeratology lenses use breathable rigid corneal contact lens materials, achieving "customization" through precise optical design and mechanical property control. For example, breathable rigid materials are developed by adding silicone (silicone acrylic material) or fluorosilicone (fluorosilicone acrylic material) to PMMA, and then curing the product using ultraviolet light.
[0025] However, orthokeratology lenses employ a reverse geometry design with a flat center and steep periphery. Currently, in actual product manufacturing, layered photopolymerization technology is typically used. This involves using ultraviolet lasers or electron beams to initiate the polymerization reaction of liquid resin, achieving deep curing through multi-layer stacking to form a three-dimensional solid. However, traditional layered photopolymerization often results in layer cracks, adhesion windows, and dimensional fluctuations, frequently exhibiting defects such as under-curing, ghosting, yellowing, and haze, making it difficult to balance high surface quality with batch consistency. While continuous liquid surface technology (such as CLIP / CAL) can be used to achieve non-adhesive continuous forming by establishing a controlled inhibition layer at the window, the thickness of the inhibition layer and the polymerization threshold are coupled and affected by resin composition, dissolved oxygen, temperature, and exposure dose, resulting in a narrow process window and insufficient reproducibility. Furthermore, existing publicly available solutions lack systematic descriptions of the synergistic regulation of O2 and chemical inhibition under a 405nm ultraviolet light source system, Dc / Esat working curve calibration, and post-curing anti-yellowing strategies, limiting their application in medical optical materials.
[0026] Therefore, to address the problems of existing orthokeratology lenses, which mostly employ traditional layered photopolymerization processes and are prone to defects such as ghosting and yellowing, this invention provides a medical optical material, specifically an orthokeratology lens based on continuous liquid surface photopolymerization technology using a 405nm light source. This medical optical material comprises the following raw materials:
[0027] The photosensitive resin, crosslinking agent, photoinitiator, inhibitor, and ultraviolet blocking monomer; wherein the photosensitive resin includes a silica-containing oxygen-permeable monomer and a hydrophilic monomer, and the dissolved oxygen in the photosensitive resin is not greater than 10 mg / L.
[0028] Preferably, the medical optical material has a transmittance of ≥92% at 550nm (i.e., a transmittance of ≥92% at a visible light wavelength of 550nm), a haze of ≤1.0%, and an oxygen flux of ≥100 Barrer in a hydrated state at 35℃.
[0029] More preferably, the total amount of leachables in the medical optical material is ≤0.5%, and its cell compatibility meets the ISO10993-5 standard.
[0030] In another preferred embodiment of the present invention, the silicon-containing oxygen-permeable monomer mainly includes two types: organosilicon monomers and fluorosiloxanes. The organosilicon monomer can be hydroxyl-terminated polydimethylsiloxane, symmetrical monomethacryloyloxypropyl modified polydimethylsiloxane, fluorosiloxane, etc. Preferably, it can be any one or more of TRIS, PDMS-MA, etc.
[0031] In another preferred embodiment of the present invention, the inhibitor is selected from any one of tetramethylpiperidine oxide, triphenyl phosphite, phenolic derivatives (such as phenol, 2,6-di-tert-butyl-4-methylphenol) free radical inhibitors or quinones (such as naphthoquinone) free radical inhibitors.
[0032] More preferably, the inhibitor is tetramethylpiperidine oxide, specifically TEMPO (2,2,6,6-tetramethylpiperidine oxide), which is a class of compounds that terminate chain reactions by capturing free radical intermediates. Its mechanism of action includes reacting with active free radicals to generate stable non-free radical substances or low-activity free radicals. In photocatalytic reaction systems, TEMPO (2,2,6,6-tetramethylpiperidine oxide) is used as a typical inhibitor to verify free radical reaction mechanisms. As a stable N-oxygen free radical, TEMPO has the function of capturing free radicals and quenching singlet oxygen, and can effectively catalyze the oxidation reactions of primary and secondary alcohols, especially when using strong oxidizing singlet oxygen donors. It has the advantages of high yield, good selectivity, good stability, and recyclability.
[0033] In another preferred embodiment of the present invention, the dissolved oxygen (DO) of the photosensitive resin is controlled at 6-8 mg / L.
[0034] In a further preferred embodiment, the raw materials of the medical optical material are pretreated before use. Specifically, the silicon-containing oxygen-permeable monomer, hydrophilic monomer, crosslinking agent, photoinitiator, inhibitor, and ultraviolet blocking monomer are premixed, then vacuum degassed (usually at -0.08 MPa for 20 min), filtered through 0.22 μm, the dissolved oxygen (DO) is adjusted to 6–8 mg / L, and finally aged at 25°C for 12–24 h.
[0035] In another preferred embodiment of the present invention, the medical optical material is prepared by pretreating raw materials such as photosensitive resin, crosslinking agent, photoinitiator, inhibitor, and ultraviolet blocking monomer, followed by continuous liquid surface photocuring and post-treatment.
[0036] In another preferred embodiment of the present invention, the surface average illuminance of the continuous liquid surface photopolymerization is 12–18 mW / cm². Specifically, continuous liquid surface photopolymerization is performed under the conditions of a surface average illuminance of 12–18 mW / cm², a platform continuous rise speed of 15±2 RPM, a total exposure dose of 1.6–2.0 × Dc, and a window temperature of 25–30°C. The continuous liquid surface photopolymerization is a 3D printing process based on photopolymerization technology. Its core principle is to use ultraviolet laser to cure liquid photosensitive resin and form a three-dimensional solid through the continuous movement of the lifting platform.
[0037] In another preferred embodiment of the present invention, the post-treatment includes secondary UV (ultraviolet) irradiation and thermal post-curing, wherein the dose of the secondary UV irradiation is 1.0–1.5 J / cm², and the temperature of the thermal post-curing is 60–100°C. Specifically, thermal post-curing refers to the process of continuing the molecular reaction by heating and maintaining a constant temperature after the material has been completely cured at room temperature. This process can increase the crosslinking density, eliminate internal stress, and enhance the stability of the material.
[0038] Preferably, the post-treatment involves secondary UV irradiation under nitrogen protection, with a UV irradiation dose of 1.0–1.5 J / cm², followed by stepped thermosetting (heating at 60℃ for 2 h, 80℃ for 2 h, 100℃ for 1 h, and 80℃ for 1 h sequentially) and then slow cooling. Through secondary UV irradiation and post-thermal curing, deep cross-linking can be achieved in a nitrogen (N2) environment, and yellowing and haze can be suppressed.
[0039] As another preferred embodiment of the present invention, the light source for continuous liquid surface photocuring can be a 365nm, 385nm, 395nm, or 405nm ultraviolet light source.
[0040] Preferably, the light source for the continuous liquid surface photopolymerization is a 405nm ultraviolet light source. The medical optical material utilizes continuous liquid surface photopolymerization (CAL) additive manufacturing technology with a 405nm light source. Under 405nm conditions, a CAL forming process chain with reproducible threshold and penetration depth is established, solving defects such as under-curing, ghosting, yellowing, and haze, and obtaining biocompatible orthokeratology lenses that meet high transmittance and oxygen permeability requirements.
[0041] Oxygen permeability is a key parameter measuring the ability of contact lens materials to allow oxygen to pass through, and it is composed of two values: oxygen permeability coefficient (Dk) and oxygen permeability (Dk / t). The oxygen flux (i.e., oxygen permeability coefficient) of the medical optical material in a hydrated state at 35°C is ≥100 Barrer. High oxygen permeability lenses can significantly improve wearing comfort and extend the safe wearing time.
[0042] Specifically, oxygen permeability (Dk) describes the material's ability to allow oxygen to pass through. A higher Dk value indicates better oxygen permeability. Unit: Barrer (cm³ O₂·cm) / (cm²·s·mmHg). Oxygen permeability (Dk / t, where t is the lens center thickness, usually in cm) describes the oxygen transport capacity of a lens of a specific thickness. This is a more direct indicator of oxygen supply during actual wear. Unit: (cm³ O₂) / (cm²·s·mmHg). A higher Dk / t value means the lens delivers more oxygen to the cornea per unit time.
[0043] In another preferred embodiment of the present invention, the medical optical material is prepared by using O2 / TEMPO dual inhibition and closed-loop control of the working curve to achieve high optical quality, high oxygen permeability, and biocompatibility, and can be used to prepare orthokeratology lenses (OK lenses). Specifically, the medical optical material mainly comprises the following raw materials by weight percentage:
[0044] Silicon-containing oxygen-permeable monomer: 35–65 wt%;
[0045] Hydrophilic monomers: 15–45 wt%
[0046] Crosslinking agent: 1.00–5.00 wt%;
[0047] Photoinitiator (can be a low-yellowing photoinitiator): 0.01–0.20 wt%;
[0048] Inhibitors (such as tetramethylpiperidine oxide, abbreviated as TEMPO): 0.01–0.10 wt%;
[0049] UV blocking monomer: 0.50–2.00 wt%.
[0050] In another preferred embodiment of the present invention, the photoinitiator is photoinitiator TPO-L (i.e., ethyl 2,4,6-trimethylbenzoylphenylphosphonate) or a combination of photoinitiator Irgacure819 / 784. Preferably, the photoinitiator is TPO-L or a combination of photoinitiator Irgacure819 / 784, with a mass fraction of 0.05–0.15 wt%.
[0051] Furthermore, preferably, the medical optical material mainly comprises the following raw materials by weight percentage:
[0052] Silicon-containing oxygen-permeable monomer: 40–60 wt%
[0053] Hydrophilic monomers: 20–40 wt%
[0054] Crosslinking agent: 1.00–5.00 wt%;
[0055] Photoinitiator (can be a low-yellowing photoinitiator): 0.05–0.15 wt%;
[0056] Inhibitors (e.g., 2,2,6,6-tetramethylpiperidine oxide, abbreviated as TEMPO): 0.01–0.05 wt%;
[0057] UV blocking monomer: 0.50–2.00 wt%.
[0058] In another preferred embodiment of the present invention, the UV blocking monomer (also known as ultraviolet blocking monomer) is mainly used to suppress the destructive effects of ultraviolet rays on materials, protecting the substrate by absorbing or reflecting ultraviolet rays. Specifically, it can be any one of benzotriazole monomers (such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole), isoborneol acrylate (such as LA-M181), 1,6-hexanediol diacrylate (such as HDDA), and pentaerythritol acrylate (such as EM235C, EM2411).
[0059] In another preferred embodiment of the present invention, the raw materials of the medical optical material further include rheology and refractive index regulating monomers. Specifically, the raw materials of the medical optical material include, in proportion:
[0060] Silica-containing oxygen-permeable monomers (such as TRIS, PDMS-MA): 40–60 wt%
[0061] Hydrophilic monomers (such as HEMA, NVP, GMA): 20–40 wt%
[0062] Crosslinking agent (e.g., EGDMA, TEGDMA): 1.00–5.00 wt%;
[0063] Photoinitiator (can be a low-yellowing photoinitiator, such as TPO-L, Irgacure 819, Irgacure 784): 0.05–0.15 wt%;
[0064] Inhibitors (e.g., 2,2,6,6-tetramethylpiperidine oxide): 0.01–0.05 wt%;
[0065] UV blocking monomers (e.g., 2-(2'-hydroxy-5'-methylphenyl)benzotriazole): 0.50–2.00 wt%;
[0066] The rest are rheology and refractive index adjusting monomers (such as IBMA (isobutyl methacrylate), EHMA (2-ethylhexyl methacrylate), etc. The actual amount and time of addition can be referred to the existing corneal reshaping lens process, which will not be elaborated here).
[0067] This invention also provides a method for preparing a medical optical material, the method comprising the following steps:
[0068] 1) Weigh out the raw materials such as photosensitive resin, crosslinking agent, photoinitiator, inhibitor, and ultraviolet blocking monomer according to the proportion, pre-treat them, then perform continuous liquid surface photocuring, and clean them to obtain the pre-dried material.
[0069] 2) The pre-dried material in step 1) is post-treated to obtain the medical optical material; wherein the post-treatment includes secondary UV (ultraviolet) irradiation and thermal curing.
[0070] This invention provides a direct molding process for orthokeratology lenses, specifically a 405nm CAL (Continuous Liquid Amplification) process. This process addresses defects such as ghosting and yellowing, resulting in orthokeratology lenses that meet high transmittance and biocompatibility requirements. Specifically, the method for preparing the medical optical material, as a direct molding process for orthokeratology lenses, employs continuous liquid surface curing (CAL) additive manufacturing technology with a 405nm light source. Through O2 / TEMPO dual inhibition and closed-loop control of the working curve (Dc / Esat), the absorption coefficient α, critical dose Dc, and saturation exposure energy Esat are calibrated under a 405nm light source to establish a dose-curing depth working curve. Simultaneously, O2 / TEMPO dual inhibition achieves a steep polymerization threshold and a stable inhibition layer, significantly reducing ghosting and window adhesion. This process can produce orthokeratology lenses (OK lenses) and other optical components with high optical quality, high oxygen permeability, and biocompatibility.
[0071] In another preferred embodiment of the present invention, in the preparation method of the medical optical material, the continuous liquid surface photocuring is carried out under the conditions of surface average illuminance of 12–18 mW / cm², continuous platform rise speed of 15±2 RPM, total exposure dose of 1.6–2.0×Dc, and window temperature of 25–30℃.
[0072] In another preferred embodiment of the present invention, in the preparation method of the medical optical material, the post-treatment includes secondary UV (ultraviolet) irradiation and thermal curing, wherein the dose of the secondary UV irradiation is 1.0–1.5 J / cm², and the temperature of the thermal curing is 60–100℃. Specifically, secondary UV irradiation is performed under nitrogen protection, with a UV irradiation dose of 1.0–1.5 J / cm², and stepped thermal curing is carried out at 60℃×2 h→80℃×2 h→100℃×1 h→80℃×1 h, followed by slow cooling at a rate ≤1℃ / min.
[0073] In another preferred embodiment of the present invention, in the preparation method of the medical optical material, the oxygen content during the secondary UV irradiation is less than 100 ppm.
[0074] As another preferred embodiment of the present invention, the preparation method of the medical optical material further includes a surface modification step, specifically, after thermal curing, it is placed in plasma (O2 or air) at 80 W × 60 s; then a hydrophilic coating is spin-coated at 3000 rpm × 30 s and cured at 405 nm at 0.5–1.0 J / cm²; finally, it is hydrated in physiological saline for 12–24 h.
[0075] In another preferred embodiment of the present invention, in the preparation method of the medical optical material, the hydrophilic coating is an acrylate hydrophilic coating that can be cured at 405 nm, and the curing dose is 0.5–1.0 J / cm².
[0076] More preferably, the preparation method of the medical optical material specifically includes the following steps:
[0077] S1. Resin Pretreatment: Premixing → Vacuum Degassing (–0.08 MPa, 20 min) → 0.22 μm filtration; DO adjusted to 6–8 mg / L; aging at 25℃ for 12–24 h. Specifically, the silica-containing oxygen-permeable monomer, hydrophilic monomer, crosslinking agent, photoinitiator, inhibitor, and UV-blocking monomer are premixed, then vacuum degassed (usually at –0.08 MPa for 20 min), filtered through 0.22 μm, dissolved oxygen (DO) adjusted to 6–8 mg / L, and finally aged at 25℃ for 12–24 h.
[0078] S2. Working Curve Calibration: 405nm stepped exposure, measuring absorption coefficient α and Dc / Esat; establishing a speed-dose matching table. Specifically, the absorption coefficient α (405nm), critical dose Dc, and saturation exposure energy Esat are calibrated under a 405nm light source to establish a dose-curing depth working curve, thereby constructing a dose-curing depth model and closing the loop with platform speed and grayscale frame rate.
[0079] S3. CAL continuous printing: average illuminance 12-18 mW / cm²; platform speed 15±2 RPM; total dose 1.6-2.0×Dc; window temperature 25-30℃, maintaining a stable "dead zone" to prevent sticking. Specifically, CAL printing is performed under the conditions of an average illuminance of 12-18 mW / cm², a platform continuous rise speed of 15±2 RPM, a total exposure dose of 1.6–2.0×Dc, and a window temperature of 25–30℃.
[0080] S4. Cleaning: Perform rapid two-stage ultrasonic cleaning of the molded parts in sequence using PGMEA and IPA. Specifically, use PGMEA (propylene glycol methyl ether acetate) for 2×60s ultrasonic cleaning → IPA (isopropanol) for 2×60s ultrasonic cleaning; then blow with nitrogen for 30–60s, and pre-dry at 40–45℃ for 20–30 min.
[0081] S5. Secondary UV irradiation and post-curing: UV irradiation dose 1.0–1.5 J / cm²; then, 60℃×2 h→80℃×2 h→100℃×1 h→80℃×1 h; slow cooling ≤1℃ / min, slow cooling relieves stress and inhibits yellowing. Specifically, secondary UV irradiation is performed under nitrogen protection, dose 1.0–1.5 J / cm², and stepped thermocuring is implemented at 60℃×2 h→80℃×2 h→100℃×1 h→80℃×1 h, followed by slow cooling. N₂ < 100 ppm, O₂ < 100 ppm.
[0082] S6. Surface Modification: This includes plasma activation, application of a hydrophilic coating, and hydration in physiological saline. Specifically, the surface is plasma activated, a hydrophilic coating is applied and cured, and finally hydrated in physiological saline to obtain a product with high optical quality and biocompatibility, i.e., the medical optical material. Specifically, the surface is plasma activated under plasma conditions (O2 or air) at 80 W × 60 s; then the hydrophilic coating is spin-coated at 3000 rpm × 30 s and cured at 405 nm at 0.5–1.0 J / cm²; finally, it is hydrated in physiological saline for 12–24 h.
[0083] S7. Quality Inspection and Release: This includes testing of resin physical and optical parameters, molding and appearance, finished product performance, stability, and consistency. Each batch must be measured at least three times repeatedly, and the mean ± standard deviation must be recorded. After passing quality control and meeting the standards for transmittance, haze, Dk, modulus, conversion rate, leachate, and cell compatibility, the batch is released.
[0084] This invention achieves a steep polymerization threshold and a stable inhibition layer through dual O2 / TEMPO inhibition, significantly reducing ghosting and window adhesion. Simultaneously, deep cross-linking is completed in a nitrogen environment via secondary UV and post-thermal curing, suppressing yellowing and haze. Compared to conventional layer printing (i.e., traditional layer photopolymerization, which often results in layer lines, window adhesion, and dimensional fluctuations), the surface is smoother, polishing requirements are reduced, and dimensional and surface consistency is improved; it also meets medical biocompatibility requirements.
[0085] This invention also provides a medical optical material prepared using the above-described method for preparing medical optical materials.
[0086] This invention also provides an application of the above-mentioned medical optical material in vision correction or corneal reshaping. It is particularly suitable as a material for manufacturing vision correction or corneal reshaping medical devices, especially for manufacturing orthokeratology lenses for corneal reshaping, i.e., the application of the medical optical material in the manufacture of orthokeratology lenses. Furthermore, it can also be used in the manufacture of other optical components.
[0087] The technical effects of the medical optical materials of the present invention will be further explained below by listing specific embodiments.
[0088] Example 1
[0089] A medical optical material, specifically comprising the following raw materials:
[0090] Silica-containing oxygen-permeable monomer (specifically 3-methacryloyloxypropyltrimethoxysilane (TRIS)): 52.00 wt%;
[0091] Hydrophilic monomer (specifically 2-hydroxyethyl methacrylate (HEMA)): 28.00 wt%;
[0092] Crosslinking agent (specifically ethylene glycol dimethacrylate (EGDMA)): 2.20 wt%;
[0093] Photoinitiator (specifically, ethyl (2,4,6-trimethylbenzoyl)phenylphosphonate (TPO-L)): 0.08 wt%;
[0094] Inhibitor (specifically 2,2,6,6-tetramethylpiperidine oxide (TEMPO)): 0.02 wt%;
[0095] UV blocking monomer (specifically 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (UV blocking agent)): 1.00 wt%;
[0096] Viscosity / refractive index modifier (specifically isobutyl methacrylate (IBMA)): 16.70 wt.
[0097] In this embodiment, the preparation method of the medical optical material is as follows:
[0098] S1. Resin pretreatment: Specifically, the silica-containing oxygen-permeable monomer, hydrophilic monomer, crosslinking agent, photoinitiator, inhibitor, UV blocking monomer, and viscosity / refractive index adjusting monomer are premixed, then vacuum degassed (usually degassed at -0.08 MPa for 20 min), filtered through 0.22 μm, dissolved oxygen (DO) is adjusted to 7 mg / L, and finally aged at 25°C for 18 h.
[0099] S2. Working Curve Calibration: 405nm stepped exposure, measuring absorption coefficient α and Dc / Esat; establishing a speed-dose matching table. Specifically, the absorption coefficient α (405nm), critical dose Dc, and saturation exposure energy Esat are calibrated under a 405nm light source to establish a dose-curing depth working curve, thereby constructing a dose-curing depth model and closing the loop with platform speed and grayscale frame rate.
[0100] S3. CAL continuous printing: average illuminance 15mW / cm²; platform speed 15RPM; total dose 1.8×Dc; window temperature 28℃, maintaining a stable "dead zone" anti-stick window. Specifically, CAL printing is performed under the conditions of an average illuminance of 15mW / cm², a platform continuous rise speed of 15RPM, a total exposure dose of 1.8×Dc, and a window temperature of 28℃.
[0101] S4. Cleaning: Perform rapid two-stage ultrasonic cleaning of the molded parts in sequence using PGMEA and IPA. Specifically, use PGMEA (propylene glycol methyl ether acetate) for 2×60s ultrasonic cleaning → IPA (isopropanol) for 2×60s ultrasonic cleaning; then blow with nitrogen for 45s and pre-dry at 43℃ for 25min.
[0102] S5. Secondary UV irradiation and post-curing: UV irradiation dose 1.2 J / cm²; then, 60℃×2 h→80℃×2 h→100℃×1 h→80℃×1 h; slow cooling ≤1℃ / min, slow cooling relieves stress and inhibits yellowing. Specifically, secondary UV irradiation is performed under nitrogen protection, dose 1.2 J / cm², followed by stepped thermocuring at 60℃×2 h→80℃×2 h→100℃×1 h→80℃×1 h, followed by slow cooling. N₂ < 100 ppm, O₂ < 100 ppm.
[0103] S6. Surface Modification: This includes plasma activation, application of a hydrophilic coating, and hydration in physiological saline. Specifically, the surface is plasma activated, a hydrophilic coating is applied and cured, and finally hydrated in physiological saline to obtain a product with high optical quality and biocompatibility, i.e., the medical optical material. Specifically, the surface is plasma activated under plasma conditions (O2 or air) at 80 W × 60 s; then the hydrophilic coating is spin-coated at 3000 rpm × 30 s and cured at 405 nm at 0.5–1.0 J / cm²; finally, it is hydrated in physiological saline for 12–24 h.
[0104] S7. Quality Inspection and Release: This includes testing of resin physical and optical parameters, molding and appearance, finished product performance, stability, and consistency. Each batch must be measured at least three times repeatedly, and the mean ± standard deviation must be recorded. After passing quality control and meeting the standards for transmittance, haze, Dk, modulus, conversion rate, leachate, and cell compatibility, the batch is released.
[0105] The key processes are: DO=7.0mg / L; illuminance 15mW / cm²; total dose 1.80×Dc; plateau speed 15RPM; UV irradiation under N2 1.20 J / cm²; thermal range 60×2 h→80×2 h→100×1 h→80×1 h; slow cooling.
[0106] Example 2
[0107] Silica-containing oxygen-permeable monomer (specifically 3-methacryloyloxypropyltrimethoxysilane (TRIS)): 47.50 wt%
[0108] Hydrophilic monomer A (specifically 2-hydroxyethyl methacrylate (HEMA)): 32.00 wt%
[0109] Hydrophilic monomer B (specifically N-vinylpyrrolidone (NVP)): 4.00 wt%
[0110] Crosslinking agent (specifically ethylene glycol dimethacrylate (EGDMA)): 2.00 wt%
[0111] Photoinitiator (specifically, a compound of ethyl (2,4,6-trimethylbenzoyl)phenylphosphonate (TPO-L) and Irgacure 784, usually a mixture of equal weights): 0.10 wt%
[0112] Inhibitor (specifically 2,2,6,6-tetramethylpiperidine oxide (TEMPO)): 0.03 wt%
[0113] UV blocking monomer (specifically 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (UV blocking agent)): 1.00 wt%
[0114] Viscosity modifier (specifically isobutyl methacrylate (IBMA)): 13.37 wt.
[0115] The process is the same as in Example 1; the dosage can be increased to 1.90 × Dc to compensate for the threshold change caused by the hydrophilic monomer. Compared to the medical optical material of Example 1, it has high hydrophilicity and improves initial wetting.
[0116] Example 3
[0117] A medical optical material, specifically comprising the following raw materials:
[0118] Silica-containing oxygen-permeable monomer (specifically 3-methacryloyloxypropyltrimethoxysilane (TRIS)): 35wt%;
[0119] Hydrophilic monomer (specifically 2-hydroxyethyl methacrylate (HEMA)): 45wt%;
[0120] Crosslinking agent (specifically ethylene glycol dimethacrylate (EGDMA)): 1.00 wt%;
[0121] Photoinitiator (specifically, ethyl (2,4,6-trimethylbenzoyl)phenylphosphonate (TPO-L)): 0.01 wt%;
[0122] Inhibitor (specifically 2,2,6,6-tetramethylpiperidine oxide (TEMPO)): 0.01 wt%;
[0123] UV blocking monomer (specifically 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (UV blocking agent)): 0.50 wt%;
[0124] Rheology and refractive index modifier monomer (specifically isobutyl methacrylate): 18.48 wt%.
[0125] In this embodiment, the preparation method of the medical optical material includes the following steps:
[0126] S1. Resin pretreatment: Specifically, the silica-containing oxygen-permeable monomer, hydrophilic monomer, crosslinking agent, photoinitiator, inhibitor, ultraviolet blocking monomer, and rheology and refractive index adjusting monomer are premixed, then vacuum degassed (usually degassed at -0.08 MPa for 20 min), filtered through 0.22 μm, dissolved oxygen (DO) is adjusted to 7 mg / L, and finally aged at 25°C for 24 h.
[0127] S2. Working Curve Calibration: 405nm stepped exposure, measuring absorption coefficient α and Dc / Esat; establishing a speed-dose matching table. Specifically, the absorption coefficient α (405nm), critical dose Dc, and saturation exposure energy Esat are calibrated under a 405nm light source to establish a dose-curing depth working curve, thereby constructing a dose-curing depth model and closing the loop with platform speed and grayscale frame rate.
[0128] S3. CAL continuous printing: Specifically, CAL forming is carried out under the conditions of an average surface illuminance of 18mW / cm², a continuous platform rise speed of 17RPM, a total exposure dose of 2.0×Dc, and a window temperature of 25–30℃.
[0129] S4. Cleaning: Perform rapid two-stage ultrasonic cleaning of the molded parts in sequence using PGMEA and IPA. Specifically, use PGMEA (propylene glycol methyl ether acetate) for 2×60s ultrasonic cleaning → IPA (isopropanol) for 2×60s ultrasonic cleaning; then blow with nitrogen for 60s, and pre-dry at 45℃ for 20min.
[0130] S5. Secondary UV irradiation and post-curing: Specifically, secondary UV irradiation is performed under nitrogen protection at a dose of 1.0 J / cm², followed by stepped heat curing at 60℃×2 h→80℃×2 h→100℃×1 h→80℃×1 h, and then slow cooling. N2 < 100 ppm, O2 < 100 ppm.
[0131] S6. Surface Modification: This includes plasma activation, application of a hydrophilic coating, and hydration in physiological saline. Specifically, the surface is plasma activated, a hydrophilic coating is applied and cured, and finally hydrated in physiological saline to obtain a product with high optical quality and biocompatibility, i.e., the medical optical material. Specifically, the surface is plasma activated under plasma conditions (O2 or air) at 80 W × 60 s; then the hydrophilic coating is spin-coated at 3000 rpm × 30 s and cured at 405 nm at 1.0 J / cm²; finally, it is hydrated in physiological saline for 24 h.
[0132] Example 4
[0133] A medical optical material, specifically comprising the following raw materials:
[0134] Silica-containing oxygen-permeable monomer (specifically 3-methacryloyloxypropyltrimethoxysilane (TRIS)): 65wt%;
[0135] Hydrophilic monomer (specifically 2-hydroxyethyl methacrylate (HEMA)): 15wt%;
[0136] Crosslinking agent (specifically ethylene glycol dimethacrylate (EGDMA)): 5.00 wt%;
[0137] Photoinitiator (specifically, ethyl (2,4,6-trimethylbenzoyl)phenylphosphonate (TPO-L)) 0.20 wt%;
[0138] Inhibitor (specifically 2,2,6,6-tetramethylpiperidine oxide (TEMPO)): 0.10 wt%;
[0139] UV blocking monomer (specifically 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (UV blocking agent)): 2.00 wt%;
[0140] Rheology and refractive index modifier monomer (specifically EHMA (i.e., 2-ethylhexyl methacrylate): 12.70 wt).
[0141] In this embodiment, the preparation method of the medical optical material can be referred to in Embodiment 1, and will not be repeated here.
[0142] Example 5
[0143] A medical optical material, specifically comprising the following raw materials:
[0144] Silicon-containing oxygen-permeable monomer (specifically PDMS-MA (polydimethylsiloxane-methyl methacrylate)): 40wt%;
[0145] Hydrophilic monomer (specifically glycidyl methacrylate (GMA)): 40 wt%;
[0146] Crosslinking agent (specifically triethylene glycol dimethacrylate (TEGDMA)): 1.00 wt%;
[0147] Photoinitiator (specifically Irgacure 784): 0.15wt%;
[0148] Inhibitor (specifically 2,2,6,6-tetramethylpiperidine oxide (TEMPO)): 0.01 wt%;
[0149] UV blocking monomer (specifically 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (UV blocking agent)): 0.50 wt%;
[0150] Rheology and refractive index modifier monomer (specifically EHMA (i.e., 2-ethylhexyl methacrylate): 18.34 wt).
[0151] In this embodiment, the preparation method of the medical optical material can be referred to in Embodiment 1, and will not be repeated here.
[0152] Example 6
[0153] A medical optical material, specifically comprising the following raw materials:
[0154] Silicon-containing oxygen-permeable monomer (specifically PDMS-MA (polydimethylsiloxane-methyl methacrylate)): 60wt%;
[0155] Hydrophilic monomer (specifically glycidyl methacrylate (GMA)): 20wt%;
[0156] Crosslinking agent (specifically triethylene glycol dimethacrylate (TEGDMA)): 5.00 wt%;
[0157] Photoinitiator (specifically Irgacure 784): 0.05 wt%;
[0158] Inhibitor (specifically 2,2,6,6-tetramethylpiperidine oxide (TEMPO)): 0.05 wt%;
[0159] UV blocking monomer (specifically 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (UV blocking agent)): 2.00 wt%;
[0160] Rheology and refractive index modifier monomer (specifically EHMA (i.e., 2-ethylhexyl methacrylate): 12.90 wt).
[0161] In this embodiment, the preparation method of the medical optical material can be referred to in Embodiment 1, and will not be repeated here.
[0162] Example 7
[0163] Compared with Example 1, the only difference is that the dissolved oxygen (DO) was adjusted to 3 mg / L during resin pretreatment.
[0164] Example 8
[0165] Compared with Example 1, the only difference is that the dissolved oxygen (DO) was adjusted to 8 mg / L during resin pretreatment.
[0166] Example 9
[0167] Compared with Example 1, the only difference is that the dissolved oxygen (DO) was adjusted to 10 mg / L during resin pretreatment.
[0168] Example 10
[0169] Compared with Example 1, except that the dose of the second UV irradiation is 1.5 J / cm² and the post-heat curing is continuous curing at 100°C for 4 hours, everything else is the same as Example 1.
[0170] Example 11
[0171] Compared with Example 1, except that the dose of the second UV irradiation is 1.0 J / cm² and the post-heat curing is continuous curing at 60°C for 6 hours, everything else is the same as Example 1.
[0172] Example 12
[0173] Compared with Example 1, except that CAL continuous printing is performed under a surface illuminance of 12mW / cm² and the total exposure dose is 1.6×Dc, everything else is the same as Example 1.
[0174] Example 13
[0175] Compared with Example 1, except that CAL continuous printing is performed under a surface illuminance of 18mW / cm² and the total exposure dose is 2.0×Dc, everything else is the same as Example 1.
[0176] Example 14
[0177] Compared with Example 1, except that CAL continuous printing is performed under a surface illuminance of 16mW / cm² and the total exposure dose is 1.7×Dc, everything else is the same as Example 1.
[0178] Comparative Example 1 (no TEMPO, O2 inhibition only)
[0179] Compared with Example 1, except that the amount of TEMPO is 0.00wt%, everything else is the same as Example 1. That is, there is no TEMPO inhibition, only O2 inhibition.
[0180] Specifically, its raw materials include:
[0181] 3-Methacryloxypropyltrimethoxysilane (TRIS): 52.00 wt%
[0182] 2-Hydroxyethyl methacrylate (HEMA): 28.00 wt%
[0183] Ethylene glycol dimethacrylate (EGDMA): 2.20 wt%
[0184] Ethyl (2,4,6-trimethylbenzoyl)phenylphosphonate (TPO-L): 0.08 wt%
[0185] 2,2,6,6-Tetramethylpiperidine oxide (TEMPO): 0.00 wt%
[0186] 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (UV blocker): 1.00 wt%
[0187] Isobutyl methacrylate (IBMA): 16.72 wt%.
[0188] The specific preparation method is described in Example 1 and will not be repeated here.
[0189] Observations revealed increased edge ghosting, a less steep threshold curve, and increased size fluctuations; an increased probability of under-curing at the same dosage; and the need to increase the total dosage to ≥2.10×Dc for stability, leading to an increased risk of thermal yellowing.
[0190] Comparative Example 2 (using BAPO-initiated system)
[0191] Compared to Example 1, the only difference is that 0.08 wt% of TPO-L is replaced with 0.08 wt% of BAPO; otherwise, the BAPO initiation system is used instead.
[0192] Specifically, its raw materials include:
[0193] 3-Methacryloxypropyltrimethoxysilane (TRIS): 52.00 wt%
[0194] 2-Hydroxyethyl methacrylate (HEMA): 28.00 wt%
[0195] Ethylene glycol dimethacrylate (EGDMA): 2.20 wt%
[0196] Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (BAPO): 0.08 wt%
[0197] 2,2,6,6-Tetramethylpiperidine oxide (TEMPO): 0.02 wt%
[0198] 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (UV blocker): 1.00 wt%
[0199] Isobutyl methacrylate (IBMA): 16.70 wt%.
[0200] The specific preparation method is described in Example 1 and will not be repeated here.
[0201] Observations showed that the YI value and haze increased after post-curing; the yellowing was significantly higher after long-term aging; and the conversion rate was insufficient if the UV dose was reduced to control yellowing.
[0202] Comparative Example 3 (Dissolved oxygen (DO) decreased to 5.00 mg / L)
[0203] Compared with Example 1, the only difference is that the dissolved oxygen (DO) was reduced to 5.00 mg / L (below the recommended range).
[0204] Specifically, its raw materials include:
[0205] 3-Methacryloxypropyltrimethoxysilane (TRIS): 52.00 wt%
[0206] 2-Hydroxyethyl methacrylate (HEMA): 28.00 wt%
[0207] Ethylene glycol dimethacrylate (EGDMA): 2.20 wt%
[0208] Ethyl (2,4,6-trimethylbenzoyl)phenylphosphonate (TPO-L): 0.08 wt%
[0209] 2,2,6,6-Tetramethylpiperidine oxide (TEMPO): 0.02 wt%
[0210] 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (UV blocker): 1.00 wt%
[0211] Isobutyl methacrylate (IBMA): 16.70 wt%.
[0212] Observations revealed that: insufficient inhibition layer thickness caused the formed parts to easily stick to the window; edge accuracy decreased; the platform speed needed to be reduced to 10-12 RPM to stabilize the forming process, but this reduced production efficiency; and surface quality decreased, requiring additional polishing.
[0213] Comparative Example 4 (TEMPO increased to 0.05 wt% with excessive inhibition)
[0214] Compared with Example 1, the only difference is that the amount of TEMPO was increased to 0.05 wt% (over-inhibition).
[0215] Specifically, its raw materials include:
[0216] 3-Methacryloxypropyltrimethoxysilane (TRIS): 52.00 wt%
[0217] 2-Hydroxyethyl methacrylate (HEMA): 28.00 wt%
[0218] Ethylene glycol dimethacrylate (EGDMA): 2.20 wt%
[0219] Ethyl (2,4,6-trimethylbenzoyl)phenylphosphonate (TPO-L): 0.08 wt%
[0220] 2,2,6,6-Tetramethylpiperidine oxide (TEMPO): 0.05 wt%
[0221] 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (UV blocker): 1.00 wt%
[0222] Isobutyl methacrylate (IBMA): 16.67 wt%.
[0223] Observations revealed severe under-curing, which was difficult to fully cure even with an increased dosage of 2.5×Dc; insufficient curing depth and loss of detail; conversion rate below 90% and excessive leaching content; and the need to increase TPO-L to more than 0.15wt% for partial compensation, but this would exacerbate yellowing.
[0224] By comparing the samples in the examples and the comparative examples, it can be seen that by using continuous liquid surface photocuring technology, a steep polymerization threshold and a stable inhibition layer are achieved by utilizing O2 / TEMPO dual inhibition, significantly reducing ghosting and window sticking. At the same time, combined with secondary UV irradiation and thermal post-curing, deep cross-linking is completed in the N2 environment, and yellowing and haze are suppressed.
[0225] Performance testing
[0226] The medical optical materials prepared in Example 1 were subjected to performance testing, including resin properties and optical parameters, molding and appearance, finished product performance, cleaning and post-curing, stability and consistency. Each batch was measured at least three times, and the mean ± standard deviation was recorded. Specific test results are shown in Tables 1-5.
[0227] Table 1 shows the test results for resin physical properties and optical parameters. Table 2 shows the test results for molding and appearance. Table 3 shows the test results for cleaning and post-curing conditions. Table 4 shows the test results for finished product performance. Table 5 shows the test results for stability and consistency.
[0228] In addition, to explore the curing process, dose-curing depth working curves and Dc / Esat fitting plots were plotted for the samples in Example 1, as detailed in [link to example]. Figure 1 The figure shows the dose-curing depth working curve and Dc / Esat fitting graph at 405nm, where R² = 0.9923, which meets the standard of R² ≥ 0.98. To verify the effect of DO and TEMPO on the thickness of the inhibition layer, referring to the preparation method of the traditional Chinese medicine optical material in Example 1, the amount of TEMPO was adjusted to 0.01wt%, 0.02wt%, and 0.03wt%, respectively. The thickness of the inhibition layer of the obtained products was then measured, and the specific results are shown in [Figure 1]. Figure 2 The figure shows the effect of DO and TEMPO on the thickness of the inhibition layer and the edge MTF. To observe the post-thermosetting thermal range and yellowness index / conversion rate, the sample from Example 1 was tested, and the results were obtained... Figure 3 The graph shown illustrates the relationship between the post-thermosetting thermal range and the yellowness index / conversion rate. To observe the morphology of the product prepared in Example 1, surface morphology observations were performed, and the results are as follows. Figure 4 As shown, specifically, the molded part of Example 1 and the product obtained by conventional layer printing (comparison sample) are subjected to atomic force microscopy (AFM) / white light interferometry to obtain surface morphology and atomic force microscopy (AFM) / white light interferometry results.
[0229] Table 1. Results of Resin Physical Properties and Optical Parameters Tests
[0230]
[0231] Table 2. Results of Molding and Appearance Inspection
[0232]
[0233] Table 3. Results of Cleaning and Post-Curing Condition Tests
[0234]
[0235] Table 4. Results of Finished Product Performance Testing
[0236]
[0237] Table 5. Results of Stability and Consistency Testing
[0238]
[0239] The results above demonstrate that the embodiments of this invention, through the rational use of raw materials such as photosensitive resin, crosslinking agent, photoinitiator, inhibitor, and UV-blocking monomer, and employing continuous liquid surface photocuring technology, achieve a steep polymerization threshold and a stable inhibition layer through O2 / TEMPO dual inhibition, significantly reducing ghosting and window sticking. Simultaneously, combined with secondary UV irradiation and post-thermal curing in an N2 environment, deep crosslinking is completed, suppressing yellowing and haze. This solves the problem that most existing orthokeratology lenses use traditional layered photocuring processes, resulting in defects such as ghosting and yellowing. Furthermore, the preparation method provided by these embodiments is simple and can be replicated using common 405 nm LED+DLP equipment; the process parameters can be programmed, making it suitable for stable mass production of orthokeratology lenses and other optical components, and possessing broad market prospects.
[0240] It should be noted that in the above embodiments of the present invention, for under-cured materials: the total dosage can be increased (+0.1×Dc per step) → TPO-L can be increased (+0.01–0.02wt%) → DO can be decreased (-0.5mg / L per step). For ghosting / illusion: resolution and uniformity can be improved → TEMPO can be reduced to within 0.03wt% → Gamma / speed fine-tuning can be applied. For yellowing / haze: the use of BAPO / TiO2 can be avoided; the UV spectrum should be mainly at 405nm; N2 protection and stepped thermal path control can be used.
[0241] It should also be noted that the photoinitiators TPO-L (i.e., ethyl 2,4,6-trimethylbenzoylphenylphosphonate), Irgacure 819, Irgacure 784, and TEMPO used in this invention are all products from existing manufacturers. For example, photoinitiator TPO-L can be produced by Nanjing Milan Chemical Co., Ltd., or Jiangsu Grory Chemical Co., Ltd., etc. These are all conventional additives used in the production of orthokeratology lenses; the specific selection is based on requirements and will not be elaborated upon here.
[0242] The preferred embodiments of the present invention have been described in detail above, outlining the basic principles, main features, and advantages of the invention. However, those skilled in the art should understand that the embodiments of the present invention are not limited to the above-described embodiments. The embodiments and descriptions in the specification are merely preferred examples of the present invention and are not intended to limit the invention. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the embodiments of the present invention. It is neither necessary nor possible to exhaustively describe all embodiments here. However, obvious changes or modifications derived therefrom are still within the protection scope of the embodiments of the present invention.
Claims
1. A medical optical material, characterized in that, The medical optical material comprises the following raw materials: photosensitive resin, crosslinking agent, photoinitiator, inhibitor, and ultraviolet-blocking monomer; wherein the photosensitive resin comprises a silica-containing oxygen-permeable monomer and a hydrophilic monomer, and the medical optical material specifically comprises the following raw materials in weight percentages: silica-containing oxygen-permeable monomer 35–65 wt%; hydrophilic monomer 15–45 wt%; crosslinking agent 1.00–5.00 wt%; photoinitiator 0.01–0.20 wt%; inhibitor 0.01–0.03 wt%; ultraviolet-blocking monomer 0.50–2.00 wt%. The medical optical material is prepared by pretreating photosensitive resin, crosslinking agent, photoinitiator, inhibitor, and ultraviolet blocking monomer, followed by continuous liquid surface photocuring and post-treatment. The post-treatment includes secondary UV irradiation and thermal post-curing. The dissolved oxygen content of the photosensitive resin is 6-8 mg / L. The hydrophilic monomer is selected from any one or more of HEMA, NVP, and GMA. The silicon-containing oxygen-permeable monomer is any one or more of hydroxyl-terminated polydimethylsiloxane, monomethacryloyloxypropyl modified polydimethylsiloxane, and fluorosiloxane. The photoinitiator is any one or more of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, photoinitiator Irgacure819, and photoinitiator Irgacure784.
2. The medical optical material according to claim 1, characterized in that, The medical optical material has a transmittance of ≥92% in the 550nm band, a haze of ≤1.0%, and an oxygen flux of ≥100 Barrer in a hydrated state at 35℃.
3. The medical optical material according to claim 2, characterized in that, The inhibitor is selected from any one of tetramethylpiperidine oxide, triphenyl phosphite, phenolic derivatives, or quinone compounds.
4. The medical optical material according to claim 3, characterized in that, in, The dose of the secondary UV irradiation is 1.0–1.5 J / cm², and the temperature range of the post-curing is 60–100℃.
5. A method for preparing a medical optical material as described in any one of claims 1-4, characterized in that, Includes the following steps: 1) Weigh out the photosensitive resin, crosslinking agent, photoinitiator, inhibitor, and UV blocking monomer according to the proportion for pretreatment. Control the dissolved oxygen of the photosensitive resin to be 6-8 mg / L, then perform continuous liquid surface photocuring, and obtain the pre-dried material after cleaning. 2) The pre-dried material obtained in step 1) is post-treated to obtain the medical optical material; wherein, the post-treatment includes secondary UV irradiation and thermal curing, specifically, secondary UV irradiation is performed under nitrogen protection, the dose is 1.0–1.5 J / cm², and step-curing is carried out sequentially at 60℃ for 2 h, 80℃ for 2 h, 100℃ for 1 h, and 80℃ for 1 h.
6. The method for preparing medical optical materials according to claim 5, characterized in that, In the preparation method of the medical optical material, the continuous liquid surface photocuring is carried out under the condition of surface average illuminance of 12–18 mW / cm².
7. A medical optical material prepared by the method for preparing medical optical material according to claim 6.
8. The use of a medical optical material as described in claim 1, 2, 3, 4, or 7 in the manufacture of vision correction medical devices.
9. The application of a medical optical material as described in claim 1, 2, 3, 4, or 7 in the preparation of orthokeratology medical devices.
Citation Information
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