阅读说明：本技术 一种防紫外线结构色彩色隐形眼镜及其制备方法 (Ultraviolet-proof structure color contact lens and preparation method thereof ) 是由 汪长春 沈秀清 于 2019-08-07 设计创作，主要内容包括：本发明属于隐形眼镜技术领域,具体为一种防紫外线结构色彩色隐形眼镜及其制备方法。本发明的彩色隐形眼镜基于三维周期性排列的微球形成光子晶体结构,拥有鲜艳的结构色。本发明制备方法包括：在隐形眼镜的两片模具之间夹入密实无气泡的单体微球混合物前驱体,改变凹模和凸模的相对位置,使所述前驱体材料发生流动,最终前驱体中微球均匀排列而显示出鲜艳的结构色,前驱体包含微球与可聚合单体混合液,微球包括核心层、中间层和壳层,可聚合单体混合液包含单官能团分子、交联剂和引发剂；将前驱体固化成聚合物隐形眼镜,再经脱模、溶胀,得到具有鲜艳结构色的隐形眼镜。本发明采用物理成色,颜色鲜艳,佩戴安全、舒适,市场前景广阔。(The invention belongs to the technical field of contact lenses, and particularly relates to an ultraviolet-proof structure color contact lens and a preparation method thereof. The colored contact lens forms a photonic crystal structure based on three-dimensional periodically arranged microspheres and has bright structural color. The preparation method comprises the following steps: the method comprises the following steps of clamping a compact bubble-free monomer microsphere mixture precursor between two molds of the contact lens, changing the relative positions of a female mold and a male mold, enabling the precursor material to flow, and finally enabling microspheres in the precursor to be uniformly arranged to display a bright structural color, wherein the precursor comprises a microsphere and polymerizable monomer mixed solution, the microsphere comprises a core layer, an intermediate layer and a shell layer, and the polymerizable monomer mixed solution comprises monofunctional group molecules, a cross-linking agent and an initiator; and curing the precursor into a polymer contact lens, demolding and swelling to obtain the contact lens with bright structural color. The invention adopts physical color, has bright color, is safe and comfortable to wear and has wide market prospect.)

1. A method for preparing ultraviolet-proof structure color contact lenses, wherein three-dimensional photonic crystals are adopted in the lenses, is characterized by comprising the following specific steps:

(1) selection of contact lens molds:

according to the requirements of the photonic crystal contact lens, selecting a mold with a specific structure for preparing a structural color contact lens; the die comprises a female die and a male die;

(2) preparing a precursor of the monomer microsphere mixture:

mixing the microspheres with the polymerizable monomer mixed solution, and fully and uniformly dispersing the monodisperse microspheres in the mixed solution to obtain a monomer microsphere mixture precursor;

(3) preparing the ultraviolet-proof structural color contact lens:

clamping a compact bubble-free monomer microsphere mixture precursor between a female die and a male die of a contact lens die, changing the relative positions of the female die and the male die, and enabling the limiting surface of the female die and the limiting surface of the male die to generate relative displacement, so that the monomer microsphere mixture precursor material flows, namely the precursor flows in a shearing manner relative to the limiting surface of the die, and finally microspheres in the precursor are uniformly arranged to display a bright structural color;

(4) curing the ultraviolet-proof structural color contact lens:

and curing the precursor into a polymer contact lens, demolding the contact lens, and immersing the contact lens in a standard salt solution until the swelling is balanced, thereby finally obtaining the contact lens with bright structural color.

2. The method according to claim 1, wherein the contact lens mold in step (1) is made of polyethylene terephthalate, polypropylene, glass, quartz, polystyrene or polycarbonate.

3. The preparation method according to claim 1, wherein the microsphere in the step (2) is a core-shell structure nano microsphere, and the microsphere comprises a core layer, an intermediate layer and a shell layer; wherein the core layer accounts for 30-55% of the weight of the microsphere, the shell layer accounts for 30-60% of the weight of the microsphere, the shell layer and the core layer are connected by the intermediate layer, the intermediate layer accounts for 5-20% of the weight of the microsphere, and the total amount of the three layers is 100%; the size of the nano microsphere is 100-1000 nm, and the size dispersity of the same nano microsphere is lower than 5%.

4. The method according to claim 3, wherein the core layer of the microsphere in step (2) consists of a core layer 1 and a core layer 2; wherein, the core layer 1 accounts for 10 to 90 percent of the weight of the core layer, and the core layer 2 accounts for 10 to 90 percent of the weight of the core layer; the core layer 2 is coated outside the core layer 1; wherein:

the material of the core layer 2 is selected from polymethyl methacrylate, polyethyl methacrylate, polyisobutyl methacrylate, polyacrylonitrile, polycyclohexyl methacrylate and polyisobornyl methacrylate; the material of the core layer 1 is selected from polystyrene, polymethyl methacrylate, polyacrylonitrile, polycyclohexyl methacrylate, isobornyl methacrylate, silicon dioxide, ferroferric oxide, gold and silver.

5. The method according to claim 4, wherein the monomer mixture in step (2) comprises a monofunctional molecule, a crosslinking agent, and an initiator; wherein, the weight of the cross-linking agent is 0.01-25% of that of the monofunctional molecule, and the weight of the initiator is 0.01-8% of that of the monofunctional molecule.

6. The method according to claim 5, wherein the monofunctional molecule is selected from the group consisting of hydroxyethyl methacrylate, methacrylamide, methyl methacrylate, cellulose acetate butyrate, silicone methacrylate, fluorosilicone methacrylate, glycidyl methacrylate and ethylene glycol dimethacrylate, or a mixture of a plurality thereof;

the cross-linking agent is selected from one of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1, 4-butanediol diacrylate, methylene bisacrylamide, N '-cysteamine, N' - (1, 2-dihydroxyethylene) bisacrylamide-tripropylene glycol diacrylate, dipropylene glycol diacrylate or a mixture of a plurality of ethylene glycol dimethacrylate and diethylene glycol dimethacrylate;

the initiator is a photoinitiator or a thermal initiator;

the photoinitiator is selected from one or a mixture of a plurality of benzoin derivatives, anthraquinone derivatives, thioxanthones, diphenylethanedione derivatives, benzophenone derivatives and acetophenone derivatives;

the thermal initiator is selected from one or a mixture of sodium persulfate, potassium persulfate, ammonium persulfate and azo initiators.

7. The method according to any one of claims 1 to 6, wherein the precursor in step (2) contains 40% to 75% by weight of microspheres.

8. The manufacturing method according to claim 7, wherein in the step (3), the relative positions of the female die and the male die are changed by fixing one die and controlling the spherical limiting surface of the other die to rotate around the spherical center; and a shear rate in excess of 0.1 s in a thickness of 0-2 microns near the confining surface^-1。

9. The method according to claim 8, wherein in the step (4), when the initiator is a photoinitiator, 0.001W/cm is used²-100W/cm²Ultraviolet light with the power of 1 second to 1 hour is used for curing the precursor; when the initiator is a thermal initiator, the initiator is heated at 40-150 ℃ for 10 min-48 hThe precursor is cured in a manner.

10. Uv-protected contact lenses of structural chromatic color obtainable by the production process according to one of claims 1 to 9.

Technical Field

The invention belongs to the technical field of contact lenses, and particularly relates to an ultraviolet-proof structure color contact lens and a preparation method thereof.

Background

With the improvement of science and technology and living standard, the pursuit of beauty, fashion and safety of the public is gradually increased. Contact lenses are increasingly taking up the frame lens market due to their fashionability and aesthetics. By incomplete statistics, the colored contact lens market has been accounting for 35% of the contact lens market over the past decades.

The contact lens can correct the eyesight, wherein the method of changing the color of the contact lens part by using the pigment and the pigment can change the appearance color of the iris, plays the role of decoration and beautification and is popular. Colored contact lenses have long been proposed, primarily using the technique of printing patterns on the iris region of contact lenses (US 3,476,499), and later, with colored interlayers being prepared on the inside of contact lenses (US 3, 712, 718). While related patents continue to improve upon contact lens technology, the color portion is always based on a pigment color material. As an intermediate layer, the pigment layer hinders the exchange of oxygen between the eye and the outside. In addition, the pigment color material with biotoxicity also poses hidden danger for eye health.

Recently, there have been team reports on the research work of preparing photonic crystal contact lenses using the templating method (CN 102193213 a, CN 103941418A), but the preparation process uses hazardous agents such as hydrogen fluoride, etc., which increases the complexity of the product preparation. As a contact lens manufactured based on the structural color, there is a patent report that a photonic crystal structure layer is manufactured on a contact lens mold by femtosecond pulse two-photon polymerization to obtain a contact lens mold (CN 105116564 a) having a photonic crystal structure, and a structural color contact lens is manufactured using the mold. However, this method has a complicated apparatus and a high manufacturing cost because the structural color is present only on the surface.

A number of visual optics and ophthalmology studies have shown that ultraviolet band a (uva) and band b (uvb) are among the causes of eye diseases such as macular degeneration, cataracts, keratitis, etc. The ultraviolet absorption effect of the contact lenses sold in the domestic market at present belongs to ANSI CLASS II standard, UVB absorption is about 95%, UVA absorption is about 70%, and high-effect ultraviolet-resistant ANSI CLASS I contact lens products are fewer.

Therefore, there is a need in the market for a colored contact lens that is uv-resistant, aesthetically pleasing, safe, and low in manufacturing cost.

Disclosure of Invention

The invention aims to provide an attractive, comfortable and safe ultraviolet-proof structure color contact lens and a preparation method thereof, so as to avoid the problems of low comfort level and poor safety caused by using a pigment color layer in the prior art and serious foreign body sensation brought to a wearer.

The invention provides a method for preparing ultraviolet-proof structure color contact lenses, wherein the lenses adopt three-dimensional photonic crystals, and the method comprises the following specific steps:

(1) selection of contact lens molds:

according to the requirements of the photonic crystal contact lens, selecting a mold with a specific structure for preparing a structural color contact lens; the die comprises a female die and a male die;

(2) preparing a precursor of the monomer microsphere mixture:

mixing the microspheres with the polymerizable monomer mixed solution, and fully and uniformly dispersing the monodisperse microspheres in the mixed solution to obtain a monomer microsphere mixture precursor;

(3) preparing the ultraviolet-proof structural color contact lens:

clamping a compact bubble-free monomer microsphere mixture precursor between a female die and a male die of a contact lens die, changing the relative positions of the female die and the male die, and enabling the limiting surface of the female die and the limiting surface of the male die to generate relative displacement, so that the monomer microsphere mixture precursor material flows, namely the precursor flows in a shearing manner relative to the limiting surface of the die, and finally microspheres in the precursor are uniformly arranged to display a bright structural color;

(4) curing the ultraviolet-proof structural color contact lens:

and curing the precursor into a polymer contact lens, demolding the contact lens, and immersing the contact lens in a standard salt solution until the swelling is balanced, thereby finally obtaining the contact lens with bright structural color.

Preferably, in the step (1), the material of the contact lens mold is polyethylene terephthalate, polypropylene, glass, quartz, polystyrene or polycarbonate.

Preferably, in the step (2), the microsphere is a core-shell structure nano microsphere, and the microsphere includes a core layer, an intermediate layer and a shell layer. Wherein the core layer accounts for 30-55% of the weight of the microsphere, the shell layer accounts for 30-60% of the weight of the microsphere, the shell layer and the core layer are connected by the intermediate layer, the intermediate layer accounts for 5-20% of the weight of the microsphere, and the total amount of the three layers is 100%; the size of the nano microsphere is generally 100-1000 nm, and the size dispersity of the same nano microsphere is generally lower than 5%.

Preferably, in step (2), the core layer of the microsphere consists of the core layer 1 and the core layer 2 together. Wherein, the core layer 1 accounts for 10 to 90 percent of the weight of the core layer, and the core layer 2 accounts for 10 to 90 percent of the weight of the core layer; the core layer 2 is coated outside the core layer 1.

Preferably, the material of the core layer 2 is selected from the group consisting of polymethyl methacrylate, polyethyl methacrylate, isobutyl methacrylate, polyacrylonitrile, polycyclohexyl methacrylate, and isobornyl methacrylate. The material of the core layer 1 is selected from polystyrene, polymethyl methacrylate, polyacrylonitrile, polycyclohexyl methacrylate, isobornyl methacrylate, silicon dioxide, ferroferric oxide, gold and silver.

Preferably, in the step (2), the monomer mixture comprises a monofunctional molecule, a crosslinking agent and an initiator; wherein, the weight of the cross-linking agent is 0.01-25% of that of the monofunctional molecule, and the weight of the initiator is 0.01-8% of that of the monofunctional molecule.

Preferably, the monofunctional molecule comprises one of hydroxyethyl methacrylate, methacrylamide, methyl methacrylate, cellulose acetate butyrate, silicone methacrylate, fluorosilicone methacrylate, glycidyl methacrylate and ethylene glycol dimethacrylate, or a mixture of a plurality thereof. The monofunctional molecule is not limited thereto, and monofunctional molecules commonly used for producing contact lenses at present are all possible.

Preferably, the cross-linking agent comprises one or more of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1, 4-butanediol diacrylate, methylene bisacrylamide, N '-cysteamine, N' - (1, 2-dihydroxyethylene) bisacrylamide-tripropylene glycol diacrylate, dipropylene glycol diacrylate in a mixture. The crosslinking agent is not limited thereto, and any crosslinking agent commonly used for producing contact lenses at present is acceptable.

Preferably, the initiator comprises a photoinitiator or a thermal initiator.

Preferably, the photoinitiator is selected from one of benzoin, anthraquinone, thioxanthone, diphenylethanedione, benzophenone and acetophenone derivatives, or a mixture of several of them.

Preferably, the thermal initiator is selected from one of sodium persulfate, potassium persulfate, ammonium persulfate and azo initiator, or a mixture of several of the above initiators.

Preferably, in the step (2), the content of the microspheres is 40-75% of the precursor by weight percentage.

Preferably, in step (3), the entrapment of air bubbles should be avoided when sandwiching the precursor between the female mold and the male mold.

Preferably, in step (3), the sandwiching of the compact bubble-free precursor between the female mold and the male mold should be such that the confined face space is filled with the compact bubble-free precursor.

Preferably, in the step (3), the relative positions of the female die and the male die are changed by fixing one die (the female die or the male die) and controlling the spherical limiting surface of the other die (the male die or the female die) to rotate around the spherical center.

Preferably, in step (3), the shear rate exceeds 0.1 s in a thickness of 0 to 2 μm near the confining surface^-1。

Preferably, in step (3), the thickness of the contact lens is determined and minimized by the concave and convex mold limiting surfaces when the microspheres in the precursor are uniformly arranged to exhibit a vivid structural color. The microspheres in and on the contact lens exhibit a degree of periodic alignment.

Preferably, in step (4), when the initiator is a photoinitiator, 0.001W/cm is used²-100W/cm²The precursor is cured by ultraviolet irradiation at the power of 1 second to 1 hour.

Preferably, in the step (4), when the initiator is a thermal initiator, the precursor is cured by heating at 40-150 ℃ for 10 min-48 h.

Preferably, in step (4), the brine is a 0.9 wt% sodium chloride solution.

The invention has the beneficial effects that: the invention prepares the ultraviolet-proof structure color contact lens based on the three-dimensional photonic crystal, overcomes the problem that the existing commercialized color contact lens is based on a color forming method of chemical dye, avoids the potential safety problems of biological toxicity and the like caused by a chemical pigment layer, and provides a high-efficiency ultraviolet-proof function. A photonic crystal structure is formed by utilizing a shear induction effect, so that colorful and bright structural colors are realized, and the safety and the attractiveness of the lens are improved; by utilizing the scattering effect, the contact lens has a high-efficiency ultraviolet-proof function and a wide market prospect.

Drawings

FIG. 1 is a schematic view of the UV-blocking contact lens according to the present invention.

FIG. 2 is a scanning electron micrograph of a cross section of a UV-blocking structural color contact lens.

FIG. 3 is a chart of the UV-visible transmission spectrum of the UV-blocking linear color contact lens of example 1.

Detailed Description

The foregoing aspects and many of the attendant advantages and features of this invention will become more readily appreciated by those skilled in the art as the same become better understood by reference to the following detailed description, taken in conjunction with the accompanying drawings. It will be understood that numerous modifications and adaptations can be made without departing from the principles of the embodiments of the present invention, and such modifications and adaptations are intended to be within the scope of the embodiments of the present invention.