CN115678193B - Wearable transparent contact lens - Google Patents
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- CN115678193B CN115678193B CN202211410419.5A CN202211410419A CN115678193B CN 115678193 B CN115678193 B CN 115678193B CN 202211410419 A CN202211410419 A CN 202211410419A CN 115678193 B CN115678193 B CN 115678193B
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- 239000002105 nanoparticle Substances 0.000 claims abstract description 72
- 239000000017 hydrogel Substances 0.000 claims abstract description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 9
- BESKSSIEODQWBP-UHFFFAOYSA-N 3-tris(trimethylsilyloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C BESKSSIEODQWBP-UHFFFAOYSA-N 0.000 claims description 9
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 9
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 9
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 8
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 8
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 6
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical group C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 6
- 238000001723 curing Methods 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 29
- 238000002834 transmittance Methods 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 10
- 238000001514 detection method Methods 0.000 abstract description 4
- 230000008447 perception Effects 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012154 double-distilled water Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000006870 function Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000004297 night vision Effects 0.000 description 2
- 241000282412 Homo Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
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- 238000000703 high-speed centrifugation Methods 0.000 description 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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Abstract
The invention discloses a wearable transparent contact lens, which is obtained by dispersing hydrochloric acid stripping modified up-conversion nano particles in a silicon-based hydrogel precursor liquid, and then carrying out curing film forming reaction and subsequent treatment. The invention improves the hydrophilicity and dispersibility of the up-conversion nano particles by using a hydrochloric acid stripping method, so that the prepared contact lens can still keep higher visible light transmittance when the up-conversion nano particles are added into hydrogel with higher filling content, and meanwhile, the intelligent contact lens can convert near infrared light invisible to naked eyes into visible light, thereby realizing the purpose of near infrared light perception detection; the contact lens has reasonable design, simple structure and high feasibility of a preparation scheme, and the comprehensive optical performance of the contact lens is close to that of a commercial contact lens, so that the contact lens has important application prospects in the fields of commerce, military and the like.
Description
Technical Field
The invention belongs to the field of multifunctional contact lenses, and particularly relates to a wearable transparent contact lens with a near infrared light conversion effect.
Background
Visible light refers to electromagnetic radiation having a wavelength between 390nm and 780 nm. However, in nature, there are also a large number of electromagnetic waves invisible to the naked eye, such as near infrared light waves widely existing at night or in dark environments, and the characteristic wavelength range is 780-2526nm, which cannot be seen by the naked eye. Thus, if conversion of near infrared light into visible light is enabled, humans can achieve night vision.
With the rapid development of nanotechnology in recent years, researchers have been able to develop various light conversion nanomaterials with special functions. The up-conversion luminescent nano material is a functional material capable of converting infrared light with lower energy into visible light with higher energy, and is of great interest to global researchers. The up-conversion luminescent material has important application value in various fields such as anti-counterfeiting, display, fluorescent imaging, medical treatment and the like due to the characteristics of long fluorescence lifetime, larger specific surface area, narrow luminous band and the like. For example, patent CN 105063889a reports a preparation method of an up-conversion film based on rare earth ion doping, and its good light conversion effect gives it a potential application space in the field of fluorescence detection.
Since the invention, the contact lens has the advantages of easy wearing, high transparency, wide visual field, good biocompatibility and the like, and therefore, the contact lens plays a special role in the fields of vision correction, eye treatment and the like. Based on the advantages of convenient wearing and the like, the near infrared light can be possibly converted into visible light by introducing the up-conversion nano particles into the contact lens, and finally the visible light is visible to naked eyes of human beings. For example, patent CN 111154489a reports a smart contact lens based on up-converting luminescent nanomaterials, which has a certain night vision effect. However, the up-conversion contact lens developed at present has complicated preparation process, and when the particle content is high, the light conversion effect is increased, but the whole light transmittance of the contact lens is inevitably reduced, so that the visibility is seriously affected. In order to ensure high light transmittance, the particle content must be controlled to a small range, and the light conversion effect of the contact lens is reduced. Therefore, how to ensure that the light conversion effect of the up-conversion contact lens is improved under the premise of higher transparency is a key problem to be solved in order to realize commercialization of the intelligent lens in the early days.
Disclosure of Invention
In order to solve the problems in the prior art, the invention successfully develops a high-transparency silicon-based hydrogel contact lens filled with modified up-conversion nano-particles, which is mainly obtained by mixing the modified up-conversion nano-particles into a silicon-based hydrogel precursor liquid, and then performing photo-curing and soaking treatment. The invention provides the contact lens with the conversion effect on the near infrared light, and the nano particles are uniformly mixed, so that the contact lens has high transparency while light conversion is realized. Therefore, the contact lens of the present invention is of greater commercial utility.
The invention adopts the following technical scheme for realizing the purpose:
in one aspect, the invention provides a wearable transparent contact lens, which is obtained by dispersing modified up-conversion nanoparticles in a silicon-based hydrogel precursor solution to obtain a mixed solution, and then curing the mixed solution to form a film and performing subsequent treatment.
In one embodiment of the invention, the mass concentration of the modified up-conversion nanoparticles in the mixed solution is 0.1% -6%, that is, the mass ratio of the modified up-conversion nanoparticles to the silicon-based hydrogel precursor solution is 1:999-3:47.
In one embodiment of the invention, the modified up-conversion nanoparticle is a modified NaYF 4 Nanoparticles or modified NaLnF 4 And (3) nanoparticles.
In one embodiment of the invention, the modification method of the modified up-conversion nanoparticle is to remove oleic acid on the surface of the up-conversion nanoparticle by using an HCl stripping method to increase the hydrophilicity thereof. The method comprises the following specific steps:
step 1, diluting concentrated HCl by using secondary distilled water to prepare dilute HCl solution with the concentration range of 0.024-0.11 mol/L;
step 2, adding the up-conversion nano particles into a dilute HCl solution, uniformly dispersing by ultrasonic, and peeling by magnetic stirring or mechanical stirring for 0.5-2h;
and step 3, centrifuging and drying the mixture obtained in the step 2 to obtain the modified up-conversion nano particles.
In one embodiment of the invention, the silicon-based hydrogel precursor solution is prepared by uniformly mixing the following raw materials in percentage by mass in a light-resistant environment: 20% -50% of methacryloxypropyl tris (trimethylsiloxy) silane; 15% -50% of N, N-dimethylacrylamide; 10% -20% of N-vinyl pyrrolidone; 8% -15% of hydroxyethyl methacrylate; ethylene glycol dimethacrylate 0.3% -1%; 0.1% -0.6% of photoinitiator.
In one embodiment of the invention, the photoinitiator in the silicon-based hydrogel precursor solution is 1-hydroxycyclohexyl phenyl ketone or 2-hydroxy-2-methyl-1-phenyl-1-propanone.
In one embodiment of the invention, the curing film-forming reaction is accomplished using a contact lens mold under curing conditions of 365nm uv light for 20-60 minutes.
In one embodiment of the invention, the subsequent treatment comprises placing the cured film in an ethanol/distilled water mixture and soaking at 40-60 ℃ for 12-24h. The volume ratio of ethanol to secondary distilled water is 1:1.
In another aspect, the invention also provides a method for preparing the wearable transparent contact lens, comprising the following steps:
step 1, uniformly mixing all raw materials of a silicon-based hydrogel precursor liquid in a light-shielding environment to obtain the silicon-based hydrogel precursor liquid;
step 2, adding the modified up-conversion nano particles into a silicon-based hydrogel precursor solution, and uniformly mixing by ultrasonic to obtain a mixed solution;
step 3, dripping the mixed solution obtained in the step 2 into a contact lens mold, solidifying under the irradiation of an ultraviolet lamp, and taking out the composite film after cooling;
and 4, soaking the composite membrane obtained in the step 3 into an ethanol/secondary distilled water mixed solution, heating and soaking the composite membrane in an oven at 40-60 ℃ for 12-24 hours, taking out the composite membrane, and washing the composite membrane with secondary distilled water to obtain the wearable transparent contact lens.
Compared with the prior art, the invention has the beneficial effects that:
the invention improves the hydrophilicity and dispersibility of the up-conversion nano particles by using a hydrochloric acid stripping method, so that the prepared contact lens can still keep higher visible light transmittance when the up-conversion nano particles are added into hydrogel with higher filling content, and meanwhile, the intelligent contact lens can convert near infrared light invisible to naked eyes into visible light, thereby realizing the purpose of near infrared light perception detection. The contact lens has reasonable design, simple structure and high feasibility of a preparation scheme, and the comprehensive optical performance of the contact lens is close to that of a commercial contact lens, so that the contact lens has important application prospects in the fields of commerce, military and the like.
Drawings
FIG. 1 is a scanning electron microscope image of the original oily upconverting nanoparticles used in examples 1-4 of the present invention;
FIG. 2 is a scanning electron microscope image of the hydrophilically modified up-conversion nanoparticles treated with hydrochloric acid in inventive example 1;
FIG. 3 is a photograph of a contact lens prepared with original oily upconverting nanoparticles (4%);
FIG. 4 is a graph showing the visible light transmittance test results for contact lenses prepared with varying amounts of the original oily upconverting nanoparticles;
FIG. 5 is a photograph of a contact lens prepared with modified up-conversion nanoparticles (4%);
FIG. 6 is a graph showing the visible light transmittance test results for contact lenses prepared with different levels of modified up-conversion nanoparticles;
fig. 7 is a photograph of a contact lens prepared with modified up-conversion nanoparticles (4%) converted to visible light under irradiation with 980nm near infrared light.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
The upconverting nanoparticle used in the following examples was NaYF 4 Up-converting the nanoparticles.
1. Preparation of modified up-conversion nanoparticles
Example 1
The preparation steps of the modified up-conversion nanoparticle of this example are as follows:
step 1, 50. Mu.L of concentrated HCl is diluted with 10.5mL of double distilled water to prepare a dilute HCl solution with a concentration of 0.057 mol/L.
Step 2, adding 70mg of up-conversion nano particles into a dilute HCl solution, uniformly dispersing by ultrasonic, and magnetically stirring for 1.5 hours;
and 3, performing high-speed centrifugation (the centrifugal speed is 8000 rpm) on the mixture obtained in the step 2 by using a centrifugal machine, and drying at 50 ℃ for 12 hours to obtain the modified up-conversion nano particles.
Example 2
The preparation steps of the modified up-conversion nanoparticle of this example are as follows:
step 1, diluting 30 mu L of concentrated HCl by using 15mL of double distilled water to prepare a dilute HCl solution with the concentration of 0.024 mol/L.
Step 2, adding 50mg of up-conversion nano particles into a dilute HCl solution, uniformly dispersing by ultrasonic, and magnetically stirring for 2 hours;
step 3, the same as in example 1.
Example 3
The preparation steps of the modified up-conversion nanoparticle of this example are as follows:
step 1, diluting 80 mu L of concentrated HCl by using 9mL of double distilled water to prepare a dilute HCl solution with the concentration of 0.11 mol/L.
Step 2, adding 40mg of up-conversion nano particles into a dilute HCl solution, uniformly dispersing by ultrasonic, and stirring for 0.5h by magnetic force;
step 3, the same as in example 1.
Example 4
The preparation steps of the modified up-conversion nanoparticle of this example are as follows:
and step 1, diluting 80 mu L of concentrated HCl by using 12mL of double distilled water to prepare a dilute HCl solution with the concentration of 0.08 mol/L.
Step 2, adding 90mg of up-conversion nano particles into a dilute HCl solution, uniformly dispersing by ultrasonic, and stirring by magnetic force for 1h;
step 3, the same as in example 1.
2. Preparation of contact lenses
Example 5
The contact lens is prepared in this example as follows:
step 1, uniformly mixing methacryloxypropyl tris (trimethylsiloxy) silane, N-dimethylacrylamide, N-vinyl pyrrolidone, hydroxyethyl methacrylate, ethylene glycol dimethacrylate and 1-hydroxycyclohexyl phenyl ketone in a light-resistant environment to obtain a silicon-based hydrogel precursor solution.
Step 2, according to the mass ratio of the modified up-conversion nano particles to the silicon-based hydrogel precursor liquid of 0.5 percent: 99.5 percent, adding the modified up-conversion nano particles prepared in the embodiment 3 into the silicon-based hydrogel precursor liquid, and uniformly mixing by ultrasonic to obtain mixed liquid; the mass percentages of the raw materials in the mixed solution are as follows:
methacryloxypropyl tris (trimethylsiloxy) silane: 40 percent of
N, N-dimethylacrylamide: 35%
N-vinylpyrrolidone: 10 percent of
Hydroxyethyl methacrylate: 13.1%
Ethylene glycol dimethacrylate: 0.9%
2-hydroxy-2-methyl-1-phenyl-1-propanone: 0.5%
Modified up-conversion nanoparticles: 0.5%.
Step 3, dripping the mixed solution obtained in the step 2 into a contact lens mold, solidifying for 20min under the irradiation of a 365nm ultraviolet lamp, and taking out the composite film after cooling;
and step 4, soaking the composite membrane obtained in the step 3 into an ethanol/secondary distilled water mixed solution, heating and soaking the composite membrane in a 50 ℃ oven for 12 hours, taking out the composite membrane, and washing the composite membrane with secondary distilled water to obtain the contact lens.
Example 6
This example a contact lens was prepared in the same manner as in example 5, except that: in the step 2, the mass ratio of the modified up-conversion nano particles to the silicon-based hydrogel precursor liquid is 2 percent: 98%, the mass percentages of the raw materials in the obtained mixed solution are as follows:
methacryloxypropyl tris (trimethylsiloxy) silane: 35%
N, N-dimethylacrylamide: 40 percent of
N-vinylpyrrolidone: 11%
Hydroxyethyl methacrylate: 11%
Ethylene glycol dimethacrylate: 0.5%
2-hydroxy-2-methyl-1-phenyl-1-propanone: 0.5%
Modified up-conversion nanoparticles: 2%.
Example 7
This example a contact lens was prepared in the same manner as in example 5, except that: in the step 2, the mass ratio of the modified up-conversion nano particles to the silicon-based hydrogel precursor liquid is 3 percent: 97%, the mass percentages of the raw materials in the obtained mixed solution are as follows:
methacryloxypropyl tris (trimethylsiloxy) silane: 38.4%
N, N-dimethylacrylamide: 30.2%
N-vinylpyrrolidone: 18%
Hydroxyethyl methacrylate: 10 percent of
Ethylene glycol dimethacrylate: 0.3%
1-hydroxycyclohexyl phenyl ketone: 0.1%
Modified up-conversion nanoparticles: 3%
Example 8
This example a contact lens was prepared in the same manner as in example 5, except that: in the step 2, the mass ratio of the modified up-conversion nano particles to the silicon-based hydrogel precursor liquid is 4 percent: 96% of the mass percentage of each raw material in the obtained mixed solution is as follows:
methacryloxypropyl tris (trimethylsiloxy) silane: 26.7%
N, N-dimethylacrylamide: 38%
N-vinylpyrrolidone: 18%
Hydroxyethyl methacrylate: 12%
Ethylene glycol dimethacrylate: 0.8%
2-hydroxy-2-methyl-1-phenyl-1-propanone: 0.5%
Modified up-conversion nanoparticles: 4%.
Example 9
This example a contact lens was prepared in the same manner as in example 5, except that: in the step 2, the mass ratio of the modified up-conversion nano particles to the silicon-based hydrogel precursor liquid is 6 percent: 94%, the mass percentages of the raw materials in the obtained mixed solution are as follows:
methacryloxypropyl tris (trimethylsiloxy) silane: 45%
N, N-dimethylacrylamide: 17%
N-vinylpyrrolidone: 17%
Hydroxyethyl methacrylate: 14%
Ethylene glycol dimethacrylate: 0.8%
1-hydroxycyclohexyl phenyl ketone: 0.2%
Modified up-conversion nanoparticles: 6%.
Comparative example 1
This comparative example a contact lens was prepared in the same manner as in example 5 except that: the modified up-conversion nano particles are not added, namely, the mass ratio of the modified up-conversion nano particles to the silicon-based hydrogel precursor liquid in the step 2 is 0 percent: 100%, the mass percentages of the raw materials in the obtained mixed solution are as follows:
methacryloxypropyl tris (trimethylsiloxy) silane: 40 percent of
N, N-dimethylacrylamide: 35.5%
N-vinylpyrrolidone: 10 percent of
Hydroxyethyl methacrylate: 13%
Ethylene glycol dimethacrylate: 1%
1-hydroxycyclohexyl phenyl ketone: 0.5.
comparative example 2
In this comparative example, the modified up-conversion nanoparticles in examples 5 to 9 were replaced with the original oily up-conversion nanoparticles in equal amounts, respectively, and contact lenses were produced in the same manner.
The wearable up-conversion contact lens can convert near infrared light invisible to naked eyes into visible light, has detection and perception functions of near infrared light, and can improve the surface hydrophilicity of up-conversion particles by adopting a hydrochloric acid stripping method, so that the interface effect of the particles and hydrogel is facilitated, and finally the light transmittance of the contact lens is obviously improved.
Fig. 1 is a scanning electron microscope image of original oily up-conversion nanoparticles used in examples 1 to 4 of the present invention dispersed in water, and fig. 2 is a scanning electron microscope image of modified up-conversion nanoparticles treated with hydrochloric acid dispersed in water, and it can be seen that the dispersibility of the modified up-conversion nanoparticles in water is significantly improved. And in the concentration range of 0.024-0.11mol/L, the obtained dispersion liquid of the modified conversion nano particles is better along with the increase of the concentration of the dilute HCl used for modification.
Fig. 3 is a photograph of a contact lens prepared with original oily upconverting nanoparticles, which can be seen to be severely whitened, and the light transmittance thereof is also seen to be poor from the visible light transmittance test result of fig. 4.
Fig. 5 is a photograph of a contact lens prepared with modified upconverting nanoparticles, which can be seen to have a higher transparency. From the visible light transmittance test results of fig. 6, it can be seen that the visible light transmittance of the upconversion contact lens with different particle content still reaches 80%, which is close to commercial application.
Fig. 7 is a photograph of a contact lens prepared with modified upconversion nanoparticle particles that converts to visible light upon illumination with 980nm near infrared light, and it can be seen that the contact lens can convert near infrared light to visible light, enabling near infrared light detection and naked eye perception.
The foregoing description of the preferred embodiment of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (7)
1. A wearable transparent contact lens, characterized by: the contact lens is obtained by dispersing modified up-conversion nano particles in a silicon-based hydrogel precursor solution to obtain a mixed solution, and then carrying out curing film-forming reaction and subsequent treatment on the mixed solution;
the modification method of the modified up-conversion nano-particles is to remove oleic acid on the surfaces of the up-conversion nano-particles by using an HCl stripping method so as to improve the hydrophilicity of the oleic acid; the modified up-conversion nano particles are modified NaYF 4 Nanoparticles or modified NaLnF 4 A nanoparticle;
the silicon-based hydrogel precursor liquid is prepared by uniformly mixing the following raw materials in percentage by mass in a light-resistant environment: 20% -50% of methacryloxypropyl tris (trimethylsiloxy) silane; 15% -50% of N, N-dimethylacrylamide; 10% -20% of N-vinyl pyrrolidone; 8% -15% of hydroxyethyl methacrylate; ethylene glycol dimethacrylate 0.3% -1%; 0.1% -0.6% of photoinitiator.
2. The wearable transparent contact lens of claim 1, wherein: the mass concentration of the modified up-conversion nano particles in the mixed solution is 0.1% -6%.
3. The wearable transparent contact lens of claim 1, wherein: the curing film forming reaction is completed by using a contact lens mold, and the curing condition is that a 365nm ultraviolet lamp irradiates for 20-60min.
4. The wearable transparent contact lens of claim 1, wherein: the subsequent treatment comprises the steps of placing the solidified membrane in ethanol/secondary distilled water mixed solution, and soaking at 40-60 ℃ for 12-24h.
5. The wearable transparent contact lens of claim 1, wherein: the photoinitiator is 1-hydroxycyclohexyl phenyl ketone or 2-hydroxy-2-methyl-1-phenyl-1-acetone.
6. The wearable transparent contact lens of claim 1, wherein the modified up-conversion nanoparticles are prepared by the steps of:
step 1, diluting concentrated HCl by using secondary distilled water to prepare dilute HCl solution with the concentration range of 0.024-0.11 mol/L;
step 2, adding the up-conversion nano particles into a dilute HCl solution, uniformly dispersing by ultrasonic, and peeling by magnetic stirring or mechanical stirring for 0.5-2h;
and step 3, centrifuging and drying the mixture obtained in the step 2 to obtain the modified up-conversion nano particles.
7. A method of producing a wearable transparent contact lens according to any one of claims 1 to 6, comprising the steps of:
step 1, uniformly mixing all raw materials of a silicon-based hydrogel precursor liquid in a light-shielding environment to obtain the silicon-based hydrogel precursor liquid;
step 2, adding the modified up-conversion nano particles into a silicon-based hydrogel precursor solution, and uniformly mixing by ultrasonic to obtain a mixed solution;
step 3, dripping the mixed solution obtained in the step 2 into a contact lens mold, solidifying under the irradiation of an ultraviolet lamp, and taking out the composite film after cooling;
and 4, soaking the composite membrane obtained in the step 3 into an ethanol/secondary distilled water mixed solution, then placing the composite membrane in an oven at 40-60 ℃ for heating and soaking 12-24h, taking out the composite membrane, and washing the composite membrane with secondary distilled water to obtain the wearable transparent contact lens.
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| TW201900786A (en) * | 2017-05-25 | 2019-01-01 | 日商日油股份有限公司 | Solution for silicone hydrogel contact lens and distribution solution including the same improving the surface hydrophilicity and surface lubricity of a silicone hydrogel contact lens |
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