Contact lens based on up-conversion device and preparation method thereof

Abstract

The invention relates to the technical field of contact lenses, in particular to a contact lens based on an up-conversion device and a preparation method of the contact lens. The contact lens includes: a contact lens substrate; an up-conversion device connected to the contact lens substrate; the up-conversion device comprises an anode, a hole barrier layer, a charge generation layer, a hole transport layer, a light-emitting layer, an electron transport layer and a cathode which are stacked in sequence. The up-conversion device in the contact lens can endow the contact lens with a night vision function.

Description

Technical Field

[0001] The present invention relates to the technical field of contact lenses, and in particular to a contact lens based on an up-conversion device and a preparation method thereof. Background Art

[0002] Ordinary frame glasses are now popular and have a wide range of applications. For example, the more common ones include vision correction, anti-dizziness, anti-glare, etc., and the more advanced ones include smart wearable glasses, infrared night vision goggles, etc., while existing contact lenses are mostly used for vision correction, beauty or medical treatment. Due to the wearing method, the current existing technology has no or few smart wearable contact lenses or special function contact lenses, such as night vision contact lenses.

[0003] Infrared is an electromagnetic wave between visible light and microwaves, with a wavelength range of 0.76-1000μm, also known as infrared thermal radiation. Among them, the wavelength of near infrared or short-wave infrared is 0.76-1.5μm, and the wavelength of far infrared or long-wave infrared is 1.5-400μm. Infrared rays cannot generally be observed by the human eye, but there is no visible light or only faint light in the dark night, which is full of infrared rays. Physics research shows that all objects with temperatures above absolute zero, that is, minus 273 degrees Celsius, emit infrared radiation in the infrared band at all times. The size of the thermal radiation energy of the object is related to the temperature of the object. The thermal radiation emitted by objects with high temperatures is stronger, and the thermal radiation emitted by objects with low temperatures is weaker. By converting the light reflected by different objects from infrared radiation into visible light, the human eye can observe the scene of the night. The smart wearable glasses and infrared night vision goggles currently on the market are not simple and bulky, and there are no smart wearable contact lenses or contact lenses with night vision functions. Summary of the invention

[0004] The invention provides a contact lens based on an up-conversion device and a preparation method thereof. The night vision function of the contact lens is realized by arranging the up-conversion device in the contact lens.

[0005] According to a first aspect of the present invention, the present invention provides a contact lens based on an up-conversion device, the contact lens comprising: Contact lens substrates; The up-conversion device is connected to the contact lens substrate; the up-conversion device comprises an anode, a hole blocking layer, a charge generating layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode stacked in sequence.

[0006] Further, the material of the charge generation layer includes an enhanced light absorption material, PC61BM, and a narrow bandgap material based on isoindigo and diketopyrrole units; Wherein, the enhanced light absorption material is any one of titanium dioxide, cadmium sulfide, cadmium selenide, cadmium telluride, copper indium gallium selenide, zinc oxide and copper oxide; Preferably, the titanium dioxide is multiphase titanium dioxide; more preferably, the particle size of the multiphase titanium dioxide is 5-50 nm.

[0007] Further, the material of the charge generation layer includes 0.5%-10% of enhanced light absorption material, 45%-50% of PC61BM and 45%-50% of isoindigo / diketopyrrolopyrrole-based narrow bandgap material; Preferably, the weight percentage of the enhanced light absorption material in the charge generation layer is 1%-7.5%, preferably 1%-5%.

[0008] Furthermore, the material of the light-emitting layer includes one of 4,4'-di(9-carbazole)biphenyl or 9,9'-(1,3-phenyl)di-9H-carbazole and a thermally activated delayed fluorescent material; the thermally activated delayed fluorescent material includes one or more of a thermally activated delayed green fluorescent material, a thermally activated delayed blue fluorescent material or a thermally activated delayed red fluorescent material.

[0009] Further, the material of the cathode is any one of Ag, Ca / Ag, Mg / Ag, Ca and graphene dopants, Yb / Ag, and Yb / Au; And / or, the material of the hole transport layer is selected from one or more of 2,2'-dimethyl-N,N'-di-1-naphthyl-N,N'-diphenyl[1,1'-biphenyl]-4,4'-diamine, N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, and 4,4',4''-tri(carbazole-9-yl)triphenylamine; And / or, the material of the electron transport layer is selected from one or more of 1,3,5-tri(1-phenyl-1H-benzimidazol-2-yl)benzene, 8-hydroxyquinoline aluminum, 2-(4-biphenyl)-5-phenyloxadiazole, 2-(4'-tert-butylphenyl)-5-(4'-biphenyl)-1,3,4-oxadiazole, and 4,4'-bis(2,2-distyryl)-1,1'-biphenyl; And / or, the material of the hole blocking layer is one or more of zinc oxide, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 4,4'-di(2,2-diphenylvinyl)-1,1'-biphenyl, and 1,3,5-tri(1-phenyl-1H-benzimidazol-2-yl)benzene; And / or, the material of the anode is selected from one of indium tin oxide, tin oxide, indium oxide, zinc oxide, and indium zinc oxide.

[0010] Further, the contact lens is a scleral contact lens or a corneal contact lens; Preferably, the contact lens is a corneal contact lens, and the corneal contact lens is a soft corneal contact lens, a hard corneal contact lens or a hybrid corneal contact lens, wherein the hard corneal contact lens includes a hard non-gas permeable corneal contact lens, a hard gas permeable corneal contact lens or a corneal reshaping lens.

[0011] Furthermore, the contact lens is a soft corneal contact lens; Preferably, the thickness of the contact lens substrate is 0.03-0.10 mm; the thickness of the up-conversion device is 0.3-1.0 μm.

[0012] Further, the contact lens substrate is selected from one of a silicone hydrogel composition and a hydrogel composition; Preferably, the silicone hydrogel composition comprises, by weight percentage, 15%-60% of a first unsaturated hydrophilic monomer, 10%-35% of a siloxane polymer, 10%-45% of a polymerizable siloxane monomer, 0.1%-5% of a first crosslinking agent, 0.1%-5% of a first functional monomer, and 0.5%-5% of a first initiator; In terms of weight percentage, the hydrogel composition includes 90%-95% of a second unsaturated hydrophilic monomer, 0.1%-5% of a second cross-linking agent, 0.1%-5% of a second functional monomer and 0.5%-5% of a second initiator.

[0013] Furthermore, the contact lens includes an optical zone located in the central area of ​​the lens, and the up-conversion device is at least arranged on the optical zone of the contact lens. The optical zone refers to a part located in the central area of ​​the contact lens that has optical properties and can thereby realize the main function of adjusting the refractive power of the lens or the refractive power of the human cornea.

[0014] Further, the contact lens substrate comprises a first substrate and a second substrate, and the up-conversion device is disposed between the first substrate and the second substrate; Preferably, the up-conversion device is packaged between the first substrate and the second substrate, and is covered by the first substrate and the second substrate.

[0015] Furthermore, the thickness of the cathode is 50-100nm; the thickness of the anode is 50-100nm; the thickness of the charge generation layer is 20-50nm; the thickness of the hole blocking layer is 20-50nm; the sum of the thicknesses of the hole transport layer, the light emitting layer and the electron transport layer is 100-150nm.

[0016] Furthermore, the up-conversion device is a flexible transparent electronic device.

[0017] According to a second aspect of the present invention, the present invention provides a method for preparing the above-mentioned contact lens, wherein the contact lens substrate comprises a first substrate and a second substrate, and the up-conversion device is disposed between the first substrate and the second substrate; the preparation method comprises the following steps: preparing a first substrate; Sequentially preparing an anode, a hole blocking layer, a charge generating layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode on the first substrate to form an up-conversion device on the first substrate; A second substrate is prepared on a side of the up-conversion device facing away from the first substrate.

[0018] Furthermore, the preparation method comprises the following steps: Step (1) Preparation of the first substrate: The first substrate mixture is prepared according to the first substrate formula so that all components are mixed evenly and without particulate impurities to obtain a first substrate mixture; the first substrate mixture is loaded into a mold for preparing contact lenses, and then irradiated with ultraviolet light for polymerization reaction, and demolded to obtain a first substrate; Step (2) Preparation of up-conversion device: An ITO film is plated on the first substrate prepared in step (1) to form an anode; zinc oxide is spin-coated on the anode by zinc acetate and PEIE in a precursor solution and baked to form a hole blocking layer; a charge generation layer is then deposited by spin-coating a chloroform solution of isoindigo / diketopyrrole-based narrow bandgap material, PC61BM and multiphase titanium dioxide dopant; a hole transport layer, a light-emitting layer and an electron transport layer are then sequentially deposited on the charge generation layer using vacuum thermal evaporation technology; finally, a Mg / Ag thin film layer is deposited on the electron transport layer to form a cathode; preferably, during the packaging process, an organic transparent film is introduced onto the surface of the up-conversion device to completely isolate the up-conversion device from moisture and organic solvents; Step (3) Contact lens preparation: An upconversion device is added to a mold, and a second substrate formula that is identical to the first substrate except for an initiator is injected into the mold, the mold injected with the second substrate formula is heated and cured, and demolded to obtain a rough lens blank; the rough lens blank is processed into a finished lens; the finished lens is extracted in ethanol, then hydrated in pure water, and then placed in a PBS solution for equilibrium and sterilization.

[0019] Beneficial effects of the present invention: The present invention discloses a contact lens comprising a contact lens substrate and an up-conversion device connected to the contact lens substrate, wherein the up-conversion device can endow the contact lens with a night vision function. The night vision function of the contact lens can be better realized by arranging the up-conversion device to include a cathode, a light-emitting layer, a charge generation layer, a hole transport layer, an electron transport layer, a hole blocking layer and an anode stacked in sequence. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0021] Figure 1 This is one of the structural schematic diagrams of the contact lens provided by an embodiment of the present invention.

[0022] Figure 2 Schematic diagram of the structure of the up-conversion device in the contact lens of the present invention and the infrared light emitting principle.

[0023] Figure 3 The second structural schematic diagram of the contact lens provided by the embodiment of the present invention.

[0024] Reference numerals: 1: contact lens substrate; 11: first substrate; 12: second substrate; 2: up-conversion device; optical zone 110; non-optical zone 120. DETAILED DESCRIPTION

[0025] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in conjunction with the drawings of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0026] In a first typical embodiment of the present invention, the present invention provides a contact lens based on an up-conversion device, and a night vision function can be achieved by an up-conversion device disposed inside the contact lens. According to some specific embodiments of the present invention, Figure 1 As shown, the contact lens comprises a contact lens substrate 1 and an up-conversion device 2, wherein the up-conversion device 2 is connected to the contact lens substrate 1; Figure 2 As shown, the up-conversion device 2 includes an anode, a hole blocking layer, a charge generating layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode stacked in sequence.

[0027] In the above scheme, the contact lens of the present invention comprises a contact lens substrate and an up-conversion device connected to the contact lens substrate, and the up-conversion device can give the contact lens a night vision function. The up-conversion device comprises an anode, a hole blocking layer (HBL), a charge generation layer (CGL), a hole transport layer (HTL), a light emitting layer (EML), an electron transport layer (ETL) and a cathode stacked in sequence. The function of the anode is to inject holes, and the function of the cathode is to inject electrons. The charge generation layer (CGL) can generate charges. When photons are incident on the charge generation layer material, if the energy of the photons is greater than the energy gap of the material, it will excite electrons to transition from the valence band to the conduction band, generating electron-hole pairs, and the holes and electrons will be transmitted to the anode and cathode interfaces respectively, so as to be collected by the anode and cathode to form a current. The function of the hole blocking layer (HBL) is to prevent the holes injected by the anode from directly passing through the device, reduce the possibility of the holes reaching the cathode, and thus improve the efficiency and stability of the device. The role of the electron transport layer (ETL) is to allow the electrons injected from the cathode to flow through the electron transport layer (ETL) to the light-emitting layer and to block the holes from the anode from flowing directly to the cathode. The role of the hole transport layer (HTL) is to allow the holes from the charge generation layer (CGL) to flow through the hole transport layer (HTL) to the light-emitting layer (EML), and to block the electrons from the charge generation layer (CGL) from being directly transferred to the anode. The role of the light-emitting layer (EML) is to stimulate the recombination of the injected electrons and holes to emit visible light. At night, any object with a temperature higher than -273°C will continuously radiate infrared rays. During the day, there is no lack of infrared radiation. The characteristic of up-conversion devices is that they do not require an external power supply to drive the conversion of photon energy. They rely on the energy of the incident photons to excite the electrons in the material to achieve energy up-conversion. Under infrared irradiation, the charge generation layer in the up-conversion device generates holes and electrons, and the excitons generated by the combination of electrons and holes are captured by the light-emitting layer (EML), and the energy of these excitons is converted into light energy, thereby achieving night vision function without the need for an additional power source. The materials of the contact lens of the present invention can be obtained by commercial, homemade or customized means, and thus can be produced.

[0028] According to some specific embodiments of the present invention, the material of the charge generation layer includes an enhanced light absorption material, PC61BM and an isoindigo / diketopyrrolopyrrole-based narrow bandgap material.

[0029] It should be noted that PC61BM refers to [6,6]-phenyl-C61-butyric acid methyl ester.

[0030] In the above scheme, the material of the charge generation layer of the present invention includes an enhanced light absorption material, PC61BM and an isoindigo / diketopyrrolopyrrole-based narrow bandgap material, the enhanced light absorption material has the effect of enhancing light absorption, PC61BM is a fullerene organic small molecule electron acceptor material, and the isoindigo / diketopyrrolopyrrole-based narrow bandgap material belongs to an organic conjugated small molecule material, has a good coplanar structure, has a strong electron-withdrawing effect, leads to a decrease in HOMO and LUMO energy levels, and achieves excellent light absorption performance. By enhancing the synergistic effect between the light absorption material, PC61BM and the isoindigo / diketopyrrolopyrrole-based narrow bandgap material, the light absorption efficiency can be more effectively improved, and the energy conversion efficiency of the up-conversion device can be improved.

[0031] According to some specific embodiments of the present invention, the enhanced light absorption material is any one of titanium dioxide, cadmium sulfide, cadmium selenide, cadmium telluride, copper indium gallium selenide, zinc oxide and copper oxide.

[0032] In the above scheme, by selecting a suitable type of enhanced light absorption material, it is more conducive to improving the light absorption effect of the charge generation layer.

[0033] Preferably, the titanium dioxide is multiphase titanium dioxide; more preferably, the particle size of the multiphase titanium dioxide is 5-50 nm.

[0034] In the above scheme, titanium dioxide is the most widely studied photocatalytic material, which is green, low-priced, chemically stable and highly catalytically active. Multiphase titanium dioxide is composed of anatase titanium dioxide, rutile titanium dioxide and brookite titanium dioxide. The three work together to promote the transfer of electrons and holes between titanium dioxides with different crystal structures, effectively improving the electron-hole separation efficiency. Therefore, the light absorption enhancement effect of multiphase titanium dioxide is better than that of ordinary titanium dioxide, cadmium sulfide and other materials. Contact lenses need to have good light transmittance, and nano-scale multiphase titanium dioxide is more suitable for charge generation layer materials. When the particle size is small and the specific surface area is large, the light absorption enhancement effect is better.

[0035] According to some specific embodiments of the present invention, the materials of the charge generation layer include, by weight percentage, 0.5%-10% of enhanced light absorption material, 45%-50% of PC61BM and 45%-50% of isoindigo / diketopyrrolopyrrole-based narrow bandgap material.

[0036] Preferably, the weight percentage of the enhanced light absorption material in the charge generation layer is 1%-7.5%, preferably 1%-5%.

[0037] In the above scheme, the amount of each material in the charge generation layer is limited to a reasonable range value, so that each material can play a better synergistic role, better improve the light absorption efficiency, and better improve the energy conversion efficiency of the up-conversion device. Further, by limiting the weight percentage of the enhanced light absorption material in the charge generation layer to a certain amount, the light absorption effect of the charge generation layer satisfies the performance of the up-conversion device, which can ensure the good light transmittance of the up-conversion device and avoid excessive cost.

[0038] According to some specific embodiments of the present invention, the material of the cathode is any one of Ag, Ca / Ag, Mg / Ag, Ca and graphene dopants, Yb / Ag, and Yb / Au.

[0039] According to some specific embodiments of the present invention, the material of the light-emitting layer includes one of 4,4'-di(9-carbazole)biphenyl or 9,9'-(1,3-phenyl)di-9H-carbazole and a thermally activated delayed fluorescent material; the thermally activated delayed fluorescent material includes one or more of a thermally activated delayed green fluorescent material, a thermally activated delayed blue fluorescent material or a thermally activated delayed red fluorescent material.

[0040] In the above scheme, the materials of the light-emitting layer include red light material, blue light material, and green light material. By combining various devices based on the three-color principle, the contact lens of the present invention can produce full-color light and has a relatively excellent night vision effect. Traditional luminescence is fluorescence and phosphorescence, which are respectively the exciton singlet state and triplet state returning to the ground state in the form of radiative luminescence. Generally, the energy level difference between the lowest singlet state and the lowest triplet state is relatively large, resulting in the exciton being unable to return to the singlet state once it reaches the triplet state from the singlet state through the intersystem crossing (RISC) process, while the energy difference between the singlet state and the triplet state of the thermally activated delayed fluorescent material is small. The small energy difference is conducive to the triplet exciton reaching the singlet state through an effective anti-intersystem crossing process to form a singlet exciton and then generate radiative transition luminescence. Due to the resistance transition from the singlet state to the ground state, the exciton utilization rate of this material can also reach 100%. The material of the light-emitting layer also includes one of 4,4'-di(9-carbazole)biphenyl or 9,9'-(1,3-phenyl)di-9H-carbazole. These two materials have low triplet energy levels and can be used in combination with thermally activated delayed fluorescent materials to improve the luminous efficiency of the light-emitting layer.

[0041] Specifically, the thermally activated delayed green fluorescent material can be any one of 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (4CzIPN), 2-(4-(9,9-dimethylacridine-10(9H)-phenyl)thianthrene 5,5,10,10-tetraoxide (ACRDSO2), and 2-(4-(10H-phenoxazine-10-phenyl)thianthrene 5,5,10,10-tetraoxide (PXZDSO2).

[0042] The thermally activated delayed blue fluorescent material may be any one of 4,5-di(9-carbazolyl)-phthalonitrile (2CzIPN), 2,3,4,6-tetra(9-carbazolyl)-5-fluorobenzonitrile (4CzFCN), and 2,4,6-tri(9-carbazolyl)-3,5-difluorobenzonitrile (3CzFCN).

[0043] The thermally activated delayed red fluorescent material can be any one of 2,3,5,6-tetrakis(3,6-diphenyl-9-carbazolyl)-terephthalonitrile (4CzTPN-ph), N,N-diphenyl-4-(9-phenylnaphtho[2,3-c][1,2,5]thiadiazol-4-yl)aniline (TPA-NZP), and 2-(4-diphenylamino-phenyl)-anthraquinone (TPA-AQ).

[0044] In order to achieve a better luminous effect, in some embodiments, in the material of the light-emitting layer (EML), the doping ratio of the thermally activated delayed fluorescent material to 4,4'-di(9-carbazole)biphenyl (CBP) is 4%-10%, and the doping ratio to 9,9'-(1,3-phenyl)di-9H-carbazole (mCBP) is 3%-8%.

[0045] In order to better realize the function of the hole transport layer, in some embodiments, the material of the hole transport layer (HTL) is selected from one or more of 2,2'-dimethyl-N,N'-di-1-naphthyl-N,N'-diphenyl [1,1'-biphenyl]-4,4'-diamine (α-NPD), N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), and 4,4',4''-tri(carbazole-9-yl)triphenylamine (TCTA).

[0046] In order to better realize the function of the electron transport layer, in some embodiments, the material of the electron transport layer (ETL) is selected from one or more of 1,3,5-tri(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), 8-hydroxyquinoline aluminum (Alq3), 2-(4-biphenyl)-5-phenyloxadiazole (PBD), 2-(4'-tert-butylphenyl)-5-(4'-biphenyl)-1,3,4-oxadiazole (Butyl-PBD), and 4,4'-di(2,2-diphenylvinyl)-1,1'-biphenyl (DPVBi).

[0047] In order to better realize the function of the hole blocking layer, in some embodiments, the material of the hole blocking layer (HBL) is one or more of zinc oxide, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,4'-di(2,2-diphenylvinyl)-1,1'-biphenyl (DPVBi), and 1,3,5-tri(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi).

[0048] According to some specific embodiments of the present invention, the material of the anode is selected from one of indium tin oxide, tin oxide, indium oxide, zinc oxide, and indium zinc oxide. The material of the anode needs to be a metal with a higher work function or a transparent conductive oxide to match the energy of the valence band of the organic material.

[0049] The contact lenses of the present invention refer to all ophthalmic lenses worn on the front surface of the eyeball, and belong to medical optical instruments. In terms of diameter, contact lenses include scleral contact lenses and corneal contact lenses. Scleral contact lenses have a larger diameter and can cover the entire black eyeball (cornea) and the surrounding part of the white of the eye (conjunctiva). Corneal contact lenses have a smaller diameter and are usually only worn on the black eyeball (cornea). According to some specific embodiments of the present invention, the contact lenses are corneal contact lenses, and the corneal contact lenses are soft corneal contact lenses (commonly known as contact lenses), hard corneal contact lenses, or hybrid corneal contact lenses, wherein the hard corneal contact lenses include hard non-gas permeable corneal contact lenses, hard gas permeable corneal contact lenses (Rigid Gas Permeable, RGP lenses) or orthokeratology lenses (Ortho-K, OK lenses).

[0050] According to some specific embodiments of the present invention, the contact lens is a soft corneal contact lens.

[0051] According to some specific embodiments of the present invention, the thickness of the contact lens substrate is 0.03-0.10 mm; the thickness of the up-conversion device is 0.3-1.0 μm.

[0052] Preferably, the thickness of the cathode is 50-100nm; the thickness of the anode is 50-100nm; the thickness of the charge generation layer is 20-50nm; the thickness of the hole blocking layer is 20-50nm; the sum of the thicknesses of the hole transport layer, the light emitting layer and the electron transport layer is 100-150nm.

[0053] In the above scheme, by limiting the thickness of the contact lens substrate, the thickness of the up-conversion device and the thickness of each layer of the up-conversion device within a reasonable range, the wearing comfort can be ensured while ensuring efficient night vision.

[0054] According to some specific embodiments of the present invention, the contact lens substrate is selected from one of a silicone hydrogel composition and a hydrogel composition; Preferably, the silicone hydrogel composition comprises, by weight percentage, 15%-60% of a first unsaturated hydrophilic monomer, 10%-35% of a siloxane polymer, 10%-45% of a polymerizable siloxane monomer, 0.1%-5% of a first crosslinking agent, 0.1%-5% of a first functional monomer, and 0.5%-5% of a first initiator; More preferably, the silicone hydrogel composition comprises, by weight percentage, 35%-60% of the first unsaturated hydrophilic monomer, 10%-35% of the siloxane polymer, 25%-35% of the polymerizable siloxane monomer, 0.2%-0.6% of the first crosslinking agent, 0.5%-2% of the first functional monomer, and 0.5%-1.5% of the first initiator; By weight percentage, the hydrogel composition includes 90%-99% of the second unsaturated hydrophilic monomer, 0.1%-5% of the second cross-linking agent, 0.1%-5% of the second functional monomer and 0.5%-5% of the second initiator.

[0055] Preferably, the hydrogel composition comprises, by weight percentage, 97%-99% of the second unsaturated hydrophilic monomer, 0.5%-1% of the second crosslinking agent, 0.5%-1% of the second functional monomer and 0.5%-1% of the second initiator.

[0056] In the above scheme, by selecting a suitable type of contact lens substrate, better synergy can be achieved with the set up-conversion device, ensuring that the contact lens has a suitable water content, excellent oxygen permeability, infrared luminescence function and light transmittance.

[0057] According to some specific embodiments of the present invention, the first unsaturated hydrophilic monomer and the second unsaturated hydrophilic monomer each independently include one or more of NVP, HEMA, DMA or MAA.

[0058] According to some specific embodiments of the present invention, the molecular formula of the siloxane polymer is the following formula (a):

[0059] Formula (a); The molecular weight of the siloxane polymer is 500-15000, m is an integer from 4 to 20, n is an integer from 1 to 200, b is an integer from 2 to 100, and R1 is selected from one of the substituents represented by the following formula (I) to (VI):

[0060] Formula (I), Formula (II),

[0061] Formula (III), Formula (IV),

[0062] Formula (V), Formula (VI); wherein R2 is selected from one of the substituents represented by the following formulae (VII) to (X),

[0063] Formula (VII),

[0064] Formula (VIII),

[0065] Formula (IX),

[0066] Formula (X).

[0067] According to some specific embodiments of the present invention, the polymerizable siloxane monomer comprises one or more of the following substances: 3-[tri(trimethylsiloxy)silyl]propyl methacrylate, 3-(trimethoxysilyl)propyl acrylate, 3-[diethoxy(methyl)silyl]propyl methacrylate, 3-(trimethoxysilyl)propyl methacrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, 3-(methoxydimethylsilyl)propyl acrylate, 3-(triethoxysilyl)propyl methacrylate, allyl tris(trimethylsiloxy)silane, allyl trimethoxysilane, 1,1,1,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy]-3-vinyltrisiloxane, allyl triethoxysilane, vinyl trimethoxysilane, Triethoxyvinylsilane, vinyltri(2-methoxyethoxy)silane, 2-(trimethylsiloxy)ethyl methacrylate, tetrakis[dimethyl(vinyl)siloxy]silane, acrylamidopropyltrimethoxysilane, (3-methacrylamidopropyl)triethoxysilane, 3-acrylamidopropyltri(trimethylsiloxy)silane, (3-methacrylamidopropyl)tri(trimethylsiloxy)silane.

[0068] According to some specific embodiments of the present invention, the first cross-linking agent and the second cross-linking agent independently include ethylene glycol dimethacrylate (EGDMA), trimethylolpropane trimethacrylate (TMPTMA), tri(ethylene glycol) dimethacrylate (TEGDMA), tri(ethylene glycol) divinyl ether (TEGDVE) and propylene glycol dimethacrylate (TMGDMA), glycerol dimethacrylate, and 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol.

[0069] According to some specific embodiments of the present invention, the first functional monomer and the second functional monomer independently include one or more of phenoxyethyl acrylate, phenoxyethyl methacrylate, phenylethyl acrylate, phenylethyl methacrylate, styrene and isobornyl acrylate.

[0070] According to some specific embodiments of the present invention, the first initiator and the second initiator each independently include one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, azobisisoheptonitrile and benzoyl peroxide.

[0071] According to some specific embodiments of the present invention, the contact lens has an optical zone, and the "optical zone" refers to the portion located in the central area of ​​the contact lens that has optical properties and can achieve the main function of adjusting the refractive power of the lens or the refractive power of the human cornea. Figure 3 As shown, the contact lens comprises an optical zone 110 and a non-optical zone 120, wherein the optical zone 110 is usually located in the central area of ​​the contact lens, and the up-conversion device 2 is arranged in the central area of ​​the contact lens and completely overlaps with the optical zone 110 of the lens; or Figure 1 As shown, the up-conversion device 2 is disposed over an area exceeding the optical zone 110 and overlaps with most areas of the lens or the entire lens area.

[0072] According to some specific embodiments of the present invention, Figure 1 , Figure 3 As shown, the contact lens substrate 1 includes a first substrate 11 and a second substrate 12, and the up-conversion device 2 is disposed between the first substrate 11 and the second substrate 12. Specifically, the up-conversion device 2 is packaged between the first substrate 11 and the second substrate 12, and is covered by the first substrate 11 and the second substrate 12.

[0073] According to some specific embodiments of the present invention, the up-conversion device 2 is a flexible transparent electronic device to better meet the wearing requirements of contact lenses.

[0074] In a second typical embodiment of the present invention, the present invention also provides a method for preparing the above-mentioned contact lens, comprising the following steps: preparing contact lens substrates; An anode, a hole blocking layer, an electron transport layer, a hole transport layer, a charge generating layer, a light emitting layer and a cathode are sequentially prepared on a contact lens substrate to form an up-conversion device on the contact lens substrate.

[0075] According to some specific embodiments of the present invention, the contact lens substrate comprises a first substrate and a second substrate, and the up-conversion device is disposed between the first substrate and the second substrate; the preparation method comprises the following steps: Step (1) Preparation of the first substrate: The first substrate mixture is prepared according to the first substrate formula so that all components are mixed evenly and free of particulate impurities; the first substrate mixture is loaded into a mold for preparing contact lenses, and then irradiated with ultraviolet light for polymerization reaction, and demolded to obtain the first substrate; Step (2) Preparation of up-conversion device: An ITO film is plated on the first substrate prepared in step (1) to form an anode; zinc oxide is spin-coated on the anode by zinc acetate and PEIE in a precursor solution and baked to form a hole blocking layer; a charge generation layer is then deposited by spin-coating a chloroform solution of isoindigo / diketopyrrole-based narrow bandgap material, PC61BM and multiphase titanium dioxide dopant; a hole transport layer, a light-emitting layer and an electron transport layer are then sequentially deposited on the charge generation layer using vacuum thermal evaporation technology; finally, a Mg / Ag thin film layer is deposited on the electron transport layer to form a cathode; preferably, during the packaging process, an organic transparent film is introduced onto the surface of the up-conversion device to completely isolate the up-conversion device from moisture and organic solvents; Step (3) Contact lens preparation: An upconversion device is added into a mold, and a second substrate formula that is identical to the first substrate except for an initiator is injected into the mold, the mold injected with the second substrate formula is heated and cured, and the rough lens is demolded to obtain the rough lens; the rough lens is processed into a finished lens; the finished lens is extracted in ethanol, then hydrated in pure water, and then placed in a PBS solution for equilibrium and sterilization.

[0076] Hereinafter, the present invention will be further illustrated by taking a preferred contact lens as a soft contact lens (commonly known as a contact lens) as an example.

[0077] All raw materials used in the following examples and comparative examples are commercially available unless otherwise specified.

[0078] The functional monomer specifically refers to a mixture of one or more of phenoxyethyl acrylate, phenoxyethyl methacrylate, phenylethyl acrylate, phenylethyl methacrylate, styrene, and isobornyl acrylate. By way of example and not limitation, the functional monomers in the following embodiments specifically include: phenoxyethyl acrylate (Examples 7 and 8), phenoxyethyl methacrylate (Examples 5 and 6), phenylethyl acrylate (Examples 1 and 2), phenylethyl methacrylate (Example 4), styrene (Example 3), isobornyl acrylate (Example 9), etc.

[0079] The polymerizable siloxane monomer a is specifically TRIS: methacryloxypropyl tris(trimethylsiloxane)silane.

[0080] The polymerizable siloxane monomer b is specifically SiGMA: (3-methacryloxy-2-hydroxypropoxy)propylmethylbis(trimethylsiloxy)silane.

[0081] The siloxane polymer is specifically PDMS, a bis-methacryloyloxy-terminated polydimethylsiloxane having a molecular weight of 2,000 to 10,000.

[0082] The crosslinking agent a is specifically EGDMA: ethylene glycol dimethacrylate.

[0083] The crosslinking agent b is specifically TEGDMA: polyethylene glycol dimethacrylate.

[0084] The crosslinking agent c is specifically TMPTMA: trimethylolpropanetrimethacrylate.

[0085] Examples 1-9

[0086] The present embodiments 1-9 each independently provide a contact lens based on an up-conversion device, such as Figure 1 As shown, the contact lens includes a contact lens substrate 1 and an up-conversion device 2, wherein the contact lens substrate 1 includes a first substrate 11 and a second substrate 12, and the up-conversion device 2 is arranged between the first substrate 11 and the second substrate 12. The up-conversion device 2 includes an anode, a hole blocking layer (HBL), a charge-generation layer (CGL), a hole transport layer (HTL), an emission material layer (EML), an electron transport layer (ETL) and a cathode stacked in sequence. The material composition of the first substrate 11 is shown in Table 1 below, the structural composition of the up-conversion device 2 is shown in Table 2 below, and the material composition of the second substrate 12 is shown in Table 3 below.

[0087] Table 1

[0088] Table 2

[0089] Table 3

[0090] The preparation method of the contact lens of embodiment 1-9 comprises the following steps: (1) Preparation of the first substrate

[0091] The siloxane polymer, polymerizable siloxane monomer, unsaturated hydrophilic monomer and initiator are prepared according to the first substrate formula (Table 1) so that all the components are evenly mixed and free of particulate impurities. The first substrate mixture is loaded into a double-sided casting mold of polypropylene for preparing contact lenses, and then irradiated with 385nm ultraviolet light for 10 minutes to carry out polymerization reaction, and demolded to obtain the first substrate.

[0092] (2) Preparation of up-conversion devices

[0093] The first substrate prepared in step (1) was ultrasonically cleaned in deionized water and isopropanol for 10 minutes and then dried to remove surface pollutants and impurities, and then subjected to UV / ozone treatment for 30 minutes. An ITO film was deposited on the first substrate by magnetron sputtering or vacuum evaporation deposition. 20 nm of zinc oxide was spin-coated on the substrate by a precursor solution of zinc acetate (1.00 g) and PEIE (80% ethoxylated aqueous solution; 0.12 g) in 2-methoxyethanol (10 mL), and then baked at 120°C for 20 minutes. Then, a chloroform solution of isoindigo / diketopyrrolopyrrole-based narrow bandgap material, PC61BM and multiphase titanium dioxide dopant (isoindigo / diketopyrrolopyrrole-based narrow bandgap material 49%, PC61BM 49%, multiphase titanium dioxide 2%, w / w) was spin-coated to deposit a charge generation layer (CGL), and the remaining organic layers were thermally evaporated on the charge generation layer under vacuum at a deposition rate of <0.5 nms -1 Finally, a Mg / Ag thin film layer is deposited. During the packaging process, an organic transparent film is introduced on the device surface to completely isolate the device from moisture and organic solvents. The detailed configuration of the up-conversion device is shown in Table 2.

[0094] (3) Contact lens preparation

[0095] The up-conversion device is added into a special mold, and a second substrate formula which is the same as the first substrate except for the initiator is injected into the mold, wherein the initiator is a thermosetting initiator, and the second substrate formula is shown in Table 3. The mold injected with the second substrate formula is placed in an oven and heated at 60°C for 1 hour for curing. After curing, the mold is demolded to obtain a rough lens blank, which is processed into a finished lens by turning. The lens is extracted twice in ethanol, 30 minutes per time, and then hydrated in pure water three times, 15 minutes per time, and then equilibrated in PBS solution for 30 minutes and then sterilized.

[0096] Comparative Example 1

[0097] This comparative example provides a contact lens, which is different from Example 6 in that the contact lens only includes a first substrate and a second substrate, and does not include an up-conversion device. The preparation method of the contact lens is the same as that of Example 6.

[0098] The above Examples 1-9 and Comparative Example 1 were subjected to the following performance tests

[0099] Test according to method 4.3 in GB / T 11417.7-2012 “Ophthalmic optics - Contact lenses Part 7: Test methods for physical and chemical properties”.

[0100] Test according to method 4.5 in GB / T 11417.7-2012 “Ophthalmic optics - Contact lenses Part 7: Test methods for physical and chemical properties”.

[0101] According to GB / T 16886.5-2003 / iso 10993-5-1999, biological evaluation of medical devices part 5: in vitro cytotoxicity test.

[0102] The near infrared (810 nm) power density is 70 mW cm −2 Evaluate contact lens performance.

[0103] E. Light transmittance

[0104] Test according to Method 5 in GB / T 11417.5-2012 “Ophthalmic optics - Contact lenses - Part 5: Test methods for optical properties”.

[0105] The test results are shown in Table 4: Table 4

[0106] It can be seen from the experimental results in Table 4 that a contact lens based on an up-conversion device can achieve night vision function by setting up an up-conversion device, and indicators such as water content, oxygen permeability, cytotoxicity and transmittance can meet the wearing requirements of contact lenses.

[0107] Examples 10-13

[0108] Examples 10-13 each independently provide a contact lens based on an up-conversion device, which is different from Example 4 in that the structural composition of the up-conversion device is different, as shown in Table 5 below. The preparation method of the contact lens is the same as that of Example 4.

[0109] Comparative Examples 2-4

[0110] This comparative example provides a contact lens based on an up-conversion device, which is different from Example 4 in that the structural composition of the up-conversion device is different, as shown in Table 5 below. The preparation method of the contact lens is the same as that of Example 4.

[0111] The contact lenses of Example 4, Examples 10-13, and Comparative Examples 2-4 were irradiated using a SourceMeter source measurement unit (SMU) instrument and a spectroradiometer (810 nm infrared light source, 70 mW cm −2 ) measured the current density-voltage-brightness characteristics, and the test results are shown in Table 6 below.

[0112] Table 5 Up-conversion device structural layer materials

[0113] Table 6 Performance of up-conversion devices

[0114] It can be seen from the experimental results in Table 6 that the present invention, by setting a material of a charge generation layer with a specific composition and applying it to an up-conversion device, can more effectively improve the light absorption efficiency and the energy conversion efficiency of the up-conversion device, thereby better realizing the night vision function of the contact lens.

[0115] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A contact lens based on an upconversion device, characterized in that: The contact lens comprises: Contact lens substrates; The up-conversion device is connected to the contact lens substrate; the up-conversion device comprises an anode, a hole blocking layer, a charge generating layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode stacked in sequence.

2. The contact lens according to claim 1, characterized in that The materials of the charge generation layer include enhanced light absorption material, PC61BM and isoindigo / diketopyrrolopyrrole-based narrow bandgap material; Wherein, the enhanced light absorption material is any one of titanium dioxide, cadmium sulfide, cadmium selenide, cadmium telluride, copper indium gallium selenide, zinc oxide and copper oxide; Preferably, the titanium dioxide is multiphase titanium dioxide; more preferably, the particle size of the multiphase titanium dioxide is 5-50 nm.

3. The contact lens according to claim 2, characterized in that The materials of the charge generation layer include, by weight percentage, 0.5%-10% of an enhanced light absorption material, 45%-50% of PC61BM, and 45%-50% of a narrow bandgap material based on isoindigo and diketopyrrole units; Preferably, the weight percentage of the enhanced light absorption material in the charge generation layer is 1%-7.5%, preferably 1%-5%.

4. The contact lens according to claim 1, characterized in that The material of the light-emitting layer includes one of 4,4'-di(9-carbazole)biphenyl or 9,9'-(1,3-phenyl)di-9H-carbazole and a thermally activated delayed fluorescent material; the thermally activated delayed fluorescent material includes one or more of a thermally activated delayed green fluorescent material, a thermally activated delayed blue fluorescent material or a thermally activated delayed red fluorescent material.

5. The contact lens according to claim 1, wherein: The material of the cathode is any one of Ag, Ca / Ag, Mg / Ag, Ca and graphene dopants, Yb / Ag, and Yb / Au; And / or, the material of the hole transport layer is selected from one or more of 2,2'-dimethyl-N,N'-di-1-naphthyl-N,N'-diphenyl[1,1'-biphenyl]-4,4'-diamine, N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, and 4,4',4''-tri(carbazole-9-yl)triphenylamine; And / or, the material of the electron transport layer is selected from one or more of 1,3,5-tri(1-phenyl-1H-benzimidazol-2-yl)benzene, 8-hydroxyquinoline aluminum, 2-(4-biphenyl)-5-phenyloxadiazole, 2-(4'-tert-butylphenyl)-5-(4'-biphenyl)-1,3,4-oxadiazole, and 4,4'-bis(2,2-distyryl)-1,1'-biphenyl; And / or, the material of the hole blocking layer is one or more of zinc oxide, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 4,4'-di(2,2-diphenylvinyl)-1,1'-biphenyl, and 1,3,5-tri(1-phenyl-1H-benzimidazol-2-yl)benzene; And / or, the material of the anode is selected from one of indium tin oxide, tin oxide, indium oxide, zinc oxide, and indium zinc oxide.

6. The contact lens according to claim 1, characterized in that The contact lens is a scleral contact lens or a corneal contact lens; Preferably, the contact lens is a corneal contact lens, and the corneal contact lens is a soft corneal contact lens, a hard corneal contact lens or a hybrid corneal contact lens, wherein the hard corneal contact lens includes a hard non-gas permeable corneal contact lens, a hard gas permeable corneal contact lens or a corneal reshaping lens.

7. The contact lens according to claim 6, characterized in that The contact lens is a soft corneal contact lens; Preferably, the thickness of the contact lens substrate is 0.03-0.10 mm; the thickness of the up-conversion device is 0.3-1.0 μm.

8. The contact lens according to claim 7, characterized in that The contact lens substrate is selected from one of a silicone hydrogel composition and a hydrogel composition; Preferably, the silicone hydrogel composition comprises, by weight percentage, 15%-60% of a first unsaturated hydrophilic monomer, 10%-35% of a siloxane polymer, 10%-45% of a polymerizable siloxane monomer, 0.1%-5% of a first crosslinking agent, 0.1%-5% of a first functional monomer, and 0.5%-5% of a first initiator; In terms of weight percentage, the hydrogel composition includes 90%-95% of a second unsaturated hydrophilic monomer, 0.1%-5% of a second cross-linking agent, 0.1%-5% of a second functional monomer and 0.5%-5% of a second initiator.

9. The contact lens according to claim 1, wherein: The contact lens comprises an optical zone located in the central region of the lens, and the up-conversion device is disposed at least on the optical zone of the contact lens.

10. The contact lens according to claim 1, wherein: The contact lens substrate comprises a first substrate and a second substrate, and the up-conversion device is disposed between the first substrate and the second substrate; Preferably, the up-conversion device is packaged between the first substrate and the second substrate, and is covered by the first substrate and the second substrate.

11. The contact lens according to any one of claims 1 to 10, characterized in that The thickness of the cathode is 50-100nm; the thickness of the anode is 50-100nm; the thickness of the charge generation layer is 20-50nm; the thickness of the hole blocking layer is 20-50nm; the sum of the thicknesses of the hole transport layer, the light emitting layer and the electron transport layer is 100-150nm.

12. The contact lens according to claim 1, wherein: The up-conversion device is a flexible transparent electronic device.

13. The method for preparing a contact lens according to any one of claims 1 to 12, characterized in that: The contact lens substrate comprises a first substrate and a second substrate, and the up-conversion device is arranged between the first substrate and the second substrate; the preparation method comprises the following steps: preparing a first substrate; Sequentially preparing an anode, a hole blocking layer, a charge generating layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode on the first substrate to form an up-conversion device on the first substrate; A second substrate is prepared on a side of the up-conversion device facing away from the first substrate.

14. The preparation method according to claim 13, characterized in that: The preparation method comprises the following steps: Step (1) Preparation of the first substrate: The first substrate mixture is prepared according to the first substrate formula so that all components are mixed evenly and without particulate impurities to obtain a first substrate mixture; the first substrate mixture is loaded into a mold for preparing contact lenses, and then irradiated with ultraviolet light for polymerization reaction, and demolded to obtain a first substrate; Step (2) Preparation of up-conversion device: Plating an ITO film on the first substrate prepared in step (1) to form an anode; spin-coating zinc oxide on the anode by zinc acetate and PEIE in a precursor solution and baking to form a hole blocking layer; Then, a chloroform solution of isoindigo / diketopyrrole-based narrow bandgap material, PC61BM and multiphase titanium dioxide dopant was spin-coated to deposit a charge generation layer; Then, a hole transport layer, a light-emitting layer and an electron transport layer are sequentially deposited on the charge generation layer using vacuum thermal evaporation technology; finally, a Mg / Ag thin film layer is deposited on the electron transport layer to form a cathode; preferably, during the packaging process, an organic transparent thin film is introduced onto the surface of the up-conversion device to completely isolate the up-conversion device from moisture and organic solvents; Step (3) Contact lens preparation: An upconversion device is added to a mold, and a second substrate formula that is identical to the first substrate except for an initiator is injected into the mold, the mold injected with the second substrate formula is heated and cured, and demolded to obtain a rough lens blank; the rough lens blank is processed into a finished lens; the finished lens is extracted in ethanol, then hydrated in pure water, and then placed in a PBS solution for equilibrium and sterilization.

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