Long-acting luminous rare earth long-afterglow material as well as preparation method and application thereof

Abstract

The invention discloses a long-acting luminous rare earth long-afterglow material and a preparation method and application thereof, the rare earth long-afterglow material is a europium and terbium doped rare earth long-afterglow material and comprises the following components in parts by mass: 30-80 parts of a substrate material, 2-45 parts of a rare earth compound, 0.5-10 parts of a surfactant and 1.5-20 parts of a surface modifier, according to the preparation method, europium and terbium rare earth ions are taken as a luminescence center, and ball milling is combined with modification treatment, so that the stability and biocompatibility of the material are improved; the long-acting luminous rare earth long-afterglow material is applied to preparation of luminous contact lenses, is good in compatibility with the lenses, excellent in luminous effect and high in biological safety, and has a great application prospect.

Description

Technical Field

[0001] The invention relates to a rare earth long afterglow material, in particular to a long-acting luminescent rare earth long afterglow material, and also to a preparation method and application of the rare earth long afterglow material. Background Art

[0002] The colors of the colored contact lenses currently on the market can only be observed in a lighted environment, and cannot be seen by the human eye in dark conditions. Normal pigments cannot emit light in dark conditions, which reduces the visual effect, while rare earth ions can exhibit unique fluorescence properties due to their special electronic structure and bonding characteristics. Rare earth long afterglow luminescent materials are an important class of light-to-photoconversion materials that can effectively absorb and store part of the energy of sunlight during the day and release energy in the form of visible light at night, thereby achieving the effect of night vision.

[0003] In order to make colored contact lenses have a luminous effect, the prior art usually uses materials with fluorescent properties to coat or transfer print on the contact lenses. These practices often bring about problems such as poor biocompatibility, extremely complicated preparation methods, and poor luminous effects. For example, the invention patent with publication number CN111154489 discloses a smart contact lens based on upconversion luminescent nanomaterials and a preparation method thereof, wherein rare earth upconversion luminescent nanomaterials are prepared and coated on the front or back of the contact lens body to obtain night vision glasses; the method converts optical fibers that reflect near-infrared radiation into visible light, focusing on the development of upconversion materials for contact lenses, and the preparation method is complicated and cumbersome and cannot be mass-produced. The invention patent with publication number CN110396190 discloses a method for preparing ultraviolet-proof colored fluorescent contact lenses, which achieves the effect of preventing ultraviolet rays by integrating fluorescent agents and ultraviolet-proof pigments into contact lenses in the form of colored transfer printing inks; the method focuses on preparing ultraviolet-proof contact lenses, and pigments are added during the preparation process, which cannot guarantee good biocompatibility. The invention patent with publication number CN106773119 discloses a contact lens and a method for preparing the same. The color-changing material used can absorb and store light when there is sufficient light, and emit light of different colors when there is insufficient light or darkness. The invention focuses on preparing contact lenses. The color-changing material used is conventional rare earth aluminosilicate; the color-changing material used in this method has a short afterglow time and a weak fluorescence effect. Therefore, materials that can achieve good luminous effects and biocompatibility and are applied to the field of contact lens manufacturing are in urgent need of development. Summary of the invention

[0004] Purpose of the invention: The purpose of the present invention is to provide a long-lasting luminescent rare earth long afterglow material with long afterglow time and good biocompatibility, and also to provide a method for preparing the above-mentioned rare earth long afterglow material and its application in contact lenses.

[0005] Technical solution: The long-lasting luminescent rare earth long afterglow material described in the present invention is a rare earth long afterglow material doped with europium and terbium, and comprises the following components by mass: 30-80 parts of base material, 2-45 parts of rare earth compound, 0.5-10 parts of surfactant, and 1.5-20 parts of surface modifier.

[0006] Wherein, the base material is strontium carbonate (SrCO 3 ), aluminum oxide (Al 2 O 3 )、MgO、BaCO 3 ), manganese carbonate (MnCO 3 ) in combination of two or more;

[0007] Wherein, the rare earth compound is yttrium nitrate hexahydrate (Y(NO 3 ) 3 6H 2 O), yttrium chloride hexahydrate (YCl 3 6H 2 O), europium nitrate hexahydrate (Eu(NO 3 ) 3 6H 2 O), terbium nitrate hexahydrate (Tb(NO 3 ) 3 6H 2 O), europium chloride hexahydrate (EuCl 3 6H 2 O), terbium chloride hexahydrate (TbCl 3 6H 2 O) or a combination of three or more thereof.

[0008] Wherein, the surfactant is one or more of sodium dodecylbenzene sulfonate, stearic acid, hexadecyltrimethylammonium bromide or potassium monododecyl phosphate;

[0009] Wherein, the surface modifier includes surface modifier I and surface modifier II, surface modifier I is one or more of polyethylene glycol, polyvinyl alcohol, aminopropyltriethoxysilane (KH550) or polymaleic anhydride, and surface modifier II is one or more of N-vinyl pyrrolidone, polyvinyl pyrrolidone, polyethylene glycol or polyacrylic acid.

[0010] The method for preparing the long-lasting luminescent rare earth long afterglow material comprises the following steps:

[0011] (1) dissolving a rare earth compound in an organic solvent, adjusting the pH value and performing a heating reaction, filtering, washing, and drying to obtain a solid 1;

[0012] (2) dispersing solid 1 into an organic solvent containing a surfactant to obtain a suspension, heating and stirring, filtering, washing with water, and drying to obtain solid 2;

[0013] (3) mixing solid 2 with a base material, grinding and calcining, and then cooling to room temperature and grinding and dispersing to obtain a powder;

[0014] (4) dispersing the powder into an organic solvent containing a surface modifier I to obtain a suspension, ultrasonicating, heating and stirring, filtering, washing with water, and drying to obtain a rare earth long afterglow material;

[0015] (5) The rare earth long afterglow material is modified by ball milling. The rare earth long afterglow material is dispersed in a surface solvent to prepare a suspension, and surface modifier II and grinding beads are added to grind for 1-3 hours at a grinding speed of 1000-3000 r / pm; the supernatant is removed and then dried, and the long-lasting luminescent rare earth long afterglow material is obtained by grinding to 400-1000 nm.

[0016] Wherein, the organic solvent is any one or more of ethanol, N,N-dimethylformamide (DMF), ethyl acetate or methanol.

[0017] Wherein, in step (1), the pH value is adjusted to 7-12, the heating reaction conditions are 50-100° C., and the time is 6-12 h.

[0018] Wherein, in step (2), the mass volume ratio of surfactant to solvent is 1-10 g:20-300 ml, the heating and stirring conditions are 50-100° C., and the time is 1-10 h.

[0019] Wherein, in step (3), the mass ratio of solid 2 to base material is 2-45:30-80, the grinding conditions are 1000-3000r / pm, the time is 1-5h, and the calcination conditions are 800-1600°C, and the time is 2-14h.

[0020] Wherein, in step (4), the mass volume ratio of the surface modifier I to the organic solvent is 1-5 g:50-250 ml, the ultrasonic time is 0.5-6 h, and the heating and stirring conditions are 50-150° C. for 0.5-8 h.

[0021] Wherein, in step (5), the concentration ratio of the rare earth long afterglow material / surface solvent and the surface modifier II is 10-100 mg / mL: 2-10%.

[0022] The above-mentioned long-lasting luminescent rare earth long afterglow material can also be used in contact lenses.

[0023] Among them, the contact lenses are luminous contact lenses, and the added amount of long-lasting luminescent rare earth long afterglow material is 0.1%-2% of the weight of the lens raw materials; the lens raw materials are three or more of hydroxyethyl methacrylate, ethylene glycol dimethacrylate, glycidyl methacrylate, 3-acrylamidopropyl tris(trimethylsiloxy)silane, divinyl polyethylene glycol ester, azobisisobutyronitrile, and azobisisoheptylonitrile.

[0024] The method for preparing the contact lens comprises mixing the rare earth long afterglow material and the contact lens raw material in proportion, dripping the mixture into a contact lens mold, curing the mixture at 50-130° C. for 1-42 hours, demoulding, hydrating, packaging and sterilizing.

[0025] Principle of the invention: The long-lasting luminescent rare earth long afterglow material of the present invention converts ultraviolet light into visible light through the down-conversion process of absorbing high-energy short-wave photons to emit low-energy long-wave photons. It can effectively absorb and store part of the energy of sunlight during the day, and release energy in the form of visible light at night, thereby achieving the effect of night vision. The material of the present invention uses europium and terbium rare earth ions as the luminescence center, and has a higher luminescence brightness than conventional rare earth materials. At the same time, ball milling combined with modification treatment can fully mix the modifier with the granular material and make it evenly dispersed. At the same time, by optimizing the ball milling process, the particle size of the material can be reduced and the particles can be homogenized, thereby improving the stability and biocompatibility of the material, and achieving better luminous intensity and luminous performance; the rare earth long afterglow material after ball milling modification treatment has a uniform particle size and is evenly fused with the modifier. It is applied to the preparation of contact lenses, and the obtained luminous contact lenses have good luminous effect and long afterglow time.

[0026] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) The long-lasting luminescent rare earth long afterglow material of the present invention has a long afterglow time, which can be up to 11 hours, and has good biocompatibility; (2) The preparation method is simple, the raw materials are cheap and easy to obtain, and it is suitable for large-scale production and supply; (3) The long-lasting luminescent rare earth long afterglow material has good compatibility with lenses, and is used in the preparation of luminous contact lenses, with excellent luminous effect and high biosafety. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The luminous effect diagram of the new rare earth long afterglow material (placed in a glass dish) prepared in Example 1 after being irradiated with 365nm ultraviolet light for 8 hours and then placed in a dark place at 0h (a), 5h (b), and 10h (c);

[0028] Figure 2 These are the luminous effect diagrams of the new rare earth long afterglow material (placed in a glass dish) prepared in Example 2 after being irradiated with natural light for 8 hours (a) and placed in the dark for 0 hours (b), 2 hours (c), 4 hours (d), and 8 hours (e);

[0029] Figure 3 This is a luminous effect diagram of the luminous lens prepared in Example 8 after being irradiated with natural light for 8 hours and then placed in a dark place for 0 hours;

[0030] Figure 4 This is a luminous effect diagram of the luminous lens prepared in Example 8 after being irradiated with natural light for 8 hours and then placed in the dark for 6 hours;

[0031] Figure 5 This is a luminous effect diagram of the luminous lens prepared in Example 9 after being irradiated with 365nm ultraviolet light for 8 hours and then placed in the dark for 0 hours;

[0032] Figure 6 This is a picture of the luminous effect of the luminous lens prepared in Example 9 after being irradiated with 365nm ultraviolet light for 8 hours and then placed in the dark for 8 hours. DETAILED DESCRIPTION

[0033] The technical scheme of the present invention is further described below in conjunction with the examples. The test materials used in the examples can all be purchased through conventional channels.

[0034] Example 1

[0035] The long-lasting luminescent rare earth long afterglow material of the present invention is prepared as follows:

[0036] (1) Weigh 1.2 g Eu(NO 3 ) 3 6H 2 O, 0.8g Tb(NO 3 ) 3 6H 2 O, 15gY(NO 3 ) 3 6H 2 O was dissolved in a water / ethanol (6:1) solution, the pH was adjusted to 7, heated at 80°C for 8 h, cooled to room temperature, filtered, washed with water, and dried to obtain solid 1-1.

[0037] (2) The obtained solid 1-1 was dispersed in 250 mL of DMF solution, 8 g of hexadecyltrimethylammonium bromide was added, and the mixture was heated and stirred at 100° C. for 1 h. The mixture was cooled to room temperature, filtered, washed with water, and dried to obtain solid 1-2.

[0038] (3) The obtained solid 1-2, 10g SrCO 3 , 10g Al 2 O 3 10 g of MgO was ground evenly with a grinder (3000 r / pm, 1 h), then poured into a crucible, calcined at 1600 °C for 2 h, cooled to room temperature, and the obtained product 1-3 was ground evenly again with a grinder.

[0039] (4) Product 1-3 was dispersed in a DMF solution (250 mL) containing 5 g of aminopropyltriethoxysilane (KH550), ultrasonicated for 6 h, heated and stirred at 150 °C for 1 h, filtered, washed with water and stored at room temperature to obtain a rare earth long afterglow material.

[0040] (5) The prepared rare earth long afterglow material was added to cyclopentanone to prepare a 10 mg / mL suspension, 3% polyvinyl pyrrolidone was added, and the mixture was ground at a speed of 1000 r / pm for 3 h. After drying, the mixture was ground and dispersed to a particle size of 800 nm to obtain a modified rare earth long afterglow material.

[0041] Example 2

[0042] The long-lasting luminescent rare earth long afterglow material of the present invention is prepared as follows:

[0043] (1) Weigh 1.0 g EuCl 3 6H 2 O, 2.4 g TbCl 3 6H 2 O, 30g YCl 3 6H 2 O was dissolved in a water / methanol (6:1) solution, the pH was adjusted to 8, the reaction was carried out at 90°C for 7 h, the mixture was cooled to room temperature, filtered, washed with water, and dried to obtain a solid 2-1.

[0044] (2) The obtained solid 2-1 was dispersed in 130 mL of anhydrous ethanol solution, 4 g of stearic acid / sodium dodecylbenzene sulfonate (mass ratio 1:3) was added, heated and stirred at 60° C. for 8 h, cooled to room temperature, filtered, washed with water, and dried to obtain solid 2-2.

[0045] (3) The obtained solid 2-2, 20g Al 2 O 3 、10g BaCO 3 、15g MnCO 3 Grind it evenly with a grinder (2000r / pm, 3h), then pour it into a crucible, calcine it at a constant temperature of 1400℃ for 4h in a tube furnace, cool it to room temperature, and grind the obtained product 2-3 evenly again with a grinder.

[0046] (4) The product 2-3 was dispersed in a DMF solution (100 mL) containing 2.5 g of polyvinyl alcohol, ultrasonicated for 0.5 h, heated and stirred at 110° C. for 3 h, filtered, washed with water, and dried to obtain a rare earth long afterglow material which was stored at room temperature.

[0047] (5) The prepared rare earth long afterglow material was added to cyclopentanone / ethyl lactate (mass ratio 3:1) to prepare a 20 mg / mL suspension, and 5% N-vinyl pyrrolidone and polyacrylic acid (mass ratio 1:2, rotation speed 2000 r / pm) were added and ground for 2.5 h. After drying, the mixture was ground and dispersed to a particle size of 500 nm to obtain a modified rare earth long afterglow material.

[0048] Example 3

[0049] The long-lasting luminescent rare earth long afterglow material of the present invention is prepared as follows:

[0050] (1) Weigh 2.0 g Eu(NO 3 ) 3 6H 2 O, 8.0g Tb(NO 3 ) 3 6H 2 O, 20g YCl 3 6H 2 O was dissolved in a water / ethyl acetate (6:1) solution, the pH was adjusted to 10, the reaction was carried out at 100°C for 6 hours, and when cooled to room temperature, it was filtered, washed with water, and dried to obtain a solid 3-1.

[0051] (2) The obtained solid 3-1 was dispersed in 200 mL of methanol solution, 35 g of hexadecyltrimethylammonium bromide and stearic acid (mass ratio 3:2) were added, heated and stirred at 50° C. for 10 h, cooled to room temperature, filtered, washed with water, and dried to obtain solid 3-2.

[0052] (3) The solid 2-2 obtained from 3-2, 20 g SrCO 3 , 52g Al 2 O 3 Grind it evenly with a grinder (1500r / pm, 4h), then pour it into a crucible, calcine it at a constant temperature of 800℃ in a tube furnace for 14h, cool it to room temperature, and the obtained product 3-3 is ground evenly again with a grinder.

[0053] (4) The product 3-3 was dispersed in a methanol solution (250 mL) containing 5 g of polyethylene glycol, ultrasonicated for 1.5 h, heated and stirred at 80 °C for 6 h, filtered, washed with water, and dried to obtain a rare earth long afterglow material which was stored at room temperature.

[0054] (5) The prepared rare earth long afterglow material is added to ethyl lactate / isooctanol to prepare a 50 mg / mL suspension, and 8% polyvinyl pyrrolidone, polyethylene glycol (mass ratio 2:3) and grinding beads are added. The mixture is ground at a speed of 1000 r / pm for 1.5 h. After drying, the mixture is ground and dispersed to a particle size of 900 nm to obtain a modified rare earth long afterglow material.

[0055] Example 4

[0056] The long-lasting luminescent rare earth long afterglow material of the present invention is prepared as follows:

[0057] (1) Weigh 5 g Eu(NO 3 ) 3 6H 2 O, 8g Tb(NO 3 ) 3 6H 2 O, 18g YCl 3 6H 2 O was dissolved in a water / methanol (6:1) solution, the pH was adjusted to 12, the reaction was carried out at 70°C for 9 hours, and when cooled to room temperature, it was filtered, washed with water, and dried to obtain a solid 4-1.

[0058] (2) The obtained solid 4-1 was dispersed in 300 mL of ethyl acetate solution, 10 g of potassium monododecyl phosphate was added, and the mixture was heated and stirred at 70° C. for 6 h. After cooling to room temperature, the mixture was filtered, washed with water, and dried to obtain solid 4-2.

[0059] (3) The obtained solid 4-2, 20 g BaCO 3 , 25g Al 2 O 3 After being evenly ground with a grinder (1000r / pm, 5h), it was poured into a crucible and calcined at a constant temperature of 1200°C for 6h in a tubular furnace. After being cooled to room temperature, the obtained product 4-3 was ground evenly again with a grinder.

[0060] (4) The product 4-3 was dispersed in an ethanol solution (200 mL) containing 4 g of polyvinyl alcohol and polymaleic anhydride (mass ratio 2:1), ultrasonicated for 3 h, heated and stirred at 90 °C for 5 h, filtered, washed with water, and dried to obtain a rare earth long afterglow material which was stored at room temperature.

[0061] (5) The prepared rare earth long afterglow material is added to isooctyl alcohol to prepare a 40 mg / mL suspension, 5% polyvinyl pyrrolidone and N-vinyl pyrrolidone (mass ratio 2:3) are added, and the mixture is ground at a speed of 3000 r / pm for 3 h. After drying, the mixture is ground and dispersed to a particle size of 400 nm to obtain a modified rare earth long afterglow material.

[0062] Example 5

[0063] The long-lasting luminescent rare earth long afterglow material of the present invention is prepared as follows:

[0064] (1) Weigh 6g EuCl 3 6H 2 O、8gTb(NO 3 ) 3 6H 2 O, 25g Y(NO3 ) 3 6H 2 O was dissolved in a water / ethanol (8:1) solution, the pH was adjusted to 7, heated and stirred at 80°C for 8 h, and when cooled to room temperature, filtered, washed with water, and dried to obtain a solid 5-1.

[0065] (2) The obtained solid 5-1 was dispersed in 180 mL of ethanol solution, 6 g of hexadecyltrimethylammonium bromide / potassium monododecyl phosphate (mass ratio 3:1) was added, and the mixture was reacted at 80° C. for 3.5 h. After cooling to room temperature, the mixture was filtered, washed with water, and dried to obtain solid 5-2.

[0066] (3) The obtained solid 5-2, 26g SrCO 3 24 g MgO was ground evenly with a grinder (1500 r / pm, 3.5 h) and poured into a crucible. It was calcined at 1300 °C in a tube furnace for 6 h and cooled to room temperature. The obtained product 5-3 was ground evenly again with a grinder.

[0067] (4) The product 5-3 was dispersed in a methanol solution (150 mL) containing 3 g of polyacrylic acid and polyethylene glycol (mass ratio 3:2), ultrasonicated for 3 h, heated and stirred at 110 °C for 4 h, filtered, washed with water, and dried to obtain a rare earth long afterglow material which was stored at room temperature.

[0068] (5) The prepared rare earth long afterglow material is added to cyclopentanone / isooctanol to prepare a 30 mg / mL suspension, 4% polyvinyl pyrrolidone and polyacrylic acid (mass ratio 3:1) are added, and the mixture is ground at a speed of 3000 r / pm for 1 h. After drying, the mixture is ground and dispersed to a particle size of 600 nm to obtain a modified rare earth long afterglow material.

[0069] Example 6

[0070] The long-lasting luminescent rare earth long afterglow material of the present invention is prepared as follows:

[0071] (1) Weigh 1.6 g Eu(NO 3 ) 3 6H 2 O, 1.8 g TbCl 3 6H 2 O, 12g Y(NO 3 ) 3 6H 2 O was dissolved in a water / ethanol (10:1) solution, the pH was adjusted to 9, the reaction was carried out at 50°C for 12 h, and when cooled to room temperature, the solid 6-1 was obtained by filtration and washing with water, and then drying.

[0072] (2) The obtained solid 6-1 was dispersed in 200 mL of methanol solution, 6 g of stearic acid / potassium monododecyl phosphate (mass ratio 3:1) was added, and the mixture was heated and stirred at 60° C. for 8 h. After cooling to room temperature, the mixture was filtered, washed with water, and dried to obtain solid 6-2.

[0073] (3) The obtained solid 6-2, 30 g SrCO 3 After being evenly ground with a grinder (2500r / pm, 1.5h), it was poured into a crucible and calcined at a constant temperature of 1600°C for 3h in a tube furnace. After being cooled to room temperature, the obtained product 6-3 was ground again with a grinder to be evenly ground.

[0074] (4) The product 6-3 was dispersed in an ethyl acetate solution (200 mL) containing 5 g of polyvinyl alcohol and polymaleic anhydride (mass ratio 1:2), ultrasonicated for 3 h, heated and stirred at 100 °C for 5 h, filtered, washed with water, and dried to obtain a rare earth long afterglow material which was stored at room temperature.

[0075] (5) The prepared rare earth long afterglow material is added to ethyl lactate / isooctanol to prepare a suspension of 85 mg / mL, 10% polyvinyl pyrrolidone and polyacrylic acid (mass ratio 1:3) are added, and the mixture is ground at a speed of 2000 r / pm for 2 h. After drying, the mixture is ground and dispersed to a particle size of 500 nm to obtain a modified rare earth long afterglow material.

[0076] Example 7

[0077] The rare earth long afterglow material prepared in Example 1 is used to prepare luminous contact lenses:

[0078] Take 10g of hydroxyethyl methacrylate, 0.2g of ethylene glycol dimethacrylate, and 0.1g of azobisisobutyronitrile, mix and shake until completely dissolved, add 0.01g of the rare earth long afterglow material prepared in Example 1 and stir evenly. Take 40μL of the prepared raw materials into a mold, place it in an oven at 100℃ for 4h, and then remove the mold. Take out the dry piece, soak it in pure water and physiological saline for 2h, and then get a luminous contact lens.

[0079] Example 8

[0080] The rare earth long afterglow material prepared in Example 2 is used to prepare luminous contact lenses:

[0081] Take 8g of hydroxyethyl methacrylate, 2g of glycidyl methacrylate, 0.2g of ethylene glycol dimethacrylate, and 0.1g of azobisisobutyronitrile, mix and shake until completely dissolved, add 0.2g of the rare earth long afterglow material prepared in Example 2 and stir evenly. Take 40μL of the prepared raw materials into a mold, place it in an oven at 130℃ for curing for 1h, and then remove the mold. Take out the dry sheet, soak it in pure water and physiological saline for 3h successively, and obtain a luminous contact lens.

[0082] Example 9

[0083] The rare earth long afterglow material prepared in Example 5 is used to prepare luminous contact lenses:

[0084] Take 4g of hydroxyethyl methacrylate, 2g of glycidyl methacrylate, 4g of 3-acrylamidopropyl tris(trimethylsiloxy)silane, 0.3g of divinyl polyethylene glycol ester, and 0.1g of azobisisoheptanenitrile, mix and shake until completely dissolved, add 0.08g of the rare earth long afterglow material prepared in Example 5 and stir evenly. Take 40μL of the prepared raw materials into the mold, place it in an oven at 50℃ for curing for 42h, and then remove the mold. Take out the dry sheet, soak it in pure water and physiological saline for 4h successively to obtain a luminous contact lens.

[0085] Comparative Example 1

[0086] A rare earth long afterglow material, the preparation method is:

[0087] (1) Weigh 1.2 g Eu(NO 3 ) 3 6H 2 O, 0.8g Tb(NO 3 ) 3 6H 2 O, 15gY(NO 3 ) 3 6H 2 O was dissolved in a water / ethanol (6:1) solution, the pH was adjusted to 10, heated at 80°C for 8 h, cooled to room temperature, filtered, washed with water, and dried to obtain solid 1-1.

[0088] (2) The obtained solid 1-1 was dispersed in 250 mL of DMF solution, 8 g of hexadecyltrimethylammonium bromide was added, the mixture was reacted at 100° C. for 1 h, cooled to room temperature, filtered, washed with water, and dried to obtain solid 1-2.

[0089] (3) The obtained solid 1-2, 10g SrCO 3 , 10g Al 2 O 3 10 g of MgO was ground evenly with a grinder (3000 r / pm, 1 h), then poured into a crucible, calcined at 1600 °C for 2 h, cooled to room temperature, and the obtained product 1-3 was ground evenly again with a grinder.

[0090] (4) The product 1-3 was dispersed in a DMF solution (250 mL) containing 5 g of aminopropyltriethoxysilane (KH550), ultrasonicated for 6 h, reacted at 150 °C for 1 h, filtered, washed with water and stored at room temperature to obtain a rare earth long afterglow material.

[0091] Experimental results: The rare earth long afterglow material prepared in the comparative example was not ground and modified. During the process of preparing luminous contact lenses, the prepared lens raw material had the problem of particle precipitation, and could not be used for the preparation of lenses.

[0092] The night vision effect of the rare earth long afterglow material prepared in the embodiment was tested:

[0093] The rare earth long afterglow materials prepared in Examples 1 to 6 were respectively irradiated with 365nm ultraviolet light and natural light for 8 hours, and the continuous afterglow phenomenon of the rare earth long afterglow materials in the dark was observed, and the continuous luminescence time of the materials was recorded. The test results are shown in Table 1. As can be seen from Table 1, the continuous luminescence time of Examples 1 to 6 is longer than 6 hours, and the longest luminescence time can reach 11 hours.

[0094] Table 1. Continuous luminescence time of Examples 1-9

[0095]

[0096] The rare earth long afterglow material of Example 1-2 (placed in a glass dish) was irradiated with 365nm ultraviolet light and natural light respectively. After 8 hours of irradiation, the continuous luminescence time was measured in the dark. The test results are as follows: Figure 1-2 shown.

[0097] Figure 1 The figure shows the luminescence of the rare earth long afterglow material in Example 1 at 0h (a), 5h (b), and 10h (c) after being irradiated with 365nm ultraviolet light for 8h and then placed in darkness. It can be seen from the figure that the rare earth long afterglow material emits green light with obvious fluorescence effect, and the fluorescence gradually weakens after 10h.

[0098] Figure 2 The following are comparisons of the rare earth long afterglow material of Example 2 after being exposed to natural light for 8 hours (a), and after being exposed to darkness for 0 hours (b), 2 hours (c), 4 hours (d), and 8 hours (e). It can be seen from the figure that after exposure to sunlight, obvious green fluorescence can be observed in the dark, and as time goes by, the fluorescence gradually weakens and almost disappears after 8 hours.

[0099] The particle size test was conducted on the rare earth long afterglow material prepared in the embodiment:

[0100] The rare earth long afterglow materials of Examples 1 to 6 were dispersed in a DMF solution, and then the particle size was tested using a dynamic light scattering instrument. The particle size test results are shown in Table 2.

[0101] Table 2. Particle size test results of Examples 1-6

[0102] Example Sample Particle size (nm) Example 1 764 Example 2 532 Example 3 798 Example 4 436 Example 5 582 Example 6 472

[0103] As shown in Table 2, the particle size of the prepared rare earth long afterglow material is between 400 and 800 nm, and the particle size is uniform, which is suitable for the subsequent preparation of contact lenses.

[0104] Cytotoxicity tests were performed on the rare earth long afterglow materials and luminous contact lenses prepared in the examples:

[0105] According to the method of GB / T 16886.5-2017, the cytotoxicity test of the rare earth long afterglow material was performed by the MTT method. The rare earth long afterglow materials of Examples 1-6 were dispersed in the cell culture medium solution to obtain a suspension of 100 μg / mL. At 37°C, L929 cells were incubated with the suspension of the rare earth long afterglow material for 24 hours, and the cell survival results are shown in Table 3. The luminous lenses of Examples 7-9 were placed in the cell culture medium solution, extracted at 37°C for 24 hours, and then the extract was taken and incubated with L929 cells at 37°C for 24 hours, and the cell survival results are shown in Table 3.

[0106] Table 3. Cytotoxicity test results of Examples 1-9

[0107]

[0108]

[0109] According to the result judgment standard in GB / T 16886.5-2017, the cell survival rate is greater than 70%, which means that the sample has no cytotoxicity. As shown in Table 3, the cell survival rates of the prepared rare earth long afterglow material suspension and luminous contact lens extract are all above 80%, indicating that the rare earth long afterglow material and luminous contact lens prepared in Examples 1-9 have excellent biocompatibility.

[0110] The night vision effect of the contact lenses prepared in the embodiment was tested:

[0111] The lenses of Examples 7-9 were irradiated with 365nm ultraviolet light for 2 hours, and then the continuous luminescence time was measured in the dark. Figure 3-6 shown.

[0112] Figure 3 and Figure 4 The results are shown for Example 8 after 8 hours of exposure to sunlight and 0 hours in the dark ( Figure 3 ) and 6h( Figure 4 ) lens luminescence. As can be seen from the figure, the lens emits green light and the fluorescence effect is obvious; as time goes by, the fluorescence weakens slightly, and the fluorescence lasts for more than 6 hours.

[0113] Figure 5 and Figure 6 The results are shown in Example 9 after irradiation with 365nm ultraviolet light for 8h, and in the dark for 0h ( Figure 5 ) and 8h( Figure 6 ) lens luminescence. As can be seen from the figure, the lens emits green light and the fluorescence effect is obvious; as time goes by, the fluorescence weakens slightly, and the fluorescence lasts for more than 8 hours.

Claims

1. A long-lasting luminescent rare earth long afterglow material, characterized in that: The rare earth long afterglow material is a rare earth long afterglow material doped with europium and terbium, and comprises the following components by mass: 30-80 parts of base material, 2-45 parts of rare earth compound, 0.5-10 parts of surfactant, and 1.5-20 parts of surface modifier.

2. The long-lasting luminescent rare earth long afterglow material according to claim 1, characterized in that: The base material is a combination of two or more of strontium carbonate, aluminum oxide, magnesium oxide, barium carbonate, and manganese carbonate; the rare earth compound is a combination of three or more of yttrium nitrate hexahydrate, yttrium chloride hexahydrate, europium nitrate hexahydrate, terbium nitrate hexahydrate, europium chloride hexahydrate, or terbium chloride hexahydrate.

3. The long-lasting luminescent rare earth long afterglow material according to claim 1, characterized in that: The surfactant is one or more of sodium dodecylbenzene sulfonate, stearic acid, hexadecyltrimethylammonium bromide or potassium monododecyl phosphate; the surface modifier includes surface modifier I and surface modifier II, surface modifier I is one or more of polyethylene glycol, polyvinyl alcohol, aminopropyltriethoxysilane or polymaleic anhydride, and surface modifier II is one or more of N-vinyl pyrrolidone, polyvinyl pyrrolidone, polyethylene glycol or polyacrylic acid.

4. A method for preparing the long-lasting luminescent rare earth long afterglow material according to claim 1, characterized in that: The following steps are included: (1) dissolving a rare earth compound in an organic solvent, adjusting the pH value and performing a heating reaction, filtering, washing, and drying to obtain a solid 1; (2) dispersing solid 1 into an organic solvent containing a surfactant to obtain a suspension, heating and stirring, filtering, washing with water, and drying to obtain solid 2; (3) mixing solid 2 with a base material, grinding and calcining, and then cooling to room temperature and grinding and dispersing to obtain a powder; (4) dispersing the powder into an organic solvent containing a surface modifier I to obtain a suspension, ultrasonicating, heating and stirring, filtering, washing with water, and drying to obtain a rare earth long afterglow material; (5) The rare earth long afterglow material is modified by ball milling. The rare earth long afterglow material is dispersed in a surface solvent to prepare a suspension, and surface modifier II and grinding beads are added to grind for 1-3 hours at a grinding speed of 1000-3000 r / pm; the supernatant is removed and then dried, and the long-lasting luminescent rare earth long afterglow material is obtained by grinding to 400-1000 nm.

5. The method according to claim 4, characterized in that: In step (1), the pH value is adjusted to 7-12, the heating reaction conditions are 50-100° C., and the time is 6-12 h; in step (2), the mass volume ratio of the surfactant to the solvent is 1-10 g: 20-300 ml, the heating and stirring conditions are 50-100° C., and the time is 1-10 h.

6. The method according to claim 4, characterized in that: In step (3), the mass ratio of solid 2 to substrate material is 2-45:30-80, the grinding conditions are 1000-3000r / pm, the time is 1-5h, the calcination conditions are 800-1600°C, and the time is 2-14h; in step (4), the mass volume ratio of surface modifier I to organic solvent is 1-5g:50-250ml, the ultrasonic time is 0.5-6h, and the heating and stirring conditions are 50-150°C and the time is 0.5-8h.

7. The method according to claim 4, characterized in that: In step (5), the ratio of the concentration of the rare earth long afterglow material / surface solvent and the surface modifier II is 10-100 mg / mL: 2-10%.

8. Use of the long-lasting luminescent rare earth long afterglow material according to claim 1 in contact lenses.

9. The use according to claim 8, characterized in that: The contact lenses are luminous contact lenses, and the added amount of the long-lasting luminous rare earth long afterglow material is 0.1%-2% of the weight of the lens raw material.

10. The use according to claim 8, characterized in that: The method for preparing the contact lens comprises the following steps: mixing the rare earth long afterglow material and the contact lens raw material in proportion, dripping the mixture into a contact lens mold, curing the mixture at 50-130° C. for 1-42 hours, demoulding, hydrating, packaging, and sterilizing.

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