CN114031706A

CN114031706A - Blue color weakness correcting lens and preparation method thereof

Info

Publication number: CN114031706A
Application number: CN202111245487.6A
Authority: CN
Inventors: 王明华; 张鹤军; 纪立军; 范为正; 司云凤; 刘洋; 郑永华; 薛晓花; 吴潇
Original assignee: Jiangsu Shike New Material Co ltd
Current assignee: Jiangsu Shike New Material Co ltd
Priority date: 2021-10-25
Filing date: 2021-10-25
Publication date: 2022-02-11
Anticipated expiration: 2041-10-25
Also published as: CN114031706B

Abstract

A blue color weakness correcting lens and a preparation method thereof, wherein the lens contains an acrylic ester/spiropyran/nano copper oxide three-layer composite core-shell structure optometry material, the inner core of the lens is a copper oxide nano microsphere, a spiropyran compound shown in a formula I is coated outside the microsphere, and the shell of the lens is acrylic ester; the mass ratio of the copper oxide nano-microspheres to the spiropyran compounds to the acrylic ester is 1: 1.1-1.3: 0.9-1; the mass ratio of the core-shell structure vision material to the lens resin base material is 1: 30-200. The visual light materialThe material has the functions of filtering and complementing color in the lens. The color of the lens is darker under indoor normal light, the blue band spectrum color purity and the dimension of a color vision vector space can be enhanced, the color distinguishing capability of a blue-poor patient is improved, abnormal color vision is corrected, the lens can be rapidly faded outdoors to be light color or colorless, and the reality of the vision of the patient is ensured. Has the advantages of high color saturation, good color discrimination effect, comfortable wearing and the like.

Description

Blue color weakness correcting lens and preparation method thereof

Technical Field

The invention belongs to the technical field of ocular optics, and particularly relates to a color vision correction visual light material and a preparation method thereof.

Background

Color vision is one of the important visual functions of the eye, seven colors of the visible spectrum in sunlight can be assigned to the three primary colors, red, green and blue, and retinal cone cells contain red-sensitive pigments, green-sensitive pigments and blue-sensitive pigments. The human eye recognizes approximately 100 different colors. Congenital color vision disorder is caused by abnormal deficiency of color-sensing pigment in cone cells. And can be generally classified into achromatopsia, achromatopsia and achromatopsia. A single vision with only one color-sensing pigment, namely, full-color blindness; the person with two color-sensitive pigments is dichromatic, so that the person without red or green pigment is red-green blind; if the color-sensitive pigment in the cone cell is normal and the color-sensitive pigment is less, the cone cell is three-color vision, i.e. red and green are weak. According to human color vision physiology, physics and the like, the color vision characteristic of a normal person is a three-dimensional vector space, and three basis vectors respectively correspond to three primary colors of red, green and blue. Each color may be represented as a point or a vector in this vector space. A color-blind patient cannot distinguish between the two colors if the vector space is of fewer dimensions than normal and the difference in brightness is not significant (i.e., color-blind examination is based on this principle).

The traditional color blindness correcting glasses can not increase the dimension of the vector space, but change the difference of the two colors in brightness, and color blindness patients can distinguish the two colors by the difference in brightness after wearing the traditional color blindness correcting glasses. However, if the glasses are worn for a long time, visual distortion is caused, and the visual health is not good; in addition, the prior art has the disadvantages of poor appearance and obvious abnormal colors of the spectacle lens, such as: the patient is worried about the red, dark and blue, so that the appearance is influenced; some achromatopsia lenses can greatly attenuate the transmission amount of normal light while correcting abnormal color vision, so that the achromatopsia lenses cannot be used under low light, the normal part of vision is interfered, and the vision is degraded after long-term wearing.

The traditional color blindness correcting glasses can not increase the dimension of the vector space, but change the difference of the two colors in brightness, and color blindness patients can distinguish the two colors by the difference in brightness after wearing the traditional color blindness correcting glasses. However, some glasses can distinguish colors according to the difference of brightness without the traditional color blindness correction glasses, and the glasses with the color blindness correction glasses cannot distinguish the colors. Moreover, the overall vision of a person wearing conventional corrective spectacles for achromatopsia is somewhat degraded and the appearance of a bright red and a bright blue is unacceptable.

Disclosure of Invention

The invention aims to provide a blue-tone correcting lens and a preparation method thereof, wherein the lens contains an organic/inorganic nano composite microsphere optometry material which is an acrylate/spiropyran/copper oxide nano microsphere three-layer composite core-shell structure, the inner core of the optometry material is copper oxide nano particles, the shell of the optometry material is coated with acrylate, and a spiropyran allochroic compound is arranged in the middle layer between the inner core and the shell to form a composite multilayer core-shell structure. The visual light material plays a role in filtering and complementing colors in the lens. The lens has darker color under indoor normal light, can automatically enhance the spectral color purity of blue wave band and the dimension of color vision vector space, improve the color discrimination capability of patients with blue weakness, correct abnormal color vision, and is suitable for patients with blue weakness, red, blue and green weakness; and after the fabric returns to the outdoor environment (under the irradiation of ultraviolet rays), the fabric can be quickly faded to be light color or colorless, so that the reality of the visual objects of a patient is ensured, the visual health is maintained, and the fabric has the advantages of high color saturation, good color complementing effect, wearing comfort and the like.

In order to achieve the purpose, the invention provides the following technical scheme:

a blue color weakness correcting lens contains an acrylic ester/spiropyran/nano copper oxide three-layer composite core-shell structure optometry material, wherein an inner core of the lens is a copper oxide nano microsphere, a spiropyran compound shown in a formula I is coated outside the microsphere, and an outer shell of the lens is acrylic ester; wherein the mass ratio of the copper oxide nano-microspheres to the spiropyran compounds to the acrylic ester is 1: 1.1-1.3: 0.9-1; the mass ratio of the core-shell structure vision material to the lens resin base material is 1: 30-200;

in the above-described lens for correcting blue tinge, it is preferable that the acrylate is polymerized from an acrylate monomer selected from at least one of methyl acrylate, ethyl acrylate, 2-methyl methacrylate and 2-ethyl methacrylate.

In the above blue amblyopia correcting lens, the mass ratio of the copper oxide nanoparticles, the spiropyran compound and the acrylic ester is preferably 30: 45: 28.

In the above blue-shading correction lens, the mass ratio of the core-shell structure visual light material to the lens resin base material is preferably 1: 55-65.

In another aspect, the present invention provides a method for preparing a blue-shading correction lens, the method comprising the steps of:

I. preparation of acrylic ester/spiropyran/nano copper oxide three-layer core-shell structure optomaterial

i. Weighing an acrylate monomer, a spiropyran compound shown in formula (I) and copper oxide nanoparticles, wherein the mass ratio of the spiropyran compound to the copper oxide nanoparticles is (0.9-1): (1.1-1.3): 1, and dissolving the spiropyran compound in an organic solvent;

adding purified water and an emulsifier into the reaction kettle, and after the pure water and the emulsifier are completely dissolved, adding copper oxide nanoparticles, wherein the concentration of the copper oxide nanoparticles in water is 1.5-5.0 wt%; dropwise adding a saturated aqueous solution of sodium acetate into the system, wherein the mass ratio of the sodium acetate to the copper oxide nanoparticles is 1: 0.5-1.0; the copper oxide nano particles are agglomerated into nano-scale clusters with uniform particles;

adding a cross-linking agent into the reaction system, introducing nitrogen, adding a spiropyran compound solution shown in the formula I, and adsorbing spiropyran particles on the surface of an oxide cluster;

iv, adding an acrylate monomer into the reaction system, stirring to obtain an O/W type emulsion, stirring and heating to 65-70 ℃, adding an initiator, carrying out thermal polymerization for 15-17h, and generating an acrylate shell outside the particles formed in the step iii; filtering, washing and drying to obtain the acrylic ester/spiropyran/nano copper oxide three-layer core-shell structure optomaterial;

II, preparing a blue color shading correction resin lens

Adding the three-layer core-shell structure optomaterial prepared in the step I and an initiator into an acrylate monomer and a solvent, and uniformly stirring, wherein the mass ratio of the three-layer core-shell structure optomaterial to the acrylate monomer is 1: 30-200; carrying out polymerization reaction for 2.5-3.5 hours at 75-85 ℃, filtering, degassing, injecting into a mold, and heating from room temperature to 85 ℃ within 18-22 hours to complete primary curing; and then, carrying out secondary curing at the constant temperature of 90-110 ℃ for 2-3 hours to obtain the blue color weakness correction resin lens.

In the above-described production method, preferably, the acrylate monomers in the steps I and II are the same and are at least one selected from the group consisting of methyl acrylate, ethyl acrylate, 2-methyl methacrylate and 2-ethyl methacrylate.

In the above preparation method, the particle size of the copper oxide nanoparticles is preferably 2 to 12 nm.

In the above preparation method, preferably, the solvent of the solution of the spiropyran compound is at least one of chloroform, acetone, propyl acetate, butyl acetate, ethyl acetate, dibutyl phthalate, and petroleum ether; the mass ratio of the spiropyran compound to the solvent is 1: 2-3.

In the preparation method as described above, preferably, the crosslinking agent in the step I is vinyl butyl methacrylate or diallyl phthalate, and the amount of the crosslinking agent is 0.5-2% of the mass of the acrylate monomer;

the emulsifier in the step I is at least one of RF-345, polyvinylpyrrolidone or sodium dodecyl benzene sulfonate, and the using amount is 2-6 g/L.

In the above-mentioned production method, preferably, the initiators in the step I and the step II are the same or different and each selected from at least one of dibenzoyl peroxide, diisopropyl peroxydicarbonate, ammonium persulfate and sodium persulfate, and the amount is 0.2 to 0.4% of the amount of the acrylate monomer.

The spiropyran compound (I) of the present invention can be synthesized by, but not limited to, the following method.

Synthesis of a spiropyran compound of formula I:

I. slowly dropwise adding 1-6g of 3, 3-dimethyl-1' -methyl-2-methylene indole to 3-10mL of concentrated H₂SO₄In the method, the temperature is controlled to be 1-10 ℃ by cooling in ice water bath; slowly dropwise adding 0.1-0.6g of fuming HNO₃To 1-3mL of concentrated H₂SO₄In the method, the mixed acid is dropwise added into a sulfuric acid solution containing 3, 3-dimethyl-1 '-methyl-2-methylene indole at the temperature of 1-10 ℃ after cooling in an ice water bath, the reaction temperature is controlled below 10 ℃, the mixed acid is stirred for 2-3h, then the mixed acid is kept stand at the temperature of 1-5 ℃ and refrigerated for 9-12h, concentrated NaOH solution is dropwise added into the mixed acid for alkalization, red solid is separated out, and the mixture is subjected to suction filtration, washing and drying to obtain the nitro-3, 3-dimethyl-1' -methyl-2-methylene indole (PS01)

Taking 0.2-1 g of PS01 and 2-6g of SnCl₂Heating and refluxing for 1.5-2.5h in 15-20mL of 37% hydrochloric acid, cooling in ice water bath to obtain clear solution, adding concentrated sodium hydroxide solution dropwise to the clear solution for alkalization, stopping adding dropwise when a large amount of white granular solids appear, extracting with diethyl ether, washing with water, filtering, and removing the solvent by rotary evaporation to obtain amino-3, 3-dimethyl-1' -methyl-2-methylindole (PS 02).

Amino-3, 3-dimethyl-1' -methyl-2-methylidene indole reaction formula

Dissolving 0.2-1 g of PS02 in 1-3mL of CH₂Cl₂Under the protection of nitrogen, cooling in ice water bath; glutaric acid chloride 0.03-0.1g is dissolved in 1-3mL CH₂Cl₂Adding glutaric acid chloride solution into PS02 solution dropwise, adding 0.5-3mL triethylamine, stirring at room temperature for 2-3h, filtering, washing with water, and removing the solvent by rotary evaporation of an organic layer to obtain a white solid containing 2-1, 3, 3-trimethyl-2-methylidene indole-diamide (PS 03).

Reaction formula of 2-1, 3, 3-trimethyl-2-methylene indole-diamide

Dissolving 0.02-0.1 g of PS03 and 0.01-0.06g of 5-nitro salicylaldehyde in 15-35mL of absolute ethyl alcohol under the protection of nitrogen, heating in a water bath at 30-50 ℃ and reacting for 12-20 h; and cooling to room temperature, crystallizing and separating out solid, performing suction filtration and drying to obtain mauve spiropyran compound powder.

Reaction formula of spiropyran compound

The beneficial effects of the invention are as follows:

1. in view of the color development requirement of color blindness correcting glasses under indoor weak light, the invention researches the application of the inverse photochromic compound as a color vision correcting visual light material, and the inverse photochromic spiropyran compound is a colorless or light-colored closed ring body under the illumination and is a colored (dark-colored) open ring body when being moved to the dark. Among the numerous spiropyran inverse photochromic compounds, it was found that the compound of formula (I) in combination with copper oxide nanoparticles has a satisfactory color correction effect on weak blue or weak red-blue-green.

2. The organic/inorganic nano composite microsphere visible light material is an acrylate/spiropyran/copper oxide nano microsphere three-layer composite core-shell structure. The spiropyran is located as a color-changing compound between the shell and the core, i.e. the intermediate layer. The copper oxide cluster of the inner core provides certain color for the visible light material and is used as a carrier of the spiropyran compound. In the preferred preparation method, the prepared inner core copper oxide cluster has a mesoporous nano structure, so that the Van der Waals area of the discoloring molecules adsorbed on the surface can be enlarged, the conjugated system can be enlarged, and the gaps between the molecules can be enlarged, thereby greatly increasing the space for the molecules to have isomerization reaction, reducing the conversion obstruction, enhancing the activity of discolorers, enabling the spectral response to be more sensitive, and being capable of changing the filtering characteristics in spectral areas with different wave bands and improving the color vividness under different illumination conditions. The acrylate shell has good rigidity, protects the color-changing compound from the external environment, and is favorable for being combined with a resin material matrix when the optical material is prepared.

3. The three-layer composite core-shell structure nano-microspheres with uniform and accurate sizes are generated by controlling reaction conditions in the process of preparing the organic/inorganic nano-composite microsphere visual material. Wherein, the sodium acetate plays an important role in the reaction process, on one hand, the copper oxide nano-crystals are gradually aggregated and nucleated, and on the other hand, the aggregation and nucleation of a large number of particles are effectively prevented. The composite microsphere prepared by the method has the outer diameter of 35-90nm, wherein the diameter of the copper oxide nanoparticle is 15-40 nm, the thickness of the middle layer is 5-15 nm, and the thickness of the shell is 5-10 nm.

4. The blue amblyopia correcting lens prepared by the organic/inorganic nano composite microsphere visual light material can keep darker color under indoor normal light, can automatically enhance the spectral color purity of blue wave band and the dimension of color vision vector space, improve the color distinguishing capability of achromate, correct abnormal color vision, and is effective for patients with blue amblyopia, red blue and green amblyopia; and after the fabric returns to the outdoor (ultraviolet irradiation), the fabric can gradually fade into light color or colorless, so that the reality of the visual objects of a patient is ensured, the visual health is maintained, and the fabric has the advantages of high color saturation, good color complementing effect, wearing comfort and the like.

Drawings

FIG. 1 is a graph of absorption spectrum of spiropyran compounds (I).

Fig. 2 is a transmission electron microscope photograph of the acrylate/spiropyran/copper oxide nanocomposite microsphere prepared in example 2.

Fig. 3 is a transmission electron microscope photograph of the acrylate/spiropyran/titanium oxide nanocomposite microsphere prepared in example 4.

FIG. 4 is an infrared spectrum of the acrylate/spiropyran/copper oxide nanocomposite microsphere prepared in example 2.

Fig. 5 is a chart showing the transmittance spectrum of the color vision correction lens prepared in example 2.

FIG. 6 shows sample N of the nano-composite microspheres prepared in examples 1 and 2₂Adsorption-desorption isotherms (6a) and pore size distribution profile (6 b).

FIG. 7 is a graph showing the comparison between the effect of the color vision correction lens prepared in example 2 before wearing (7-1) and after wearing (7-2).

FIG. 8 is a photo of the nano-composite microsphere prepared in example, wherein 8-1 and 8-2 are photos of the nano-composite microsphere prepared in example 1 and example 2, respectively.

Detailed Description

The invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention.

The spiropyran compounds in the following examples and comparative examples were prepared by the following method:

preparing a spiropyran compound of formula I:

A. slowly add 1.8g of 3, 3-dimethyl-1' -methyl-2-methylindole dropwise to 4mL of 85% H₂SO₄In the process, the temperature is controlled to be 4 ℃ by cooling in an ice water bath; 0.35g of 98% HNO₃Slowly add 1.6mL 85% H₂SO₄Adding the mixed acid dropwise into a sulfuric acid solution containing 3, 3-dimethyl-1 '-methyl-2-methylene indole, controlling the reaction temperature at 5 ℃, stirring for 3.5h, standing and refrigerating for 10h at 5 ℃, adding a 37% NaOH solution dropwise for alkalization, precipitating a red solid, performing suction filtration, washing with water and drying to obtain the nitro-3, 3-dimethyl-1'-methyl-2-methylidene indole (PS01)

B. 0.5 g of PS01 and 3.5g of SnCl were taken₂Heating and refluxing the mixture in 16mL of 37% hydrochloric acid for 2 hours, cooling the mixture in an ice-water bath to obtain a clear solution, dropwise adding 35% sodium hydroxide solution into the clear solution for alkalization to obtain a large amount of white granular solids, extracting the white granular solids by using diethyl ether, washing the white granular solids by using water, filtering the white granular solids, and performing rotary evaporation to obtain white solid amino-3, 3-dimethyl-1' -methyl-2-methylindole (PS 02).

C. 0.2 g of PS02 was dissolved in 3mL of CH₂Cl₂Under the protection of nitrogen, cooling to 5 ℃ in an ice water bath; glutaric acid chloride 0.06g was dissolved in 2.2mL CH₂Cl₂And (2) dropwise adding a glutaric acid chloride solution into the PS02 solution, adding 1.2mL of triethylamine, stirring at room temperature for 2h, filtering, washing with water, and removing the solvent by rotary evaporation of an organic layer to obtain a white solid containing 2-1, 3, 3-trimethyl-2-methylindole-diamide (PS 03).

D. Under the protection of nitrogen, 0.06g of PS03 and 0.04g of 5-nitro salicylaldehyde are dissolved in 25mL of absolute ethyl alcohol and heated in a water bath at 30-50 ℃ for reaction for 18 h. And (3) cooling to room temperature to obtain crystal particles, performing suction filtration and drying to obtain the purple red spiropyran compound powder (I).

Dissolving the spiropyran compound (I) prepared in the step in tetrahydrofuran, subpackaging and pouring into a plurality of glass test tubes, irradiating for 15min at normal temperature after marking, enabling the solution to be colorless under illumination, moving to a dark place for 12S, gradually changing to red, and circulating for many times, wherein the solution has a wider absorption peak at 245 nm-350 nm, and is shown in figure 1 in detail.

Elemental analysis C₄₃H₄₂N₆O₈Measured value (calculated value)%: c66.94 (67.00); h5.44 (5.49); n10.95 (10.90).

Example 1: preparation of organic/inorganic nanocomposite microspheres and color vision correction lens

Preparing organic/inorganic nano composite microspheres:

1. adding 2.5g of emulsifier RF-345 into 1100g of purified water, after completely dissolving, adding 30g of nano copper oxide, dropwise adding 120g of sodium acetate saturated aqueous solution within 70min, and then adding 20g of cross-linking agent DAP; introducing nitrogen into a reaction kettle, adding 145g of a methylene chloride solvent (35 g of spiropyran solvent 110g) containing a spiropyran compound (formula I), adding 18g of methyl acrylate monomer and 10g of ethyl acrylate monomer, stirring and heating to 65 ℃, adding 0.1g of initiator ammonium persulfate, preserving heat for 16h, filtering, washing and drying to obtain the acrylic ester/spiropyran/copper oxide nanosphere. The yield was 82%.

2. Observing the product prepared in the step 1 by a transmission electron microscope, as shown in fig. 2, showing that the appearance is spherical, wherein the dark-colored inner core is composed of a plurality of monodisperse copper oxide nanospheres with uniform size, the middle layer is a spiropyran compound, and the transparent layer is an acrylate shell, showing that the cobalt oxide nanospheres with larger specific surface area and pore volume absorb the spiropyran compound material and are coated by acrylate to form the core-shell structure composite microspheres, and because the outer shell of the acrylate is a colorless transparent material, the white outline is displayed in a transmission electron microscope picture. Calculated by a Sherre formula (D is K/beta cos theta) and Zeta potential analysis, the grain size of the copper oxide nano-sphere is about 4.5nm, the thickness of the shell of the spiropyran allochroic material and the acrylate coating is about 19nm, the inner core of the copper oxide nano-sphere is about 41nm, and the diameter of the whole composite microsphere is about 79 nm.

3. The sample prepared in step 1 was subjected to Fourier transform Infrared Spectroscopy (FT-IR) at 3408cm^-1And 1220cm^-1The absorption peak of (a) is generated by stretching vibration and bending vibration of the amino group, indicating the existence of the spiropyran compound; 2961cm^-1Has an absorption peak of 1730cm generated by stretching vibration of methylene^-1At 1610cm^-1At 1089cm^-1The peak is a strong peak of C ═ O vibration, and is a characteristic absorption peak of MMA (acrylic ester) at 591cm^-1And 524cm^-1The obvious absorption peak appears at 500cm^-1Nearby is Cu — O stretching vibration (see fig. 4), demonstrating the presence of copper oxide in the sample.

4. The photograph of the appearance of the product prepared in step 1 is shown in FIG. 8-1.

(II) preparing a color vision correction lens:

adding 18.0g of the acrylate/spiropyran/copper oxide nano-microspheres prepared in the step 1 into a reaction vessel containing 1200g of methyl methacrylate monomer (acrylic), adding 12g of dichloromethane, fully mixing and stirring, adding 3.5g of BPO into the monomer, stirring at a low speed of 200r/min, controlling the temperature to be 80 ℃ for polymerization reaction for 3 hours, and finishing prepolymerization; filtering and degassing the pre-polymerization mixture, injecting the pre-polymerization mixture into a mold, and heating the pre-polymerization mixture to 85 ℃ from room temperature in a curing furnace for 18 hours to finish primary curing; and (3) opening the mold and cleaning after the primary curing is finished, and finishing the secondary curing in a precisely controlled curing furnace at the constant temperature of 105 ℃ for 2 hours to obtain the color vision correction lens.

And (3) selecting a UV-8000 type ultraviolet-visible light double-spectrophotometer of Shanghai Yuan analysis instruments Co., Ltd to detect the light transmittance of the color vision correction lens prepared in the step (II), wherein the detection result is shown in detail in figure 5, and the spectrogram in figure 5 shows that the ultraviolet ray of the sample in the range of below 380nm keeps lower transmittance, and the blue ray of the sample in the range of 500nm keeps higher transmittance. The lens has high blue resolution and can be used as a blue weakness correction lens.

Example 2: preparation of color vision correction lens

Preparing organic/inorganic nano composite microspheres:

i. adding 2g of emulsifier sodium dodecyl benzene sulfonate into 1000g of purified water, after completely dissolving, adding 26g of nano titanium oxide, dropwise adding 140g of sodium acetate saturated aqueous solution within 70min, and then adding 20g of cross-linking agent butyl acrylate; introducing nitrogen into a reaction kettle, adding 130g of dichloromethane solvent (30 g of spiropyran solvent 100g) containing spiropyran compound (formula I), adding 26g of ethyl acrylate monomer, stirring and heating to 70 ℃, adding 0.1g of initiator sodium persulfate, preserving heat for 16h, filtering, washing and drying to obtain the acrylic ester/spiropyran/titanium oxide nanosphere. The yield was 78%.

Observing the product prepared in the step (i) by a transmission electron microscope, and as shown in fig. 3, showing that the appearance is spherical, wherein the inner core is white titanium oxide crystal grains to form a nanosphere, the middle layer is a spiropyran compound, the transparent layer is an acrylate shell, and through analysis and calculation, the titanium oxide nanocrystal particle size is about 4.2nm, the thickness of the spiropyran discoloration material and the acrylate shell is about 13nm, the inner core of the titanium oxide nanosphere is about 25nm, and the diameter of the whole composite microsphere is about 51 nm.

(ii) the sample prepared in step (i) has been subjected to Fourier transformA test of transform infrared spectroscopy (FT-IR) was conducted with similar absorption characteristic peaks as the acrylate/spiropyran/copper oxide microspheres prepared in example 1, except at 506cm^-1、601cm^-1And 700cm^-1The absorption peak at (A) corresponds to the characteristic absorption peak of Ti-O, thus proving the existence of titanium oxide in the sample.

A photograph of the appearance of the product prepared in step (i) is shown in fig. 8-2.

(II) preparing a color vision correction lens:

taking 12.0g of the acrylate/spiropyran/copper oxide nanosphere prepared in the example 1 and 8.0g of the acrylate/spiropyran/titanium oxide nanosphere prepared in the step (i) to be respectively added into a reaction container containing 1400g of methyl methacrylate monomer (acrylic), adding 13g of dichloromethane to fully mix and stir, then adding 3.5g of BPO into the monomer, stirring at a low speed of 200r/min, controlling the polymerization reaction at 80 ℃ for 3 hours, and finishing prepolymerization; filtering and degassing the pre-polymerization mixture, injecting the pre-polymerization mixture into a mold, and heating the pre-polymerization mixture to 85 ℃ from room temperature in a curing furnace for 18 hours to finish primary curing; and (3) opening the mold and cleaning after the primary curing is finished, and finishing the secondary curing in a precisely controlled curing furnace at the constant temperature of 105 ℃ for 2 hours to obtain the color vision correction lens.

Example 3: analysis of the Structure of the nanocomposite microspheres prepared in examples 1 and 2

N was performed on the nanocomposite microsphere samples prepared in examples 1-2₂The adsorption-desorption isotherm detection was performed to analyze the structural characteristics of the nanospheres, and the results are shown in fig. 6. Wherein P1 and P2 represent samples of the nano-composite microspheres prepared in example 1 and example 2, respectively, and FIG. 6a shows N₂Adsorption-desorption isotherms, the isotherm type of the sample having a hydrothermal reaction time of 10h being type IV at P/P₀The hysteresis loop exists at the position of 0.4-1.0, which indicates the existence of mesopores. FIG. 6b is a graph of pore size distribution, showing that there is an obvious peak at 3nm and no peak after 5nm, indicating that the pore size is small and about 3nm, and the mesopores in the sample are formed by aggregation of nanoparticles. All these results are consistent with previously observed SEM images of the morphology of the nanocomposite microspheres.

Example 4: the optical performance test was performed on the color vision correction lenses prepared in example 1 and example 2, respectively

Firstly, detecting the inverse photochromic performance:

a detection step: after the lenses prepared in example 1 and example 2 were marked, each part was placed in a sunlight simulation box for irradiation detection, and irradiated at room temperature for 6min, with a distance between the lens and the light source of 20CM and an irradiation dose hv of 2Eg, and the conditions before and after the lens irradiation were recorded, and the detection results are shown in table one.

Table-lens inverse light colour changing condition table

And (4) conclusion: the above results show that the samples prepared in this example exhibit a reverse photochromic effect, which is exactly the opposite of that exhibited by most pyran compounds, i.e., colorless or light-colored closed rings in the light, and colored (dark-colored) open rings in the dark. And the color changing speed is higher.

(II) detecting color purity (color saturation):

a detection step: marking the color vision correction lenses prepared in the embodiment 1 and the embodiment 2, respectively inserting the marked color vision correction lenses into a testing frame, and detecting the color purity on a computer optometry instrument, wherein the distance between human eyes and a color picture is 3.5m, and detecting and recording white films and color vision correction lenses of detected personnel in groups by the detection personnel, wherein the details are shown in a table II; and a color detector is adopted for detection and recording, and the detection result is shown in the table II.

TABLE II color purity (color saturation) test

And (4) conclusion: the lens prepared by the embodiment enhances the color discrimination of eyes and has high visual object color saturation.

And (III) identifying and detecting color blindness pictures:

according to the inspection result of the color blindness inspection chart, the type and the grade degree of the color vision anomaly are determined, the lenses manufactured in the example 1 and the example 2 are respectively tested by referring to the color mixing scale value of the TZ-1 type color vision detector and the effect of trying on the color blindness correction lens of a patient, and the color distinguishing correction effect is recorded, which is detailed in the table III and the figure 7. FIG. 7 is a comparison of the effect of the color vision correction lens prepared in example 1 before wearing (7-1) and after wearing (7-2), showing that the resolution of blue color is significantly improved. The participants were able to recognize at least 29 pictures and at most 39 pictures, and thus it was judged that the achromatopsia correction lenses prepared in examples 1 and 2 were suitable for patients with blue weakness and red, green and blue weakness, respectively.

Correction table for table three-colour

Chrominance correction	Color discrimination before wearing	After wearing, the color is distinguished	Corrective effect
				Example 2	Blue color is weaker	Blue colour is clear	Correcting blue color weakness level
Example 5	Green color is weaker	Clear blue green	Correcting weak red, blue and green

Claims

1. A blue color weakness correcting lens is characterized in that the lens contains an acrylic ester/spiropyran/nano copper oxide three-layer composite core-shell structure optomaterial, wherein an inner core of the lens is a copper oxide nano microsphere, a spiropyran compound shown in a formula I is coated outside the microsphere, and an outer shell of the lens is acrylic ester; wherein the mass ratio of the copper oxide nano-microspheres to the spiropyran compounds to the acrylic ester is 1: 1.1-1.3: 0.9-1; the mass ratio of the core-shell structure vision material to the lens resin base material is 1: 30-200;

2. the lens for correcting blue amblyopia of claim 1, wherein said acrylate is polymerized from an acrylate monomer selected from at least one of methyl acrylate, ethyl acrylate, 2-methyl methacrylate and 2-ethyl methacrylate.

3. The blue shading correction lens according to claim 1, wherein the mass ratio of the copper oxide nanoparticles to the spiropyran compound to the acrylate is 30: 45: 28.

4. The blue shading correction lens according to any one of claims 1 to 3, wherein the mass ratio of the core-shell structure visual light material to the lens resin base material is 1: 55-65.

5. A method of making a blue shading correction lens as claimed in any one of claims 1 to 4, characterized in that the method comprises the following steps:

II, preparing a blue color shading correction resin lens

6. The method according to claim 5, wherein the acrylate monomers in the steps I and II are the same and are at least one selected from the group consisting of methyl acrylate, ethyl acrylate, 2-methyl methacrylate and 2-ethyl methacrylate.

7. The method of claim 5, wherein the copper oxide nanoparticles have a particle size of 2 to 12 nm.

8. The method according to claim 5, wherein the solvent of the solution of the spiropyran compound is at least one selected from the group consisting of chloroform, acetone, propyl acetate, butyl acetate, ethyl acetate, dibutyl phthalate, and petroleum ether; the mass ratio of the spiropyran compound to the solvent is 1: 2-3.

9. The method according to claim 5, wherein the crosslinking agent in step I is vinyl butyl methacrylate or diallyl phthalate, and the amount of the crosslinking agent is 0.5-2% by mass of the acrylate monomer;

10. The method according to any one of claims 5 to 9, wherein the initiators in step I and step II are the same or different and each is at least one selected from the group consisting of dibenzoyl peroxide, diisopropyl peroxydicarbonate, ammonium persulfate and sodium persulfate in an amount of 0.2 to 0.4% based on the amount of the acrylate monomer.