CN114031725B

CN114031725B - Preparation method of color vision correction resin lens

Info

Publication number: CN114031725B
Application number: CN202111244279.4A
Authority: CN
Inventors: 张鹤军; 王明华; 宗立率; 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: 2023-05-09
Anticipated expiration: 2041-10-25
Also published as: CN114031725A

Abstract

A method for preparing a color vision correcting resin lens, the method comprising: I. the method comprises the steps of preparing organic/inorganic nano composite microspheres, wherein the microspheres are of a three-layer composite core-shell structure, the inner core of the microspheres is an oxide nano microsphere, the middle layer is a complementary color layer formed by a spiropyran compound, and the outer shell is acrylic ester; and II, adding the organic/inorganic nano composite microspheres into acrylate monomers to perform polymerization reaction, so as to obtain the color vision correcting resin lens. The lens has darker color under indoor normal light, can automatically enhance the spectral color purity of a certain wave band and the dimension of a color vision vector space, improves the color discrimination capability of a achromatopsia patient, and corrects color vision abnormality.

Description

Preparation method of color vision correction resin lens

Technical Field

The invention belongs to the technical field of eye vision optics, and particularly relates to a preparation method of a color vision correcting resin lens.

Background

Color vision is one of the important visual functions of the eye, and seven colors of the visible spectrum in sunlight can be attributed to three primary colors, namely red, green and blue, and retinal cone cells contain erythroesthesia, green and blue. The human eye recognizes approximately over 100 different colors. Congenital color vision abnormality is caused by abnormal deficiency of color sensing pigment in cone cells. Generally, it can be classified into full color blindness, red-green color blindness and red-green color weakness. A color vision with only one color sensing pigment, namely, a full color blindness; the person with two kinds of color sensing pigments is two-color vision, so that the person lacks red sensing pigment or green sensing pigment, namely, the person is red-green color blindness; the color sensing pigment in the cone cells is normal, and one color sensing pigment is less, and the cone cells are three-color vision, namely red, green and weak. According to human color sense physiology and physics, the color sense feature of normal human is three-dimensional vector space, and three basic 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. When the vector space of the achromatopsia patient has fewer dimensions than normal and the difference in brightness is not obvious (achromatopsia examination chart is based on the principle), the achromatopsia patient cannot distinguish the two colors.

The traditional achromatopsia correcting glasses cannot increase the dimension of the vector space, but change the difference of the two colors in brightness, and after wearing the traditional achromatopsia correcting glasses, an achromatopsia patient distinguishes the two colors by the difference in brightness. However, wearing such glasses for a long period of time may cause distortion of vision, which is rather unfavorable for vision health; in addition, the prior art has the defects of poor appearance effect and obvious abnormal colors of the spectacle lens, such as: the patient is worried about the redness and the darkness, and the attractive appearance is affected; some achromatopsia mirrors can greatly attenuate the transmission of normal light while correcting color vision abnormality, so that the achromatopsia mirrors cannot be used under low light level, normal vision parts are disturbed, and vision is reduced after long-term wearing.

The traditional achromatopsia correcting glasses cannot increase the dimension of the vector space, but change the difference of the two colors in brightness, and after wearing the traditional achromatopsia correcting glasses, an achromatopsia patient distinguishes the two colors by the difference in brightness. However, in this way, some people can distinguish the color by means of the difference in brightness without wearing the traditional achromatopsia correcting glasses, and the people cannot distinguish the color when wearing the achromatopsia correcting glasses. Moreover, with conventional achromatopsia correcting spectacles, there is always some reduction in overall vision and the appearance of reddish blue is unacceptable.

Disclosure of Invention

The invention aims to provide a preparation method of a color vision correction resin lens, which comprises the steps of firstly preparing organic/inorganic nano composite microspheres with three-layer composite core-shell structures, wherein the inner cores of the organic/inorganic nano composite microspheres are oxide nano particles, the outer shells are coated with acrylic ester, and a spiropyran color-changing compound is arranged in an intermediate layer between the inner cores and the outer shells. The material is used as a filtering and complementary color material to be added into an optical resin monomer to form a lens material through polymerization reaction. The lens is darker in color under indoor normal light, can automatically enhance the spectral purity of a certain wave band and the dimension of a color vision vector space, improves the color distinguishing capability of a patient with color blindness, corrects color vision abnormality, particularly a patient with red-green weak and secondary red-green color blindness, and can fade rapidly to light color or colorless after returning to the outdoor (ultraviolet irradiation), thereby ensuring the reality of the vision of the patient, maintaining visual health, and has the advantages of high color saturation, good color compensation effect, comfort in wearing and the like.

In order to achieve the above purpose, the present invention provides the following technical solutions:

a method for preparing a color vision correcting resin lens, comprising the steps of:

I. preparation of organic/inorganic nano composite microsphere

i. Weighing an acrylic ester monomer, a spiropyran compound shown in a formula (I) and transition metal oxide nano particles, wherein the mass ratio of the acrylic ester monomer to the spiropyran compound to the transition metal oxide nano particles is (1-2) to (2-3) to (2-4), and dissolving the spiropyran compound in an organic solvent;

adding purified water and an emulsifying agent into a reaction kettle, and adding transition metal oxide nano particles after complete dissolution, wherein the concentration of the transition metal oxide nano particles 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 oxide nano particles is 1:0.5-1.0; the transition metal 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 oxide clusters;

adding an acrylic ester monomer into the reaction system, stirring to obtain O/W emulsion, stirring and heating to 65-90 ℃, adding an initiator, performing heat preservation and polymerization for 12-18h, and generating an acrylic ester shell outside the particles formed in the step iii; the organic/inorganic nano composite microsphere optomaterials are obtained through filtration, washing and drying;

II, preparing resin lens for correcting colour vision

Adding the organic/inorganic nano composite microsphere and the initiator prepared in the step I into an acrylic ester monomer and a solvent, and uniformly stirring, wherein the mass ratio of the organic/inorganic nano composite microsphere to the acrylic ester monomer is 1:30-200; polymerizing at 65-85 deg.c for 2-3.5 hr, filtering, degassing, injecting into mold, and raising the temperature from room temperature to 85 deg.c for 12-20 hr to complete one-step solidification; then the temperature is kept at 90-110 ℃ for 1.5-3.0 hours to finish secondary curing, and the color vision correcting resin lens is obtained.

The preparation method as described above, preferably, the acrylate monomers described in the step I and the step 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.

The preparation method is characterized in that the transition metal oxide is selected from one or more of titanium oxide, iron oxide, copper oxide and cobalt oxide, and the particle size of the transition metal oxide nanoparticle is 2-12nm.

In the above preparation method, preferably, the solvent of the spiropyran compound solution is at least one of chloroform, acetone, propyl acetate, butyl acetate, ethyl acetate, dibutyl phthalate and petroleum ether.

In the above preparation method, the mass ratio of the spiropyran compound to the solvent is preferably 1:2-3.

In the preparation method, preferably, the cross-linking agent in the step I is butyl methacrylate or diallyl phthalate, and the dosage is 0.5-2% of the mass of the acrylate monomer.

In the preparation method, preferably, the emulsifier in the step I is at least one of RF-345, polyvinylpyrrolidone or sodium dodecyl benzene sulfonate, and the dosage is 2-6g/L.

In the preparation method, preferably, the initiator in the step I is at least one selected from dibenzoyl peroxide, diisopropyl peroxydicarbonate, ammonium persulfate and sodium persulfate, and the dosage is 0.2-0.4% of the dosage of the acrylate monomer.

In the preparation method, preferably, the initiator in the step II is at least one selected from dibenzoyl peroxide, diisopropyl peroxydicarbonate, ammonium persulfate and sodium persulfate, and the dosage is 0.2-0.4% of the dosage of the acrylate monomer.

The preparation method is characterized in that the mass ratio of the organic/inorganic nano composite microsphere to the acrylic ester monomer in the step II is preferably 1:55-75.

Synthesis of spiropyran compounds of formula I:

I. 3, 3-dimethyl-1' -methyl-2-methyleneindole 1-6g was slowly added dropwise to 3-10mL of concentrated H ₂ SO ₄ In the process, the cooling temperature of the ice water bath is controlled to be 1-10 ℃; slowly dripping 0.1-0.6g fuming HNO ₃ To 1-3mL of concentrated H ₂ SO ₄ Wherein, the cooling temperature of the ice water bath is controlled to be 1-10 ℃, mixed acid is dripped into a solution containing 3, 3-dimethyl-1 '-methyl-2-methyleneindole sulfuric acid, the reaction temperature is controlled to be below 10 ℃, the solution is stirred for 2-3 hours, then the solution is kept stand for 1-5 ℃ and refrigerated for 9-12 hours, concentrated NaOH solution is dripped into the solution for alkalization, red solid precipitation appears, suction filtration and water washing and drying are carried out, thus obtaining nitro-3, 3-dimethyl-1' -methyl-2-methyleneindole (PS 01)

II, taking 0.2-1 g PS01 and 2-6g SnCl ₂ Refluxing in 15-20mL37% hydrochloric acid for 1.5-2.5 hr, cooling with ice water bath to obtain clear solution, adding concentrated sodium hydroxide solution dropwise for alkalization, stopping adding dropwise after a large amount of white granular solid appears, extracting with diethyl ether, filtering with water, and removing solvent by rotary evaporation to obtain amino group-3, 3-dimethyl-1' -methyl-2-methyleneindole (PS 02).

III dissolving 0.2-1 g PS02 in 1-3mL CH ₂ Cl ₂ Nitrogen protection and ice water bath cooling; glutaric acid chloride 0.03-0.1g dissolved in 1-3mL CH ₂ Cl ₂ In the method, the glutaric acid chloride solution is dropwise added into the PS02 solution, 0.5-3mL of triethylamine is added, stirring is carried out at room temperature for 2-3h, filtering and washing are carried out, the organic layer is distilled off in a rotary way to remove the solvent, and the white solid containing 2-1, 3-trimethyl-2-methylene indole-diamide (PS 03) is obtained.

Under the protection of nitrogen, 0.02-0.1 g of PS03 and 0.01-0.06g of 5-nitro salicylaldehyde are taken and dissolved in 15-35mL of absolute ethyl alcohol, and the mixture is heated in water bath for reaction for 12-20h at the temperature of 30-50 ℃; cooling to room temperature, crystallizing and separating out solid, suction filtering and drying to obtain the purplish red spiropyran compound powder.

The beneficial effects of the invention are as follows:

1. the inverse photochromic spiropyran compound is colorless or light-colored closed ring body under illumination, and moves to dark place to be colored (dark color) open ring body. The researcher discovers that the compound of the formula I combined with the transition metal oxide nano particles has a satisfactory color correction effect in a plurality of spiropyran inverse photochromic compounds, and prepares the compound into the organic/inorganic nano composite microsphere with a three-layer composite core-shell structure, and the organic/inorganic nano composite microsphere is applied to the preparation of the achromatopsia correcting lens, so that the preparation method of the achromatopsia correcting lens with a good achromatopsia correcting effect is provided.

2. The organic/inorganic nano composite microsphere visible light material prepared by the method is of an acrylate/spiropyran/transition metal oxide nano microsphere three-layer composite core-shell structure. The spiropyran is located as a color-changing compound between the outer shell and the inner core, i.e. the intermediate layer. The transition metal oxide clusters of the inner core provide a certain color to the photopic material and act as carriers for the spiropyran compounds. In the preferred preparation method, the prepared inner core transition metal oxide cluster has a mesoporous nano structure, so that the van der Waals area of the color-changing molecules adsorbed on the surface can be increased, a conjugated system is increased, and the gaps between molecules are increased, thereby greatly increasing the space for isomerization reaction of the molecules, reducing the conversion obstruction, enhancing the activity of the color-changing body, enabling the spectral response to be more sensitive, changing the light filtering characteristics in the spectral areas of different wave bands under different illumination conditions, and improving the brightness of the color. 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. In the process of preparing the organic/inorganic nano composite microsphere visible light material, three-layer composite core-shell structure nano microspheres with uniform and accurate size are generated by controlling reaction conditions. Wherein sodium acetate plays an important role in the reaction process, so that on one hand, oxide nanocrystals 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 oxide nano microsphere is 15-40 nm, the thickness of the intermediate layer is 5-15 nm, and the thickness of the shell is 5-10 nm.

4. The achromatopsia correcting lens prepared by the method of the invention keeps darker color under indoor normal light, can automatically enhance the spectral purity of a certain wave band and the dimension of the color vision vector space, improves the color distinguishing capability of achromatopsia patients, corrects color vision abnormality, is especially effective for patients with red-green weakness, secondary-weight achromatopsia and blue weakness, and gradually fades into light color or colorless after returning to the outdoor (ultraviolet irradiation), ensures the reality of the vision of the patients, maintains visual health, and has the advantages of high color saturation, good complementary color effect, comfortable wearing and the like.

Drawings

FIG. 1 is a transmission electron micrograph of the acrylate/spiropyran/iron oxide nanocomposite microspheres prepared in example 1.

FIG. 2 is a transmission electron micrograph of the acrylate/spiropyran/copper oxide nanocomposite microspheres prepared in example 2.

FIG. 3 is a transmission electron micrograph of the acrylate/spiropyran/cobalt oxide nanocomposite microspheres prepared in example 3.

FIG. 4 is a transmission electron micrograph of the acrylate/spiropyran/titanium oxide nanocomposite microspheres prepared in example 4.

FIG. 5 is a graph showing the absorption spectrum of the spiropyran compound (I).

FIG. 6 is an infrared spectrum of the acrylate/spiropyran/ferric oxide nanocomposite microsphere prepared in example 1.

FIG. 7 is a transmittance spectrum of the color vision correcting lens prepared in example 1.

FIG. 8 is an infrared spectrum of the acrylate/spiropyran/copper oxide nanocomposite microsphere prepared in example 2.

FIG. 9 is a transmittance spectrum of the color vision correcting lens prepared in example 2.

FIG. 10 is a transmittance spectrum of the color vision correcting lens prepared in example 3.

FIG. 11 is a transmittance spectrum of the color vision correcting lens prepared in example 4.

FIG. 12 is a sample N of nanocomposite microspheres prepared in examples 1-4 ₂ Adsorption-desorption isotherms and pore size distribution plots.

Fig. 13 is a graph showing the effect of the color vision correcting lens prepared in example 1 before wearing (13-1) and after wearing (13-2).

Fig. 14 is a graph showing the effect of the color vision correcting lens prepared in example 2 before wearing (14-1) and after wearing (14-2).

Fig. 15 is a graph showing the effect of the color vision correcting lens prepared in example 3 before wearing (15-1) and after wearing (15-2).

Fig. 16 is a graph showing the effect of the color vision correcting lens prepared in example 4 before wearing (16-1) and after wearing (16-2).

FIG. 17 is a photograph of nanocomposite microspheres prepared in examples, wherein 17-1, 17-2, 17-3 and 17-4 are photographs of microsphere products prepared by the methods of example 1, example 2, example 3 and example 4, respectively.

Detailed Description

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

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

preparation of spiropyran compounds of formula I:

A. 1.8g of 3, 3-dimethyl-1' -methyl-2-methyleneindole was slowly added dropwise to 4mL of 85% H ₂ SO ₄ In the process, the cooling temperature of the ice water bath is controlled at 4 ℃; 0.35g of 98% HNO ₃ Slowly add 1.6mL of 85% H dropwise ₂ SO ₄ Dropwise adding the mixed acid into a solution containing 3, 3-dimethyl-1 '-methyl-2-methyleneindole sulfuric acid, controlling the reaction temperature at 5 ℃, stirring for 3.5h, standing and refrigerating for 10h at 5 ℃, dropwise adding a 37% NaOH solution for alkalizing, precipitating a red solid, filtering, washing with water and drying to obtain nitro-3, 3-dimethyl-1' -methyl-2-methyleneindole (PS 01)

B. 0.5 g PS01 and 3.5g SnCl are taken ₂ Heating and refluxing in 16mL of 37% hydrochloric acid for 2h, cooling in ice water bath to obtain a clear solution, adding 35% sodium hydroxide solution dropwise to the clear solution for alkalization, extracting with diethyl ether after a large amount of white granular solid appears, washing with water, filtering, and steaming in a rotary manner to obtain white solid amino-3, 3-dimethyl-1' -methyl-2-methyleneindole (PS 02).

C. 0.2 g PS02 was dissolved in 3mL CH ₂ Cl ₂ In the process, nitrogen is used for protection, and ice water bath is used for cooling to 5 ℃; glutaric acid chloride 0.06g dissolved in 2.2mL CH ₂ Cl ₂ In the process, the chlorine glutarate solution is dropwise added to the PS02 solution, 1.2mL of triethylamine is added, stirring is carried out at room temperature for 2h, filtering and washing are carried out, and the organic layer is distilled off by rotating to remove the solvent, so that white solid containing 2-1, 3-trimethyl-2-methylene indole-diamide (PS 03) is obtained.

D. Under the protection of nitrogen, 0.06g of PS03 and 0.04g of 5-nitro salicylaldehyde are taken and dissolved in 25mL of absolute ethyl alcohol, and the mixture is heated in a water bath for reaction for 18 hours at the temperature of 30-50 ℃. After cooling to room temperature, crystallization particles appear, and the powder (I) of the purple-red spiropyran compound is obtained by suction filtration and drying.

The spiropyran compound (I) prepared by the steps is taken, dissolved in tetrahydrofuran, split-packed and poured into a plurality of glass test tubes, and is irradiated for 15min at normal temperature after being marked, the solution is colorless under illumination, the solution gradually turns red after being moved to a dark place for 12S, the solution can be circulated for a plurality of times, and the solution has a wider absorption peak at a position of 245nm to 350nm, and is shown in a detailed figure 5.

Elemental analysis C ₄₃ H ₄₂ N ₆ O ₈ Measured value (calculated value)%: c66.94 (67.00); h5.44 (5.49); n10.95 (10.90).

Example 1: preparation of organic/inorganic nano composite microsphere and color vision correcting lens

(one) preparing organic/inorganic nano composite microspheres:

(1) Adding 3g of emulsifier RF-345 into 1200g of purified water, adding 35g of nano ferric oxide after complete dissolution, dropwise adding 150g of sodium acetate saturated aqueous solution within 70min, and then adding 20g of cross-linking agent DAP; introducing nitrogen into a reaction kettle, adding 150g of methylene dichloride solvent (spiropyran 35g solvent 115 g) 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 18h, filtering, washing and drying to obtain the acrylic ester/spiropyran/ferric oxide dark red nanospheres. The yield was 85%.

(2) And (3) observing the product prepared in the step (1) by using a JEM-2100 transmission electron microscope, wherein the appearance is spherical, the deep-colored inner core consists of a plurality of uniformly-sized and monodisperse ferric oxide nanospheres, the middle layer is a spiropyran compound, the transparent layer is an acrylic ester shell, and the ferric oxide nanospheres with larger specific surface area and pore volume absorb the spiropyran compound material and are coated by acrylic ester to form the core-shell structure composite microsphere. The average crystal granularity of the ferric oxide and the diameter of the nano composite microsphere are obtained through the Shelle formula (D=K/beta cos theta) and Zeta potential analysis and calculation, wherein the particle size of the ferric oxide nano crystal is about 4nm, the thickness of the spiropyran color-changing material and the coating shell of acrylic ester is about 15nm, the inner core of the ferric oxide nano sphere is about 31nm, and the diameter of the whole composite microsphere is about 61nm.

(3) The product obtained in the step (1) was subjected to a Fourier transform infrared (FT-IR) test, and as can be seen from the analysis of the curve in FIG. 6, at 3408cm ^-1 And 1220cm ^-1 The absorption peaks of (2) are generated by the stretching vibration and bending vibration of the amino group, indicating the presence of the spiropyran compound; 2961cm ^-1 The absorption peak of (C) is 1730cm generated by stretching vibration of methylene ^-1 At 1610cm ^-1 Department and 1089cm ^-1 The strong peak of C=O vibration is characterized by MMA (acrylate) characteristic absorption peak, 591cm ^-1 The absorption peak at the site evolved from a narrow shoulder to a sharp peak shape, indicating the presence of Fe-O. Illustrating that the nanocomposite microsphere prepared in example 1 is not a single iron oxide species, but also includes a spiropyran compound and an acrylate species.

(4) The photograph of the appearance of the product prepared in the step (1) is shown in FIG. 17-1.

(II) preparing a color vision correcting lens: adding 20.0g of acrylic ester/spiropyran/ferric oxide nano-microspheres prepared in the step (1) into a reaction vessel containing 1200g of methyl methacrylate monomer (acrylic), adding 15g of methylene dichloride, fully mixing and stirring, adding 3.5g of dibenzoyl peroxide (BPO) into the monomer, stirring at a low speed of 200r/min, and controlling the polymerization reaction at 80 ℃ for 3 hours to complete the prepolymerization; filtering and degassing the prepolymerization mixture, injecting the prepolymerization mixture into a mold, and heating the prepolymerization mixture from room temperature to 85 ℃ in a curing furnace for 20 hours to finish primary curing; and after the primary curing is finished, opening the mold, cleaning, and keeping the temperature in a precisely controlled curing oven at 105 ℃ for 2 hours to finish secondary curing to obtain the color vision correcting lens.

The ultraviolet-8000 ultraviolet-visible light dual-photometer of Shanghai Yuan-Jiedu Instrument Co Ltd is selected for detecting the light transmittance of the color vision correcting lens prepared in the embodiment 1, the detection result is shown in figure 7, the spectrogram of figure 7 shows that the transmittance of ultraviolet light, purple light, blue light and green light of the sample within the range below 530nm is 0, and the higher transmittance is kept for the red light within the range of 605-700 nm. The lens has high resolution to red, and can be used as a weak red correction lens.

Example 2: preparation of organic/inorganic nano composite microsphere and color vision correcting lens

(one) preparing organic/inorganic nano composite microspheres:

1. adding 2.5g of emulsifier RF-345 into 1100g of purified water, adding 30g of nano copper oxide after complete dissolution, 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 methylene dichloride solvent (spiropyran 35g solvent 110 g) 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 16 hours, filtering, washing and drying to obtain the acrylic ester/spiropyran/copper oxide nanospheres. The yield thereof was found to be 82%.

2. And (2) observing the product prepared in the step (1) by a transmission electron microscope, wherein the appearance is spherical, the deep inner core is a nanosphere composed of copper oxide crystal grains, the middle layer is a spiropyran compound, the transparent layer is an acrylic ester shell, the diameter of the copper oxide crystal grains is about 4.5nm through analysis calculation, the thickness of the spiropyran color-changing material and the acrylic ester coating shell is about 19nm, the inner core of the copper oxide nanosphere is about 41nm, and the diameter of the whole composite microsphere is about 79nm.

3. The sample prepared in step 1 was subjected to a Fourier transform infrared spectrum (FT-IR) test, and as shown in the graph analysis of FIG. 8, it has obvious characteristic absorption peaks of spiropyran and acrylate, and has the same characteristics as those of the product prepared in example 1, except that at 591cm ^-1 And 524cm ^-1 Obvious absorption peak appears at 500cm ^-1 Cu-O stretching vibration is nearby, and the existence of copper oxide in the sample is proved.

4. The photograph of the appearance of the product prepared in the step 1 is shown in FIG. 17-2.

(II) preparing a color vision correcting lens:

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

The transmittance of the color vision correction lens prepared in the step (II) is detected, the detection result is shown in fig. 9, and the spectrogram of fig. 9 shows that the ultraviolet light of the sample in the range below 380nm keeps lower transmittance, and the blue light in the range of 500nm keeps higher transmittance. The lens has high blue resolution and can be used as a blue weak correction lens.

Example 3: preparation of organic/inorganic nano composite microsphere and color vision correcting lens

(one) preparing organic/inorganic nano composite microspheres:

a. adding 2.4g of emulsifier sodium dodecyl benzene sulfonate into 1000g of purified water, adding 30g of nano cobalt oxide after complete dissolution, 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 145g of methylene dichloride solvent (40 g of spiropyran solvent 105 g) containing a spiropyran compound (formula I), adding 28g of methyl acrylate monomer, stirring and heating to 65 ℃, adding 0.1g of initiator sodium persulfate, preserving heat for 16 hours, filtering, washing and drying to obtain the acrylic ester/spiropyran/cobalt oxide nanospheres. The yield was 80%.

b. And c, observing the product prepared in the step a through a transmission electron microscope, and as shown in a figure 3, finding that the appearance is spherical, wherein the deep inner core is a nanosphere composed of cobalt oxide crystal grains, the middle layer is a spiropyran compound, the transparent layer is an acrylic ester shell, the particle size of the cobalt oxide nanocrystal is about 4.1nm through analysis calculation, the thickness of the spiropyran color-changing material and the acrylic ester coating shell is about 14nm, the inner core of the cobalt oxide nanosphere is about 32nm, and the diameter of the whole composite microsphere is about 60nm.

c. The samples prepared in step a were subjected to a fourier transform infrared (FT-IR) test having an absorption characteristic peak similar to that of the samples prepared in example 1, wherein the absorption peak at 593cm "1 was correlated with Co-0 stretching vibration, demonstrating the presence of cobalt oxide in the samples.

d. The photograph of the appearance of the product prepared in step a is shown in FIGS. 17-3.

(II) preparing a color vision correcting lens:

adding 22.0g of acrylic ester/spiropyran/cobalt oxide nano-microsphere prepared in the step a into a reaction container containing 1300g of methyl methacrylate monomer (acrylic), adding 12g of methylene dichloride, fully mixing and stirring, adding 3.3g of BPO into the monomer, stirring at a low speed at 200r/min, and controlling the polymerization reaction at 80 ℃ for 3 hours to finish the prepolymerization; filtering and degassing the prepolymerization mixture, injecting the prepolymerization mixture into a mold, and heating the prepolymerization mixture from room temperature to 80 ℃ in a curing furnace for 20 hours to finish primary curing; and after the primary curing is finished, opening the mold, cleaning, and keeping the temperature in a precisely controlled curing oven at 105 ℃ for 2.5 hours to finish secondary curing to obtain the color vision correcting lens.

The transmittance of the color vision correction lens prepared in the step (II) is detected, the detection result is shown in figure 10, and the spectrum diagram of figure 10 shows that the ultraviolet ray transmittance of the sample in the range below 380nm is kept to be 0; maintaining a certain transmittance for blue light in the 480nm range; the high transmittance is kept for the red light in the range of 650-700 nm. The lens has certain resolution ratio to blue and red light, and can be used as a red color blindness correcting lens.

Example 4: preparation of organic/inorganic nano composite microsphere and color vision correcting lens

(one) preparing organic/inorganic nano composite microspheres:

i. adding 2g of emulsifier sodium dodecyl benzene sulfonate into 1000g of purified water, adding 26g of nano titanium oxide after complete dissolution, dropwise adding 140g of sodium acetate saturated aqueous solution within 70min, and adding 20g of cross-linking agent butyl acrylate; introducing nitrogen into a reaction kettle, adding 130g of methylene dichloride solvent (30 g of spiropyran solvent 100 g) containing a 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 16 hours, filtering, washing and drying to obtain the acrylic ester/spiropyran/titanium oxide nanospheres. The yield was 78%.

And (ii) observing the product prepared in the step (i) through a transmission electron microscope, wherein the appearance is spherical, the inner core is white titanium oxide crystal grains to form nanospheres, the middle layer is a spiropyran compound, the transparent layer is an acrylic ester shell, the particle size of the titanium oxide nanospheres is about 4.2nm through analysis calculation, the thickness of the spiropyran color-changing material and the acrylic ester coating shell is about 13nm, the inner core of the titanium oxide nanospheres is about 25nm, and the diameter of the whole composite microsphere is about 51nm.

The samples prepared in step (i) were subjected to a Fourier transform infrared (FT-IR) test having an absorption characteristic peak similar to that of the samples prepared in example 1, except that the peak was measured at 506cm ^-1 、601cm ^-1 And 700cm ^-1 The absorption peak at the position accords with the characteristic absorption peak of Ti-O, and the existence of titanium oxide in the sample is proved.

Photographs of the appearance of the product prepared in step (i) are shown in fig. 17-4.

(II) preparing a color vision correcting lens:

adding 16.0g of acrylic ester/spiropyran/titanium oxide nano-microsphere prepared in the step (i) into a reaction container containing 1000g of methyl methacrylate monomer (acrylic), adding 10g of methylene dichloride, fully mixing and stirring, adding 3.0g of BPO into the monomer, stirring at a low speed under 200r/min, and controlling the polymerization reaction at 80 ℃ for 3 hours to finish the prepolymerization; filtering and degassing the prepolymerization mixture, injecting the prepolymerization mixture into a mold, and heating the prepolymerization mixture from room temperature to 80 ℃ in a curing furnace for 20 hours to finish primary curing; and after the primary curing is finished, opening the mold, cleaning, and keeping the temperature in a precisely controlled curing oven at 105 ℃ for 2.5 hours to finish secondary curing to obtain the color vision correcting lens.

The transmittance of the color vision correction lens prepared in the step (II) is detected, the detection result is shown in fig. 11, and the spectrogram of fig. 11 shows that the ultraviolet ray transmittance of the sample in the range below 410nm is kept to be 0; the blue light within the 500nm range is kept with certain transmittance; the high transmittance is kept for the red light in the 630nm range. The lens has certain resolution ratio to blue and red light, and can be used as a red-green weak correction lens.

Example 5: preparation of a correcting lens for color vision

Taking 12.0g of acrylic ester/spiropyran/copper oxide nano-microsphere prepared in example 2 and 8.0g of acrylic ester/spiropyran/titanium oxide nano-microsphere prepared in example 4, respectively adding into a reaction container containing 1400g of methyl methacrylate monomer (acrylic), adding 13g of methylene dichloride, fully mixing and stirring, adding 3.5g of BPO into the monomer, stirring at a low speed at 200r/min, and controlling the polymerization reaction at 80 ℃ for 3 hours to complete the prepolymerization; filtering and degassing the prepolymerization mixture, injecting the prepolymerization mixture into a mold, and heating the prepolymerization mixture from room temperature to 85 ℃ in a curing furnace for 18 hours to finish primary curing; and after the primary curing is finished, opening the mold, cleaning, and keeping the temperature in a precisely controlled curing oven at 105 ℃ for 2 hours to finish secondary curing to obtain the color vision correcting lens.

Example 6: preparation of a correcting lens for color vision

Taking 12.5g of acrylic ester/spiropyran/cobalt oxide nano-microsphere prepared in example 3 and 7.5g of acrylic ester/spiropyran/titanium oxide nano-microsphere prepared in example 4, respectively adding into a reaction container containing 1400g of methyl methacrylate monomer (acrylic), adding 13g of methylene dichloride, fully mixing and stirring, adding 3.5g of BPO into the monomer, stirring at a low speed at 200r/min, and controlling the polymerization reaction at 80 ℃ for 3 hours to complete the prepolymerization; filtering and degassing the prepolymerization mixture, injecting the prepolymerization mixture into a mold, and heating the prepolymerization mixture from room temperature to 85 ℃ in a curing furnace for 18 hours to finish primary curing; and after the primary curing is finished, opening the mold, cleaning, and keeping the temperature in a precisely controlled curing oven at 105 ℃ for 2 hours to finish secondary curing to obtain the color vision correcting lens.

Example 7: preparation of a correcting lens for color vision

Taking 15g of acrylic ester/spiropyran/ferric oxide nano-microsphere prepared in example 1 and 7.0g of acrylic ester/spiropyran/titanium oxide nano-microsphere prepared in example 4, respectively adding into a reaction container containing 1400g of methyl methacrylate monomer (acrylic), adding 13g of methylene dichloride, fully mixing and stirring, adding 3.5g of BPO into the monomer, stirring at a low speed at 200r/min, and controlling the polymerization reaction at 80 ℃ for 3 hours to complete the prepolymerization; filtering and degassing the prepolymerization mixture, injecting the prepolymerization mixture into a mold, and heating the prepolymerization mixture from room temperature to 85 ℃ in a curing furnace for 18 hours to finish primary curing; and after the primary curing is finished, opening the mold, cleaning, and keeping the temperature in a precisely controlled curing oven at 105 ℃ for 2 hours to finish secondary curing to obtain the color vision correcting lens.

Example 8: analysis of the nanocomposite microsphere Structure prepared in examples 1 to 4

N on nanocomposite microsphere samples prepared in examples 1 to 4 ₂ Adsorption-desorption isotherm detection, analysis of the structural characteristics of the nanoparticle, and the results are shown in fig. 12. Wherein P1, P2, P3, P4 represent nanocomposite microsphere samples prepared in examples 1-4, respectively, FIG. 12a is N ₂ Adsorption-desorption isotherms, type IV isotherms for samples with 10h hydrothermal reaction time, at P/P ₀ The hysteresis ring is arranged at the position of 0.4-1.0, which indicates the existence of mesopores. FIG. 12b is a graph of pore size distribution with a distinct raised peak at 3nm and no raised peak after 5nm, indicating a smaller pore size, about 3nm, and mesopores in the sample formed by aggregation of nanoparticles. All these results are consistent with SEM images of previously observed nanocomposite microsphere morphologies.

Example 9: optical performance test was performed on the color vision correcting lenses prepared in examples 1 to 7, respectively

And (1) detecting the backlight color change performance:

the detection step comprises: after the lens marks prepared in examples 1-7 were placed in a solar light simulation box for irradiation detection, the lens was irradiated at room temperature for 6min, the distance between the lens and the light source was 20CM, the irradiation amount hv=2eg, the conditions before and after the irradiation of the lens were recorded, and the detection results are shown in table one.

Surface-lens backlight color-changing condition meter

Conclusion: the above results demonstrate that the samples prepared in this example exhibit a reverse photochromic effect, which is diametrically opposed to the behavior of most pyran compounds, i.e., colorless or pale closed rings under illumination, moving to dark as colored (dark) open rings. And the color-changing speed is high.

(II) color purity (color saturation) detection:

the detection step comprises: taking the color vision correction lenses prepared in the examples 1-7, marking, respectively inserting the marked lenses into a test glasses frame, detecting color purity on a computer optometry, enabling human eyes to be 3.5m away from a straight line of a color picture, respectively grouping detected persons to detect white pieces and color vision correction lenses, and recording, wherein the details are shown in a second table; and detecting and recording by adopting a color detector, wherein the detection result is shown in a second table.

Color purity (color saturation) detection

Conclusion: the prepared lens enhances the color discrimination of eyes and has high apparent color saturation.

And (III) color blindness picture identification detection:

according to the inspection result of the color blindness inspection chart, the type and grade degree of the color vision abnormality are determined, the color mixing scale value of the TZ-1 type color vision detector and the effect of the patient on fitting the color blindness correcting lens are referred, the lenses prepared in examples 1-7 are respectively tested, and the color discrimination correcting effect is recorded, and the details are shown in the table III and fig. 13-16. The test participants can recognize 29 images at least and 39 images at most, so that the achromatopsia correcting lenses prepared in the examples 1-7 are respectively suitable for patients with red-green weakness, blue weakness, red-green achromatopsia secondary, red-green weakness and red-green-blue weakness.

Three-colour correction condition table

Chromaticity correction	Color differentiation before wearing	Color differentiation after wearing	Correcting effect
				Example 1	Red color difficult to distinguish	See clearly red	Correcting the level of red weakness
Example 2	Blue is weaker	Clear blue	Correcting blue weakness level
				Example 3	Less red	Clear red	Secondary grade for correcting erythroblindness
Example 4	Less red and green	See clearly red and green	Correcting the weak level of red and green
				Example 5	Green and weaker	See clearly blue-green	Correcting the weak level of red, blue and green
Example 6	Less red	Red color is effective	Correcting the level of red weakness
				Example 7	The red and blue are weaker	See clearly red, blue and green	Correcting the weak level of red, blue and green

Claims

1. The preparation method of the color vision correcting resin lens is characterized by comprising the following steps of:

I. preparation of organic/inorganic nano composite microsphere

i. Weighing an acrylic ester monomer, a spiropyran compound shown in a formula (I) and transition metal oxide nano particles, wherein the mass ratio of the acrylic ester monomer to the spiropyran compound to the transition metal oxide nano particles is (1-2): (2-3): (2-4) dissolving a spiropyran compound in an organic solvent;

adding purified water and an emulsifying agent into a reaction kettle, and adding transition metal oxide nano particles after complete dissolution, wherein the concentration of the transition metal oxide nano particles 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 oxide nano particles is 1: (0.5 to 1.0); the transition metal oxide nano particles are agglomerated into nano-scale clusters with uniform particles;

adding a cross-linking agent which is butyl methacrylate or diallyl phthalate into the reaction system, wherein the dosage of the cross-linking agent is 0.5-2% of the mass of the acrylate monomer, introducing nitrogen, adding a spiropyran compound solution shown in the formula I, and adsorbing spiropyran particles on the surface of an oxide cluster;

II, preparing resin lens for correcting colour vision

Adding the organic/inorganic nano composite microsphere and the initiator prepared in the step I into an acrylic ester monomer and a solvent, and uniformly stirring, wherein the mass ratio of the organic/inorganic nano composite microsphere to the acrylic ester monomer is 1: (30-200); the acrylic ester monomers in the step I and the step II are the same and are at least one selected from methyl acrylate, ethyl acrylate, 2-methyl methacrylate and 2-ethyl methacrylate; polymerizing at 65-85 deg.c for 2-3.5 hr, filtering, degassing, injecting into mold, and raising the temperature from room temperature to 85 deg.c for 12-20 hr to complete one-step solidification; then the temperature is kept at 90-110 ℃ for 1.5-3.0 hours to finish secondary curing, and the color vision correcting resin lens is obtained.

2. The method of claim 1, wherein the transition metal oxide is selected from one or more of titanium oxide, iron oxide, copper oxide and cobalt oxide, and the transition metal oxide nanoparticles have a particle size of 2 to 12nm.

3. The method according to claim 1, wherein the solvent of the spiropyran compound solution is at least one of chloroform, acetone, propyl acetate, butyl acetate, ethyl acetate, dibutyl phthalate, and petroleum ether.

4. The method of claim 1, wherein the mass ratio of the spiropyran compound to the solvent is 1: (2-3).

5. The method according to claim 1, wherein the emulsifier in the step I is at least one of RF-345, polyvinylpyrrolidone and sodium dodecylbenzenesulfonate, and the amount is 2-6g/L.

6. The method according to claim 1, wherein the initiator in the step I is at least one selected from dibenzoyl peroxide, diisopropyl peroxydicarbonate, ammonium persulfate and sodium persulfate, and the amount is 0.2-0.4% of the amount of the acrylate monomer.

7. The method according to claim 1, wherein the initiator in the step II is at least one selected from 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.

8. The method according to any one of claims 1 to 7, wherein the mass ratio of the organic/inorganic nanocomposite microsphere to the acrylate monomer in step II is 1: (55-75).