Color vision correction resin lens coating material and preparation method thereof

Abstract

The invention relates to a color vision correction resin lens coating material and a preparation method thereof, the coating material comprises: 30-40 parts by weight of an isocyanate compound; 15-30 parts by weight of a thiol compound; 5 to 25 parts by weight of polyvinyl butyral; 1-5 parts by weight of a photochromic solution; an initiator; a defoaming agent; and a wetting agent. The photochromic nano-composite microspheres are contained, an inner core of the photochromic nano-composite microspheres is composed of two spiropyrane compounds, and a shell of the photochromic nano-composite microspheres is coated with a modified acrylate material. The coating material has relatively high flexibility and firmness; on the other hand, the coating material can automatically filter light and complement color, and the color change complementation of the two color-changing materials is used for synergistically enhancing the red and green band spectrum color purity and the dimension of the color vision vector space, regulating and controlling the color vision abnormity and improving the color discrimination capability, so that the problem that color amblyopia and color-blindness patients wear color-blindness glasses for a long time to cause color blindness is solved. Therefore, excessive dependence on one color is caused, the visual quality is maintained, and the device has the advantages of being high in color saturation, good in color complementing effect, comfortable to wear and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of ophthalmic optics, and in particular relates to a color vision correction resin lens coating material and a preparation method thereof. Background Art

[0002] Color vision is a basic and important component of visual function and is a special sensory function of human retinal cone cells. The normal human visual organ can identify visible light with a wavelength of 380-760nm, which is composed of 7 colors: purple, blue, cyan, green, yellow, orange, and red. The color vision characteristic of normal people is a three-dimensional vector space, and the three basis vectors correspond to the three primary colors of red, green, and blue respectively. Each color can be represented as a point or a vector in this vector space. For a small number of people, the dimension of this vector space is less than that of normal people, and the difference in brightness is not obvious. For example, lack of color vision or abnormal color vision, inability to distinguish certain colors is color blindness or color weakness. Color blindness is a color vision disorder caused by the lack of certain cone cells, including red blindness, green blindness, blue blindness, and total color blindness. Among them, red blindness and green blindness are more common. Patients cannot distinguish between red, purple, cyan, and green, and can only recognize yellow and blue in the entire spectrum. It is usually called red-green color blindness. Total color blindness is extremely rare. Patients can only see light and dark, just like watching a black and white movie. Color-deficient patients have all three types of cone cells, but their ability to distinguish certain colors is weak. Color-deficient patients are mostly acquired, related to health and nutritional conditions, and can be prevented and treated.

[0003] Traditional color blindness correction glasses cannot increase the dimension of this vector space, but change the difference in color brightness through special color matching, thereby correcting color vision defects. It is currently recognized as an effective way to correct color blindness. It can effectively improve patients' color vision and improve color resolution. The disadvantages of existing color blindness correction glasses are poor appearance, and the lenses are obviously abnormal colors, which patients often have concerns about and affect the appearance. In addition, some color blindness glasses, while correcting color vision abnormalities, greatly attenuate the amount of normal light transmitted, making them unusable in dim light, interfering with the normal part of vision, and long-term wearing will lead to decreased vision. Summary of the invention

[0004] The purpose of the present invention is to provide a color vision correction resin lens coating material and a preparation method. On the one hand, the flexibility and durability of the coating material are improved by modifying and optimizing the polyurethane coating formula; on the other hand, the coating containing nano-color-changing composite microspheres can automatically filter and complement the color, and the color purity of the red and green band spectrum and the dimension of the color vision vector space are synergistically enhanced through the complementary color changes of two spiropyran color-changing compounds, so as to regulate color vision abnormalities and improve color discrimination ability, thereby avoiding excessive dependence on one color by color-weak and color-blind patients due to long-term wearing of color-blind glasses, maintaining visual quality, and having the advantages of high color saturation, good color complementation effect, and comfortable wearing.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] A color vision correction resin lens coating material, comprising the following components:

[0007] Component A: 30-40 parts by weight of isocyanate compound;

[0008] Component B: 15 to 30 parts by weight of thiol compound;

[0009] Component C: 5 to 25 parts by weight of polyvinyl butyral;

[0010] Component D: 1 to 5 parts by weight of photochromic solution;

[0011] Component E: initiator;

[0012] Component F: defoamer;

[0013] Component G: wetting agent;

[0014] The photochromic solution contains photochromic nanocomposite microspheres and an active solvent in a mass ratio of (1-3): (100-150);

[0015] The photosensitive color-changing nanocomposite microspheres are of a core-shell structure, wherein the core is composed of nanocrystals of two spiropyran compounds represented by formula (a) and formula (b), and the shell is coated with a modified acrylic ester material; the mass ratio of the core to the shell is (1-2): (3-5), and the particle size of the microspheres is 7-15 nm;

[0016] The modified acrylic ester material is polymerized from polyvinyl butyral and acrylic ester monomers or styrene monomers, and the mass ratio of the two is (0.5-1.5): (2-5);

[0017] The mass ratio of the two spiropyran compounds of formula (a) and formula (b) is 1:(0.3-3);

[0018]

[0019] Where R = C 16 H 33 ;

[0020]

[0021] Where R = C 16 H 33 .

[0022] The color vision correction resin lens coating material as described above, preferably, the isocyanate compound is a compound containing two or more isocyanate groups (-NCO);

[0023] As described above, the color correction resin lens coating material, preferably, the isocyanate compound is selected from at least one of toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, cyclohexane diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, 4,4'-diisocyanate dicyclohexylmethane, tetramethyl meta-xylene diisocyanate, dithiodipropyl diisocyanate, dithiodiethyl diisocyanate, dihexyl thiodiisocyanate, dithiodipropyl diisocyanate, diethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysine triisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate and triphenylmethane triisocyanate.

[0024] The color vision correction resin lens coating material as described above, preferably, the thiol compound is selected from: methanedithiol, methanetrithiol, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 1,3,5-trimercaptomethylbenzenethiol, 1,4-bis(mercaptomethyl)benzene, 1,4-butanediol bis(2-mercaptoacetate), trimethylolpropane trimercaptopropionate, pentaerythritol trimercaptoacetate, pentaerythritol tetramercaptopropionate, 1,2-dimercaptocyclohexane, diethylene glycol bis(3-mercaptopropionate), dimercaptomethyl-1,4-dithiol At least one of cyclohexane, 1,1,1-tris(mercaptomethyl)propane, ethylene glycol bis(3-mercaptopropionate), 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiacyclohexane, 4,6-bis(mercaptomethylthio)1,3-dithiacyclohexane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane.

[0025] The color vision correction resin lens coating material as described above, preferably, the acrylate monomer is selected from at least one of methacrylate styrene, methyl acrylate, ethyl acrylate, butyl acrylate, epoxy acrylate, isooctyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl methacrylate, pentaerythritol tetraacrylate, ethoxylated nonylphenol acrylate, ethoxylated bisphenol A diacrylate, polyethylene glycol methacrylate, bisphenol A epoxy acrylate, bisphenol A-dimethacrylate glycidyl ester, triethylene glycol dimethacrylate and trimethylolpropane trimethacrylate;

[0026] In the color vision correction resin lens coating material as described above, preferably, the styrene monomer is selected from styrene or methylstyrene.

[0027] As described above, in the color vision correction resin lens coating material, preferably, the active solvent is selected from at least one of styrene, methyl styrene, hydroxyethyl acrylate, hydroxyethyl acrylate, o-phenylphenoxyethyl acrylate, epoxy acrylate, bisphenol A epoxy acrylate, benzyl acrylate, ethoxylated nonylphenol acrylate, ethoxylated bisphenol A diacrylate ethoxyphenol acrylate, diphenylmethanol acrylate, 1,6-hexanediol diacrylate, polyethylene glycol methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate and trimethylolpropane triacrylate.

[0028] The color vision correction resin lens coating material as described above, preferably, the initiator is at least one of dibenzoyl peroxide, diisopropyl peroxydicarbonate and dimethylformamide; the amount of the initiator is 0.1 to 1 wt% of the isocyanate compound;

[0029] The color vision correction resin lens coating material as described above, preferably, the defoamer is one of T-1000A defoamer, DS100 silicone oil defoamer, AT350 polyether defoamer or D90 acrylic polymer defoamer; the amount of the defoamer is 0.1 to 1 wt% of the mercaptothiol compound;

[0030] In the color vision correction resin lens coating material as described above, preferably, the wetting agent is BYK acrylate wetting agent or F420 type wetting agent; the amount of the wetting agent is 0.5-2wt% of the isocyanate compound.

[0031] As described above, the color vision correction resin lens coating material, preferably, the photosensitive color-changing nanocomposite microspheres are prepared by the following method:

[0032] I. Preparation of color-changing solution: prepare a spiropyran color-changing solution by mixing spiropyran color-changing powder (a), spiropyran color-changing powder (b) and solvent in a mass ratio of (0.5-1.5):(0.5-1.5):(100-200);

[0033] II. Oil phase color change solution: polyvinyl butyral and acrylate monomers or styrene monomers are added to the spiropyran color change solution to obtain an oil phase color change solution; wherein the mass ratio of polyvinyl butyral, spiropyran color change powder and acrylate monomer is (0.5-1.5): (0.5-1.5): (2-5);

[0034] III. Preparation of O / W emulsion: preparing an aqueous solution by mixing an emulsifier with purified water in a mass ratio of (1-3):(200-500); homogenizing and emulsifying the aqueous solution and the oil phase solution to obtain an O / W emulsion; wherein the mass ratio of the oil phase solution to the aqueous solution is (1-2):(1-3);

[0035] IV. Preparation of core-shell nano-microspheres: Add carbodiimide crosslinking agent and initiator to O / W emulsion, keep warm at 25-40°C for 15-40 minutes, the spiropyran crystal core is coated in the polyacrylate shell to form a nano-core-shell structure, heat to 45-65°C for polymerization for 6-12 hours, filter, wash and dry to obtain nano-color-changing microsphere powder.

[0036] The color vision correction resin lens coating material as described above, preferably, the solvent in step I is selected from at least one of isopentane, n-hexane, n-pentane, cyclohexane and petroleum ether;

[0037] The color vision correction resin lens coating material as described above, preferably, the emulsifier in step III is selected from the group consisting of bubble-free isomeric alcohol FT-625, diethyl phthalate, steareth-21, oleth-10, stearate PEG-100 and silicone oil emulsifiers;

[0038] The color vision correction resin lens coating material as described above, preferably, the silicone oil emulsifier is selected from at least one of dimethyl silicone oil emulsifier, polydimethylsiloxane PEG-3, polydimethylsiloxane PEG-10, silicone emulsifier KF-6038 and Japan Shin-Etsu KF-6017 emulsifier, etc.;

[0039] The color vision correction resin lens coating material as described above, preferably, the carbodiimide crosslinking agent in step IV is selected from polyethylene glycol monomethyl ether MPEG350, N,N-dimethylethanolamine, carbodiimide CDI-1171, carbodiimide XL-701 and carbodiimide INV-2000; and its amount is 1-3wt% of polyvinyl butyral;

[0040] As described above, the color vision correction resin lens coating material, preferably, the initiator in step IV is selected from at least one of dibenzoyl peroxide, diisopropyl peroxydicarbonate and azobisisobutyronitrile, and its amount is 0.3-0.6wt% of the acrylate monomer or the amount.

[0041] In another aspect, the present invention provides a method for preparing the color vision correction resin lens coating material as described above, the method comprising the following steps:

[0042] I. Weigh components A to G according to the ratio;

[0043] II. The polyvinyl butyral and thiol compound are added to the isocyanate compound and stirred to obtain a prepolymer solution;

[0044] III. Dividing the prepolymer solution into two parts, namely a first prepolymer solution and a second prepolymer solution, the mass ratio of the two being 1:(0.5-3); adding the photochromic solution to the first prepolymer solution to obtain a first mixed solution; adding a wetting agent and a defoaming agent to the second prepolymer solution to obtain a second mixed solution;

[0045] IV. The first mixed solution and the second mixed solution are mixed, and the initiator is added thereto while stirring. After mixing evenly, a color vision correction resin lens coating material is obtained.

[0046] In one aspect, the present invention provides a color vision correction coated lens having a lens coating formed from the color vision correction resin lens coating material described above.

[0047] On the other hand, the present invention provides a method for preparing a color correction lens coating, which comprises filtering, degassing, and spin coating the photochromic coating material prepared above, and then thermally curing the coated lens and obtaining the color correction lens coating after cooling.

[0048] The spiropyran color-changing powder (a) of the present invention can be synthesized by the following method, but is not limited to the following method.

[0049] I. Under N2 protection, 4-hydroxyisophthalaldehyde and anhydrous ethanol are mixed, heated to reflux in an oil bath at 90-220°C, and an ethanol solution of 3,3-dimethyl-1′hexadecyl-2-methyleneindole is added dropwise thereto, the reaction solution turns purple, and the heating and reflux are continued for 4-8 hours. After ethanol is evaporated, ether is added with stirring to completely dissolve the purple-red viscous substance, and water is added with stirring. After standing, the liquid is separated to remove the water therein, and the ether and a small amount of water are evaporated again to remove the ether and a small amount of water to obtain a light purple solid spiropyran compound c; wherein the weight ratio of 4-hydroxyisophthalaldehyde, 3,3-dimethyl-1′hexadecyl-2-methyleneindole and anhydrous ethanol is (0.5-1):(2-5):(20-50);

[0050]

[0051] II. Take an appropriate amount of the spiropyran compound c and malonyl urea prepared in step I above and add them to a reaction vessel containing chloroform, protect with N2, stir until completely dissolved, add dropwise a chloroform solution of pyridine, heat the reactants in an oil bath under reflux, cool to room temperature, adjust the pH to neutral with dilute hydrochloric acid, wash twice with water, extract the organic layer and evaporate to dryness to obtain a green solid powder; the weight ratio of malonyl urea, spiropyran compound c, pyridine and chloroform is (0.5-1): (0.7-1.5): (5-20): (50-150); the pyridine content in the pyridine solution is 3-5%.

[0052] The preparation method of the spiropyran color-changing powder (b) described in the present invention can refer to the method described in Patent ZL201711112631.2 "A Photochromic Optical Material".

[0053] The beneficial effects of the present invention are as follows:

[0054] 1. The color vision correction resin lens coating material contains photosensitive color-changing nanocomposite microspheres, which are core-shell structure nanomicrospheres, whose core is composed of nanocrystals of two spiropyran compounds with different structures of formula (a) and formula (b), and the shell is coated with modified acrylic material. Spiropyran compound (a) is green in normal indoor light and colorless after ultraviolet light irradiation. Spiropyran compound (b) is colorless in normal indoor light and red after ultraviolet light irradiation. The two color-changing compounds have a significant complementary color effect. When applied to color vision correction optical materials, they can improve the accuracy and saturation of colors, make images more realistic and vivid, and have a satisfactory color correction effect for red-green color blindness or color weakness. At the same time, the alternating red and green color changes under different light environments can regulate the visual nerves and avoid visual fatigue caused by long-term single color.

[0055] 2. Longer branched polyvinyl butyral (PVB) molecules are introduced into the coating material to optimize and modify the film-forming process of the polyurethane polymer material, thereby improving the flexibility and durability of the coating material.

[0056] 3. Under the premise of maintaining good optical properties and fastness, the material cost can be effectively reduced by reducing the amount of high-cost materials such as isocyanate and thiol and increasing the amount of low-cost materials such as polyvinyl butyral. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 This is a comparison chart of the color vision correction lens prepared in Example 1 before and after wearing it under normal indoor light.

[0058] Figure 2 This is a comparison chart of the color vision correction lens prepared in Example 2 before and after wearing it outdoors in sunlight. DETAILED DESCRIPTION

[0059] The present invention is further described below by means of specific examples, but this is not intended to limit the protection scope of the present invention.

[0060] The spiropyran photochromic compounds in the following examples and comparative examples are prepared by the following method:

[0061] (I) Preparation of spiropyran photochromic compound a:

[0062] A. Under N2 protection, 250 g of 4-hydroxyisophthalaldehyde was mixed with 11 kg of anhydrous ethanol, and the mixture was heated to reflux in an oil bath at 180°C. An ethanol solution containing 1400 g of 3,3-dimethyl-1′-hexadecyl-2-methyleneindole was added dropwise thereto. The reaction solution turned purple and was heated to reflux for 5.5 hours. After ethanol was evaporated, ether was added with stirring to completely dissolve the purple-red viscous substance. Water was then added with stirring. After standing, the mixture was separated to remove water. The mixture was evaporated to dryness again to remove ether and a small amount of water to obtain a pale purple solid spiropyran compound (c).

[0063] The specific reaction formula is as follows:

[0064]

[0065] B. Take 100 g of the compound of formula (c) and 45 g of malonylurea and add them to 8500 g of chloroform, protect with N2, stir until completely dissolved, add 920 g of chloroform solution of pyridine dropwise thereto, heat the reactants under reflux in an oil bath, cool to room temperature, adjust the pH to neutral with a small amount of dilute hydrochloric acid, wash with water twice, extract the organic layer, and evaporate to dryness to obtain 127 g of green solid powder, i.e., spiropyran photochromic compound (a).

[0066] The specific reaction formula is as follows:

[0067]

[0068] (II) Preparation of spiropyran photochromic compound b:

[0069] Heat 250 g of 2-hydroxy-1-naphthaldehyde ethanol solution in an oil bath, heat to 60°C under nitrogen protection until reflux, add 25 g of 3,3-dimethyl-1′-hexadecyl-2-methyleneindole ethanol solution dropwise, continue to reflux for 9 hours, cool to room temperature, evaporate the solvent and concentrate to 40%, seal and place in an ice bath at -2°C for 15 hours, filter, elute and dry to obtain spiropyran photochromic powder b.

[0070] (III) Preparation of photosensitive color-changing nanocomposite microspheres:

[0071] (1) 4.5 g of spiropyran color-changing powder a and 2.0 g of spiropyran color-changing powder b were dissolved in a mixed solvent of 450 g of isopentane and 130 g of n-pentane to obtain a spiropyran color-changing solution.

[0072] (2) 5.5 g of polyvinyl butyral and 16.5 g of hydroxypropyl methacrylate monomer were added to the above spiropyran solution to obtain an oil phase solution.

[0073] (3) 1.9 g of silicone emulsifier KF-6038 was added to 750 g of pure water to prepare an aqueous phase solution, and the aqueous phase solution and the oil phase solution were homogenized and emulsified to obtain an O / W emulsion.

[0074] (4) Preparation of core-shell nanospheres: 0.08 g of carbodiimide CDI-1171 and 0.07 g of diisopropyl peroxydicarbonate were added to the O / W emulsion and reacted at 22°C for 30 minutes. The spiropyran crystal core was encapsulated in the polyacrylate shell to form a nano core-shell structure. The temperature was raised to 55°C for polymerization for 10 hours. The mixture was filtered, washed and dried to obtain photosensitive color-changing nanocomposite microsphere powder.

[0075] Example 1: Preparation of Color Correction Coated Lenses

[0076] (1) 90 g of polyvinyl butyral and 220 g of methanetrimercaptan were added to 350 g of isophorone diisocyanate and stirred to obtain a prepolymer solution;

[0077] (2) adding 0.6 g of photochromic nanocomposite microspheres to 30 g of hydroxyethyl acrylate and stirring to obtain a photochromic solution;

[0078] (3) The prepolymer solution prepared in step (1) was divided into two parts: 300 g of a first prepolymer solution and 360 g of a second prepolymer solution. The photochromic solution was added to the first prepolymer solution to obtain a first mixed solution; 4 g of F420 wetting agent and 0.6 g of DS100 silicone oil defoaming agent were added to the second prepolymer solution to obtain a second mixed solution;

[0079] (4) mixing the first mixed solution and the second mixed solution, adding 0.65 g of dibenzoyl peroxide initiator with stirring, and mixing evenly to obtain a photosensitive color-changing coating liquid;

[0080] (5) The photochromic coating liquid prepared above was filtered and degassed with a PTFE filter membrane with a pore size of 0.2 μm, and then spin-coated onto the surface of the lens substrate at a speed of 2500 rpm. The coated lens was then placed in an oven at 120° C. for thermal curing for 120 min. After cooling, a color correction coated lens was obtained.

[0081] Example 2: Preparation of Color Correction Coated Lenses

[0082] (1) 95 g of polyvinyl butyral and 290 g of trimethylolpropane trimercaptopropionate were added to 320 g of toluene diisocyanate and stirred to obtain a prepolymer solution;

[0083] (2) adding 0.6 g of photochromic nanocomposite microspheres to 30 g of epoxy acrylate and stirring to obtain a photochromic solution;

[0084] (3) The prepolymer solution was divided into two parts, namely, 400 g of a first prepolymer solution and 305 g of a second prepolymer solution, the photochromic solution was added to the first prepolymer solution to obtain a first mixed solution, and 4.2 g of F420 wetting agent and 0.6 g of DS100 silicone oil defoaming agent were added to the second prepolymer solution to obtain a second mixed solution;

[0085] (4) mixing the first mixed solution and the second mixed solution, adding 0.65 g of dibenzoyl peroxide initiator with stirring, and mixing evenly to obtain a photosensitive color-changing coating liquid;

[0086] (5) The photochromic coating liquid prepared above was filtered and degassed with a PTFE filter membrane with a pore size of 0.2 μm, and then spin-coated onto the surface of the lens substrate at a speed of 2500 rpm. The coated lens was then placed in an oven at 120° C. for thermal curing for 120 min. After cooling, a color correction coated lens was obtained.

[0087] Example 3: Preparation of Color Correction Coated Lenses

[0088] (1) 100 g of polyvinyl butyral and 185 g of pentaerythritol trimercaptoacetate were added to 300 g of hexamethylene diisocyanate and stirred to obtain a prepolymer solution;

[0089] (2) adding 0.5 g of photochromic nanocomposite microspheres into 28 g of bisphenol A epoxy acrylate and stirring to obtain a photochromic solution;

[0090] (3) the prepolymer solution was divided into two parts, namely, 300 g of a first prepolymer solution and 285 g of a second prepolymer solution, the photochromic solution was added to the first prepolymer solution to obtain a first mixed solution, and 4.2 g of a BYK acrylate wetting agent and 0.5 g of a T-1000A defoaming agent were added to the second prepolymer solution to obtain a second mixed solution;

[0091] (4) mixing the first mixed solution and the second mixed solution, adding 0.65 g of diisopropyl peroxydicarbonate initiator with stirring, and mixing evenly to obtain a photosensitive color-changing coating liquid;

[0092] (5) The photochromic coating liquid prepared above was filtered and degassed with a PTFE filter membrane with a pore size of 0.2 μm, and then spin-coated onto the surface of the lens substrate at a speed of 2500 rpm. The coated lens was then placed in an oven at 120° C. for thermal curing for 120 min. After cooling, a color correction coated lens was obtained.

[0093] Example 4: Preparation of Color Correction Coated Lenses

[0094] (1) 100 g of polyvinyl butyral and 235 g of methanetrimercaptan were added to 280 g of isophorone diisocyanate and stirred to obtain a prepolymer solution;

[0095] (2) adding 0.5 g of photochromic nanocomposite microspheres to 30 g of epoxy acrylate and stirring to obtain a photochromic solution;

[0096] (3) The prepolymer solution was divided into two parts, namely, 300 g of a first prepolymer solution and 315 g of a second prepolymer solution, the photochromic solution was added to the first prepolymer solution to obtain a first mixed solution, and 4 g of an F420 wetting agent and 0.6 g of a DS100 silicone oil defoaming agent were added to the second prepolymer solution to obtain a second mixed solution;

[0097] (4) mixing the first mixed solution and the second mixed solution, adding 0.6 g of dibenzoyl peroxide initiator with stirring, and mixing evenly to obtain a photosensitive color-changing coating liquid;

[0098] (5) The photochromic coating liquid prepared above was filtered and degassed with a PTFE filter membrane with a pore size of 0.2 μm, and then spin-coated onto the surface of the lens substrate at a speed of 2500 rpm. The coated lens was then placed in an oven at 120° C. for thermal curing for 120 min. After cooling, a color correction coated lens was obtained.

[0099] Example 5: Preparation of Color Correction Coated Lenses

[0100] (1) 90 g of polyvinyl butyral and 270 g of methanedithiol were added to 270 g of cyclohexane diisocyanate and stirred to obtain a prepolymer solution;

[0101] (2) adding 0.5 g of photochromic nanocomposite microspheres to 29 g of bisphenol A epoxy acrylate and stirring to obtain a photochromic solution;

[0102] (3) the prepolymer solution was divided into two parts, namely, 300 g of a first prepolymer solution and 330 g of a second prepolymer solution, the photochromic solution was added to the first prepolymer solution to obtain a first mixed solution, and 4 g of a BYK acrylate wetting agent and 0.6 g of a T-1000A defoaming agent were added to the second prepolymer solution to obtain a second mixed solution;

[0103] (4) mixing the first mixed solution and the second mixed solution, adding 0.6 g of diisopropyl peroxydicarbonate initiator with stirring, and mixing evenly to obtain a photosensitive color-changing coating liquid;

[0104] (5) The photochromic coating liquid prepared above was filtered and degassed with a PTFE filter membrane with a pore size of 0.2 μm, and then spin-coated onto the surface of the lens substrate at a speed of 2500 rpm. The coated lens was then placed in an oven at 120° C. for thermal curing for 120 min. After cooling, a color correction coated lens was obtained.

[0105] Example 6: Preparation of Color Correction Coated Lenses

[0106] (1) 95 g of polyvinyl butyral and 165 g of trimethylolpropane trimercaptopropionate were added to 260 g of toluene diisocyanate and stirred to obtain a prepolymer solution;

[0107] (2) adding 0.5 g of photochromic nanocomposite microspheres into 30 g of methylstyrene and stirring to obtain a photochromic solution;

[0108] (3) The prepolymer solution was divided into two parts, namely, 300 g of a first prepolymer solution and 220 g of a second prepolymer solution, the photochromic solution was added to the first prepolymer solution to obtain a first mixed solution, and 4.1 g of F420 wetting agent and 0.5 g of DS100 silicone oil defoaming agent were added to the second prepolymer solution to obtain a second mixed solution;

[0109] (4) mixing the first mixed solution and the second mixed solution, adding 0.6 g of dibenzoyl peroxide initiator with stirring, and mixing evenly to obtain a photosensitive color-changing coating liquid;

[0110] (5) The photochromic coating liquid prepared above was filtered and degassed with a PTFE filter membrane with a pore size of 0.2 μm, and then spin-coated onto the surface of the lens substrate at a speed of 2500 rpm. The coated lens was then placed in an oven at 120° C. for thermal curing for 120 min. After cooling, a color correction coated lens was obtained.

[0111] Example 7: Color saturation detection

[0112] The CM-20 color analyzer produced by Shenzhen Tongpu Technology Co., Ltd. was used to perform color saturation analysis on the color vision correction coated lens prepared in Example 1. The color vision correction coated lens was placed on a standard chromatogram, and the color contrast value, the color contrast value of the standard chromatogram without the lens placed, and the difference between the two were recorded. The test results are shown in Table 1.

[0113] Table 1 Color contrast detection table

[0114]

[0115] Conclusion: The test shows that the red light value is larger under daylight, and the green light value is higher under normal indoor light. Therefore, it can be judged that the lens has a high resolution of red and green colors in different environments.

[0116] Example 8: Color purity detection and analysis

[0117] Testing steps: The color vision correction lenses prepared in Examples 1 to 6 were marked and inserted into trial frames for color purity testing. The human eye was 3.5 m away from the chromaticity chart. A color detector was used to perform naked eye testing and trial lens testing using a chromaticity table as a scale and the test results were recorded. The test results are shown in Table 2.

[0118] Table 2 Color purity detection table

[0119]

[0120] Conclusion: The lenses prepared in Examples 1-6 enhance the color discrimination ability of the eyes and the color purity of the objects seen is high.

[0121] Example 9: Color blindness image recognition detection

[0122] According to the test results of the "Color Blindness Test Chart", the degree of color vision abnormality is determined. Referring to the mixed color scale value of the TZ-1 color vision tester and the effect of the patient's trial wearing of color blindness correction lenses, the lenses prepared in Examples 1 to 6 are respectively tested for color blindness picture recognition, and the color correction effect is recorded, as shown in Tables 3 and Figures 1-2 , the number of patterns recognized by the test participants increased significantly, thus judging that the color blindness correction lenses prepared in Examples 1-6 are suitable for patients with red-green color deficiency and sub-severe red-green color deficiency, respectively.

[0123] Table 3 Color blindness correction status table

[0124]

[0125]

[0126] Example 10: Film Flexibility Test

[0127] The coating monomer was subjected to a flexibility test in accordance with GB1731 "Determination of paint film flexibility" using a flexibility tester. The specific operating steps were as follows: the coating liquid prepared in Examples 1-6 was sprayed on a test film plate. After curing, the test plate was pressed tightly onto a shaft rod of a specified diameter with both hands with the film layer facing upward. The test plate was bent around the shaft rod within 2 to 3 seconds using the strength of both thumbs. After bending, the film layer was observed with a magnifying glass. The experimental results showed that the film layer had no damage such as reticulation, cracks, and peeling, and the film layer had high flexibility.

[0128] Example 11: Film firmness test experiment

[0129] The lens film layers prepared in Examples 1-6 were subjected to a cross-cut test using a tape method, according to the national standard GB10810.4-2012. The test method is as follows: scratch the filter surface with a utility knife, then scratch it from a vertical angle, and finally leave more than 25 small squares on the lens surface. 3M invisible tape was used to stick to the squares, and the tape was torn off in the backward direction at a slightly faster and more stable speed. The cross-cut test results show that the film layer did not fall off and the film layer had high firmness.

Claims

1. A color vision correction resin lens coating material, characterized in that: It contains the following components: The photochromic solution contains photochromic nanocomposite microspheres and an active solvent, and the mass ratio of the two is (1-3): (100-150): The photosensitive color-changing nanocomposite microspheres are of a core-shell structure, wherein the core is composed of nanocrystals of two spiropyran compounds represented by formula (a) and formula (b), and the shell is coated with a modified acrylic ester material; the mass ratio of the core to the shell is (1-2): (3-5), and the particle size of the microspheres is 7-15 nm; The modified acrylic ester material is polymerized from polyvinyl butyral and acrylic ester monomers or styrene monomers, and the mass ratio of the two is (0.5-1.5): (2-5); The mass ratio of the two spiropyran compounds of formula (a) and formula (b) is 1:(0.3-3); Where R = C 16 H 33 ; Where R = C 16 H 33 .

2. The color vision correction resin lens coating material according to claim 1, characterized in that: The isocyanate compound is a compound containing two or more isocyanate groups; preferably, it is selected from at least one of toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, cyclohexane diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 4,4'-diisocyanate dicyclohexylmethane, tetramethyl meta-xylylene diisocyanate, dithiodipropyl diisocyanate, dithiodiethyl diisocyanate, dihexyl thiodiisocyanate, dithiodipropyl diisocyanate, diethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysine triisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate and triphenylmethane triisocyanate.

3. The color vision correction resin lens coating material according to claim 1, characterized in that: The thiol compound is selected from the group consisting of methanedithiol, methanetrithiol, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 1,3,5-trimercaptomethylbenzenethiol, 1,4-bis(mercaptomethyl)benzene, 1,4-butanediol bis(2-mercaptoacetate), trimethylolpropane trimercaptopropionate, pentaerythritol trimercaptoacetate, pentaerythritol tetramercaptopropionate, 1,2-dimercaptocyclohexane, diethylene glycol bis(3-mercaptopropionate), dimercaptomethyl-1,4-dithiol cyclohexane, 1,1,1-trimercaptomethyl-1,4-dithiol cyclohexane, At least one of (mercaptomethyl)propane, ethylene glycol bis(3-mercaptopropionate), 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiacyclohexane, 4,6-bis(mercaptomethylthio)1,3-dithiacyclohexane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane.

4. The color vision correction resin lens coating material according to claim 1, characterized in that: The acrylic acid ester monomer is selected from at least one of methacrylate styrene, methyl acrylate, ethyl acrylate, butyl acrylate, epoxy acrylate, isooctyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl methacrylate, pentaerythritol tetraacrylate, ethoxylated nonylphenol acrylate, ethoxylated bisphenol A diacrylate, polyethylene glycol methacrylate, bisphenol A epoxy acrylate, bisphenol A-dimethacrylate glycidyl ester, triethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; The styrene monomer is selected from styrene or methylstyrene.

5. The color vision correction resin lens coating material according to claim 1, characterized in that: The active solvent is selected from at least one of styrene, methyl styrene, hydroxyethyl acrylate, hydroxyethyl acrylate, o-phenylphenoxyethyl acrylate, epoxy acrylate, bisphenol A epoxy acrylate, benzyl acrylate, ethoxylated nonylphenol acrylate, ethoxylated bisphenol A diacrylate ethoxyphenol acrylate, biphenylmethanol acrylate, 1,6-hexanediol diacrylate, polyethylene glycol methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate and trimethylolpropane triacrylate.

6. The color vision correction resin lens coating material according to claim 1, characterized in that: The initiator is at least one of dibenzoyl peroxide, diisopropyl peroxydicarbonate and dimethylformamide; the amount of the initiator is 0.1 to 1 wt% of the isocyanate compound; The defoamer is one of T-1000A defoamer, DS100 silicone oil defoamer, AT350 polyether defoamer or D90 acrylic acid polymerization defoamer; the amount of the defoamer is 0.1-1wt% of the mercaptothiol compound; The wetting agent is BYK acrylate wetting agent or F420 wetting agent; the amount of the wetting agent is 0.5-2wt% of the isocyanate compound.

7. The color vision correction resin lens coating material according to claim 1, characterized in that: The photosensitive color-changing nanocomposite microspheres are prepared by the following method: I. Preparation of color-changing solution: prepare a spiropyran color-changing solution by mixing spiropyran color-changing powder (a), spiropyran color-changing powder (b) and solvent in a mass ratio of (0.5-1.5):(0.5-1.5):(100-200); II. Oil phase color change solution: polyvinyl butyral and acrylate monomers or styrene monomers are added to the spiropyran color change solution to obtain an oil phase color change solution; wherein the mass ratio of polyvinyl butyral, spiropyran color change powder and acrylate monomer is (0.5-1.5): (0.5-1.5): (2-5); III. Preparation of O / W emulsion: preparing an aqueous solution by emulsifying an emulsifier and purified water in a mass ratio of (1 to 3): (200 to 500); homogenizing and emulsifying the aqueous solution and the oil phase solution to obtain an O / W emulsion; The mass ratio of the oil phase solution to the water phase solution is (1-2):(1-3); IV. Preparation of core-shell nano-microspheres: Add carbodiimide crosslinking agent and initiator to O / W emulsion, keep warm at 25-40°C for 15-40 minutes, the spiropyran crystal core is coated in the polyacrylate shell to form a nano-core-shell structure, heat to 45-65°C for polymerization for 6-12 hours, filter, wash and dry to obtain nano-color-changing microsphere powder.

8. The color vision correction resin lens coating material according to claim 7, characterized in that: The solvent in step I is selected from at least one of isopentane, n-hexane, n-pentane, cyclohexane and petroleum ether; The emulsifier in step III is selected from the group consisting of foam-free isomeric alcohol FT-625, diethyl phthalate, steareth-21, oleth-10, stearate PEG-100 and silicone oil emulsifiers; The silicone oil emulsifier is selected from at least one of dimethyl silicone oil emulsifier, polydimethylsiloxane PEG-3, polydimethylsiloxane PEG-10, silicone emulsifier KF-6038 and Japan Shin-Etsu KF-6017 emulsifier; The carbodiimide crosslinking agent in step IV is selected from polyethylene glycol monomethyl ether MPEG350, N,N-dimethylethanolamine, carbodiimide CDI-1171, carbodiimide XL-701 and carbodiimide INV-2000; and its amount is 1-3wt% of polyvinyl butyral; The initiator in step IV is selected from at least one of dibenzoyl peroxide, diisopropyl peroxydicarbonate and azobisisobutyronitrile, and its amount is 0.3-0.6wt% of the amount of the acrylic acid ester monomer or the amount of the acrylic acid ester monomer.

9. The method for preparing the color vision correction resin lens coating material according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: I. Weigh components A to G according to the ratio; II. The polyvinyl butyral and thiol compound are added to the isocyanate compound and stirred to obtain a prepolymer solution; III. The prepolymer solution is divided into two parts, namely, a first prepolymer solution and a second prepolymer solution, the mass ratio of the two being 1: (0.5 to 3); the photochromic solution is added to the first prepolymer solution to obtain a first mixed solution; adding a wetting agent and a defoaming agent to the second prepolymer solution to obtain a second mixed solution; IV. Mix the first mixed solution and the second mixed solution, add the initiator with stirring, and mix well to obtain the color vision correction resin lens coating material.

10. A color vision correction coating lens, characterized in that: The lens has a lens coating formed of the color vision correction resin lens coating material according to any one of claims 1 to 8.

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