Photochromic dye compounds and their applications in contact lenses for red-green color blindness correction

Abstract

The present invention provides a photochromic dye compound, the chemical structure of which is shown in Formula (X): wherein R1 is selected from NH2, NO3, dimethylamino, hydrogen, or piperidinyl; R2 is selected from alkoxy, carbonyl, alkyl, or hydrogen; R3 is selected from methoxy or hydrogen; R4 is selected from benzyl, vinyl, propenyl, or methacryl; and n represents an integer of 1 to 4. The photochromic dye compound is a compound with naphthopyran as the main structure. The photochromic dye compound is prepared by utilizing a specific structure and groups, and has higher photostability and thermal stability than spiropyran and spirozolinoid photochromics. The photochromic red-green color blindness correction contact lens of the present invention has the function of correcting red-green color blindness; compared to the single function of traditional contact lenses and red-green color blindness correction lenses, it also has the function of reducing light intensity sunglasses and protecting against ultraviolet and blue light.

Description

Technical Field

[0001] The invention belongs to the technical field of contact lenses and photochromic materials, and particularly relates to a photochromic dye compound and an application thereof in contact lenses for correcting red-green color blindness. Background Art

[0002] The ability of the human eye to distinguish and discern colors is primarily due to the presence of different types of photoreceptor cells, known as cones, on the human retina. Humans typically possess three types of cones, which are most sensitive to yellow-green (red), green, and blue-violet (blue) light (peak wavelengths of 560 nm, 530 nm, and 420 nm, respectively). When light of different wavelengths enters the retina, these three types of cones are stimulated to varying degrees, and the brain processes the visual signals, recombining them to produce different colors. The peak response of normal cones varies from person to person, but the absence or defect of any of the three types of cones can lead to color blindness, impaired color perception and the inability to distinguish colors correctly. This can cause numerous challenges in daily life, most notably the inability of patients to recognize the color of traffic lights.

[0003] There is still no cure for color blindness, but it can be corrected by increasing the color vision of color blind patients so that they can accurately distinguish colors close to that of normal eyes. The commonly used method to correct color blindness is to wear color blindness correction glasses, which mainly include frame lenses and contact lenses. Color blindness correction contact lenses mainly filter specific wavelengths of light by printing or coating the optical area of ​​the contact lens or adding specific dyes to the lens, thereby enhancing the color vision of color blind patients. Printing or coating technology is more commonly used in contact lenses. For example, the Chinese invention patent CN108803077B lens adopts a "sandwich" structure, and the color blindness correction film layer is placed on the inner and outer layers of the lens. However, this technology has the following series of problems, such as the complicated process, uneven printing, low lens transmittance, dye diffusion, etc. For local dyeing in finished lenses, the dye is immersed and penetrated into specific areas of the lens, so that contact lenses that filter specific wavelengths can be produced. This technology is more commonly used in early colored contact lenses. However, due to the unsatisfactory curing effect of the dye and the lens, diffusion will occur during the storage and use of the lens, causing damage to the eyes.

[0004] Chinese invention patent CN113248466B adds a specific dye, such as rhodamine B, to the starting monomer mixture for lenses. The lens and dye are then chemically bonded, thus avoiding the shortcomings of the aforementioned technologies and offering advantages such as uniform dye distribution and dye diffusion resistance. However, the lenses produced using this technology exhibit a relatively single pattern, remaining red in both bright outdoor light and dim indoor light conditions. This single functional pattern is not suitable for the actual eye characteristics of individuals with red-green color blindness. Individuals with red-green color blindness often have sensitive eyes and are prone to photophobia. Therefore, the red and green light filtering requirements for red-green color blind lenses differ in bright outdoor light and dim indoor light. In bright light, not only does it need to absorb red or green light, but it also needs to reduce light intensity. In dim light, it needs to increase light transmission to enhance the amount of light entering the eye. Furthermore, contact lenses for these individuals require additional features to meet their daily needs, such as UV protection to reduce the risk of cataracts. Frequent use of electronic products can also damage the eyes, exposing them to blue light and causing fatigue. Therefore, blue light protection has become a necessary feature in contact lenses. Summary of the Invention

[0005] The present invention aims to address the above-mentioned technical problems by providing a photochromic dye compound. Lenses containing this photochromic dye compound are required to not only absorb red or green light to correct red-green color blindness outdoors, but also reduce light intensity and other harmful light. In low-light conditions, this compound increases light transmission, allowing more light to enter the eye. In other words, contact lenses for red-green color blindness correction incorporating this photochromic dye compound simultaneously provide UV and blue light protection. Another object of the present invention is to provide the use of this compound in contact lenses for red-green color blindness correction.

[0006] To achieve the above object, the present invention adopts the following technical solutions:

[0007] A photochromic dye compound, characterized in that the photochromic dye compound has a general chemical structure as shown in formula (X):

[0008]

[0009] (X)

[0010] In formula (X), R1 is selected from -NH2, -NO3, dimethylamino, hydrogen or piperidinyl; R2 is selected from alkoxy, carbonyl, alkyl or hydrogen; R3 is selected from methoxy or hydrogen, and R4 is selected from polymerizable groups such as benzyl, vinyl, propenyl or methacryl; and n represents an integer from 1 to 4.

[0011] The mechanism of the present invention is as follows: This photochromic dye compound, based on a naphthopyran as its main structure, exhibits higher stability, particularly photostability and thermal stability, compared to spiropyran and spirozosin photochromics. By utilizing the different types and positions of substituents on the naphthopyran main structure, the naphthopyran main structure undergoes ring opening under ultraviolet activation, resulting in varying degrees of absorption of specific wavelengths of light. Ultimately, depending on the substituents and their positions, the lens exhibits a red or green hue, correcting red-green color blindness. The lens also provides UV and blue light protection, as well as light-reducing sunglasses.

[0012] Furthermore, the photochromic dye compound is a red photochromic dye compound, and its general chemical structure is shown in formula (XI):

[0013]

[0014] (Ⅺ);

[0015] In the formula (XI), R1 is selected from an alkyl group, an alkoxy group or a carbonyl group; R2 is selected from an alkoxy group; R3 is selected from a benzyl group, a vinyl group, a propenyl group or a methacryl group; and n represents an integer of 1-4.

[0016] Furthermore, the chemical structure of the red photochromic dye compound is shown in formula (I):

[0017]

[0018] (Ⅰ).

[0019] Furthermore, the photochromic dye compound is a green photochromic dye compound, and its general chemical structure is shown in formula (XII):

[0020]

[0021] (XII);

[0022] In formula (XII), R1 is selected from alkyl, alkoxy or carbonyl; R2 is selected from -NH2, -NO3, dimethylamino, pyrrolidinyl and piperidinyl; R3 is selected from benzyl, vinyl, propenyl or methacryl; and n represents an integer of 1-4.

[0023] Furthermore, the chemical structure of the green photochromic dye compound is shown in formula (V):

[0024]

[0025] (V).

[0026] The present invention provides use of the photochromic dye compound in preparing ophthalmic products.

[0027] Furthermore, the ophthalmic product is a contact lens, a photochromic red-green color blindness contact lens or other implantable ophthalmic device product.

[0028] The present invention provides an ophthalmic product as described above, comprising the photochromic dye compound as described above.

[0029] Furthermore, the amount of the photochromic dye compound used in the ophthalmic product is 0.1-5.0% of the total mass of monomers required for preparing the ophthalmic product.

[0030] The present invention provides a red-green color blindness correction contact lens, comprising the above-mentioned photochromic dye compound and contact lens monomers. The amount of the photochromic dye compound in the red-green color blindness correction contact lens is 0.1-5.0% of the total mass of the contact lens monomers.

[0031] The beneficial effects of the present invention are as follows:

[0032] (1) The present invention utilizes the color difference and functional change of naphthopyran compounds before and after color change to invent photochromic red-green color blindness correction contact lenses. The photochromic contact lenses of the present invention have the function of correcting red-green color blindness.

[0033] (2) Compared with the single function of traditional contact lenses and lenses for correcting red and green color blindness, it also has the function of sunglasses that reduce light intensity and the function of blocking ultraviolet and blue light. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 These are the appearance pictures of contact lenses for correcting type I red-green color blindness at different concentrations; A in the picture represents the indoor appearance; B represents the appearance under outdoor activation.

[0035] Figure 2 These are the appearance pictures of contact lenses for correcting V-type red-green color blindness at different concentrations; C in the picture represents the indoor appearance; D represents the appearance under outdoor activation.

[0036] Figure 3 This is the effect of wearing contact lenses for correcting type I and type V red-green color blindness on a prosthetic eye (in activated state). In the figure, E represents the prosthetic eye; F represents wearing contact lenses for correcting type I red-green color blindness on a prosthetic eye; G represents wearing contact lenses for correcting type V red-green color blindness on a prosthetic eye.

[0037] Figure 4 The appearance of contact lenses with different concentrations of BR-1 (before sterilization, after sterilization, indoors and outdoors).

[0038] Figure 5 The appearance of contact lenses with different concentrations of MG-1 (before sterilization, after sterilization, indoors and outdoors).

[0039] Figure 6 Comparison of light transmittance of BR-1 (0.5%) contact lenses before and after sterilization (indoor).

[0040] Figure 7 Comparison of light transmittance of MG-1 (0.4%) contact lenses before and after sterilization (indoor).

[0041] Figure 8 Light transmittance curves of contact lenses for correcting type I and type V red-green color blindness. DETAILED DESCRIPTION

[0042] In order to enable those skilled in the art to better understand the solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts should fall within the scope of protection of the present invention.

[0043] Unless otherwise specified, the reagents and drugs involved in the embodiments of the present invention are commercially available and can be obtained and used by those skilled in the art through channels known in the art.

[0044] Example 1 Polymerizable Photochromic Compound I (Red Dye)

[0045] This embodiment provides a polymerizable photochromic compound, the color of which after photochromism is red. The polymerizable photochromic compound is a naphthopyran compound, and its chemical structure is shown in Formula (I).

[0046]

[0047] (I).

[0048] The preparation method of the above compound is:

[0049] S1. Under nitrogen protection and maintaining the temperature at 0°C, NaH (67 g, 2.5 eq) was slowly added to a solution of 2-(4-bromophenyl)ethanol (245 g, 1.1 eq) in DMF (1700 ml, 10 V). After stirring for 1 h, p-chloromethylstyrene (245 g, 1.1 eq) was added. The solution was then heated to 25°C and stirred for 18 h. The reaction mixture was added dropwise to purified water (1500 ml), extracted twice with EA (1000 ml), washed with brine (1500 ml), and dried over anhydrous sodium sulfate to obtain the final product II (175 g, white solid, 50% yield).

[0050]

[0051] (II)

[0052] S2. Under nitrogen protection and at -70°C, slowly add to a THF (1300 ml) solution containing compound II (170.0 g, 1.0 eq) n -BuLi (236 ml, 1.1 eq), and the reaction mixture was stirred at -60°C for 1 hour. A solution of 4,N-dimethoxy-N-methyl-benzamide (115.1 g, 1.1 eq) in THF (400 ml) was slowly added to the reaction mixture, and the mixed solution was heated to 0°C and stirred for another 2 hours. The reaction mixture was added dropwise to a saturated NH4Cl solution (500 ml), extracted twice with EA (500 ml), dried over anhydrous sodium sulfate, and concentrated to obtain a crude product. The crude product was mixed with petroleum (850 ml) at 25°C for 0.5 h. The solid was filtered and washed with petroleum (100 ml) to obtain the final product III: (4-methoxy-phenyl)-{4-[2-(4-vinyl-benzyloxy)-ethyl]-phenyl}-methanone} (167 g, white solid, 83.7% yield).

[0053]

[0054] (III)

[0055] S3. Under nitrogen, maintaining the temperature at -70°C, n-BuLi (233 mL, 1.3 eq) was slowly added to a solution of trimethylsilylacetylene (57.3 g, 1.3 eq) in THF (1300 mL). The reaction mixture was then stirred at -60°C for 1 h. A solution of Compound III (167 g, 1.0 eq) in THF (400 mL) was then slowly added to the reaction mixture. The mixed solution was heated to 20°C and stirred for another 2 h. The reaction mixture was added dropwise to a saturated NH4Cl solution (1000 mL), extracted twice with EA (500 mL), dried over anhydrous sodium sulfate, and concentrated to obtain a crude product. The crude product was added to methanol (1000 mL), followed by the addition of K2CO3 (31.0 g, 0.5 eq) and stirred for 1 h. The solid was then filtered to obtain the crude product. The crude product was further purified by silica gel column chromatography and diluted with EA / PE = 10%-15% to give a yellow oily final product IV: 1-(4-methoxy-phenyl)-1-{4-[2-(4-vinyl-benzyloxy)-ethyl]-phenyl}-prop-2-yn-1-ol (151.3 g, yellow oil, yield 85%).

[0056]

[0057] (IV)

[0058] S4. Under nitrogen, maintaining the temperature at 25°C, to a solution of compound IV (46.3 g, 1.0 eq) in DCE (200 mL) was added 3,4-dimethylnaphthalen-1-ol (20.0 g, 1.0 eq), trimethyl orthoformate (14.6 g, 2.0 eq), and PPTS (1.46 g, 0.05 eq). The reaction mixture was then heated to 80°C and stirred for 6 h. The reaction mixture was cooled to 25°C, purified water (200 mL) was added, and stirred for 30 min. The aqueous phase was separated, and the organic phase was concentrated to afford the product, 2-(4-methoxyphenyl)-5,6-dimethyl-2-{4-[2-(4-vinyl-benzyloxy)-ethyl]-phenyl}-2H-benzo[h]chromene (31.0 g, off-white solid, 48% yield). H NMR spectroscopy results are as follows: 1 H NMR (CDCl3, ppm) δ8.37-8.35 (m, 1H), 7.91-7.89 (d, 1H), 7.47-7.37 (m, 6H), 7.34-7.32 (d, 2H), 7.21 (d, 2H), 7.14 (d, 2H), 6.97 (d, 1H), 6.80 (d, 2H), 6.69 (dd, 1H), 6.18 (d, 1H), 5.72 (d, 1H), 5.22 (d, 1H), 4.48 (s, 2H), 3.74 (s, 3H), 3.64 (t, 2H), 2.88 (t, 2H), 2.50 (s, 3H), 2.41 (s, 3H).

[0059]

[0060] (I)

[0061] Comparative Example 1 Photochromic compound (BR-1)

[0062] The red photochromic compound used in Comparative Example 1 is 2,2-bis-(4-methoxyphenyl)-5,6-dimethyl-2H-benzo[h]chromene, purchased from James Robinson Specialty Ingredients in the UK. This photochromic compound does not contain any polymerizable groups and has the following structure (BR-1). Its structure is similar to that of Photochromic Compound I in Example 1, except that it contains a polymerizable benzyl group. Therefore, in Comparative Example 1, it was added solely as a dye to the monomer mixture to investigate the stability, photochromic appearance, and light transmittance of the lenses.

[0063]

[0064] (BR-1).

[0065] Example 2: Polymerizable Photochromic Compound V (Green Dye)

[0066] This embodiment provides a polymerizable photochromic compound, the color of which after photochromism is green. The polymerizable photochromic compound is a naphthopyran compound, and its chemical structure satisfies the formula.

[0067]

[0068] (V).

[0069] Its preparation method is:

[0070] S1. Under nitrogen, 4-(bromomethyl)benzophenone (1000 g, 3.6 mol), K2CO3 (1256 g, 5.4 mol), Triton B (40% aqueous solution, 100 ml), dioxane (7 L), and water (3 L) were added to a flask in sequence. The mixed solution was stirred under reflux for 24 h, and a sample was taken for LCMS analysis. Saturated NH4Cl (10 L) was then added to the reaction solution, and the mixture was extracted twice with ethyl acetate (10 L). The organic extract was dried over anhydrous Na2SO4 (100 g). Finally, the solution was filtered and concentrated under vacuum to obtain the product: (4-hydroxymethyl-phenyl)phenyl-methanone (264 g, yellow oil, 34.2% yield).

[0071]

[0072] S2. Under nitrogen, a flask was charged with (4-hydroxymethyl-phenyl)phenyl-methanone (263 g, 1.2 mol), 1-chloromethyl-4-vinylbenzene (210 g, 1.1 eq), KOH (140 g, 2.0 eq), and acetonitrile (2.5 L). The mixture was stirred at 50–60°C for 16 h. After stirring, the mixture was cooled to 10–20°C and sampled for LCMS analysis. The mixture was filtered, washed with acetonitrile (0.5 L), and then concentrated to dryness under vacuum. The dried mixture was stirred in n-heptane (0.9 L) at 10–20°C for 3 h, filtered, and washed with n-heptane (0.1 L). The wet cake was dried under vacuum at 40–50°C for 6 h to obtain a brown solid product: phenyl-[4-(4-vinyl-benzyloxymethyl)-phenyl]-methanone (390 g, 95.8% yield).

[0073]

[0074] S3. Under nitrogen protection, add ethynyltrimethylsilane (233.3 g, 2.0 eq) and anhydrous THF (2.4 L) to the flask in sequence, and then cool the solution to -75 to -65°C. n A solution of 1-BuLi (570 ml, 1.2 eq) was added dropwise to the solution and stirred for 0.5 h. A solution of phenyl-[4-(4-vinyl-benzyloxymethyl)-phenyl]-methanone in THF (390 g, 1.6 L THF, 1.0 eq) was added dropwise to the mixed solution. After stirring for 1 h, the mixture was naturally warmed to 10-20°C and sampled for LCMS analysis. Saturated NH4Cl (5 L) was added to the reaction solution, and the mixture was extracted with ethyl acetate (3 L x 2). The organic extract was dried over anhydrous Na2SO4 (100 g), filtered, and concentrated under vacuum. The resulting mixture, K2CO3 (328 g, 2.0 eq), and methanol (4 L) were added to a flask and stirred at 10-20°C for 2 h. The mixture was filtered, and the filtrate was concentrated under vacuum. The resulting mixture was dissolved in ethyl acetate (3 L) and washed with saturated NH4Cl (3 L x 2). The organic solution was dried over anhydrous Na2SO4 (100 g) and concentrated under vacuum to give a black oil: 1-phenyl-1-[4-(4-vinyl-benzyloxymethyl)-phenyl]-prop-2-yn-1-ol (390 g, yield: 92.7%).

[0075]

[0076] S4. 1-Phenyl-1-[4-(4-vinyl-benzyloxymethyl)-phenyl]-prop-2-yn-1-ol (250 g, 1.0 eq), 6-dimethylamino-4-hydroxynaphthalene-2-carboxylic acid methyl ester (190 g, 1.1 eq), camphorsulfonic acid (246 g, 1.5 eq), and dichloromethane (2.5 L) were added to a flask in sequence. The mixture was stirred at 25-30°C for 16 h, and a sample was taken for LCMS analysis. The pH of the mixture was adjusted to 7-8 with 5% NaHCO3. After filtering the mixture, the organic layer was concentrated under vacuum to obtain a green solid product, 9-dimethylamino-2-phenyl-2-[4-(4-vinyl-benzyloxymethyl)-phenyl]-2H-benzo[ h ]chromene-5-carboxylic acid methyl ester (110 g, yield 26.8%). The results of H NMR spectrum are as follows: 1 H NMR (CDCl3, ppm) δ7.92 (s, 1H), 7.64 (d, 1H), 7.58 (d, 1H), 7.42-7.45 (m, 4H), 7.15-7.23 (m, 6H), 7.07 (dd, 1H), 6.62 (dd, 1H), 6.12 (d, 1H), 5.65 (dd, 1H), 5.15 (dd, 1H), 4.44 (s, 2H), 4.40 (s, 2H), 3.82 (s, 3H), 3.03 (s, 6H).

[0077]

[0078] V.

[0079] Comparative Example 2 Photochromic Compound (MG-1)

[0080] The photochromic compound used in Comparative Example 2 was methyl 9-dimethylamino-2-phenyl-2-(4-piperidinyl-phenyl)-2H-benzo[h]chromene-5-carboxylate, purchased from James Robinson Specialty Ingredients in the UK. This photochromic compound does not contain any polymerizable groups and has the following structure: MG-1. It has a similar structure to the photochromic compound V in Example 2, differing in that the polymerizable benzyl group in V is an alkyl linker, while the linker in Comparative Example MG-1 is a piperidinyl group and cannot participate in polymerization. Therefore, Comparative Example MG-1 was added solely as a dye to the monomer mixture to compare the stability, photochromic appearance, and light transmittance of the lenses.

[0081]

[0082] (MG-1).

[0083] Example 3: Preparation of Type I Photochromic Red-Green Blindness Contact Lenses (Red Lenses)

[0084] This embodiment provides a method for preparing type I photochromic red-green color blindness contact lenses, as follows:

[0085] P1. Preparation of lens main body mixed liquid

[0086] The polymerizable type I photochromic compound, polymerization monomer, crosslinking agent and initiator are mixed evenly. A UV absorber and a blue light absorber can be added as needed to obtain a lens mixture. The specific raw materials are as follows:

[0087] 8.73 g of hydroxyethyl methacrylate (HEMA), 8.50 g of N-vinyl pyrrolidone (NVP), 0.03 g of methacrylic acid (MAA), 2.00 g of glycerol monomethacrylate (GMMA), 1.00 g of ethylene glycol dimethacrylate (EGDMA), and 0.04 g of azobisisobutyronitrile (AIBN), where the amount of type I photochromic compound added is 0.6% of the total mass of the above raw material monomers, and the mixture is stirred for 8 h.

[0088] P2. Lens curing

[0089] The lens mixture prepared in P1 is injected into the mold (female mold), and then combined with the male mold to form a chemically cross-linked contact lens dry piece under thermal or UV curing conditions.

[0090] P3. Lens hydration

[0091] The finished contact lenses are obtained through subsequent hydration, extraction, microscopic examination, potting, and high-temperature steam sterilization. The finished products are packaged in a preservative containing standard saline solution. The sterilization conditions for contact lenses are 121°C and 20 min in accordance with GBT19973.2-2018.

[0092] Example 4-6: Preparation of Type I Photochromic Red-Green Blindness Contact Lenses (Red Lenses)

[0093] The preparation method was the same as that in Example 3. The type I photochromic compound used in this example was added in amounts of 0.1%, 0.2%, and 0.4% of the total mass of the raw material monomers, respectively. The mixture was stirred for 8 hours. The subsequent production steps were the same as in Example 3 to prepare contact lenses of Examples 4-6.

[0094] Example 7: Preparation of V-type photochromic red-green color blindness contact lenses (green lenses)

[0095] The preparation method was the same as that of Example 3. The V-type photochromic compound used in this example was added in an amount of 0.6% of the total mass of the raw material monomers. The mixture was stirred for 8 h. The subsequent production steps were the same as those of Example 3 to prepare Example 7.

[0096] Examples 8-11: Preparation of V-type photochromic red-green color blindness contact lenses (green lenses)

[0097] The preparation method was the same as that of Example 3. The V-type photochromic compound used in this example was added in amounts of 0.1%, 0.2%, 0.4% and 0.8% of the total mass of the raw material monomers, respectively. The mixture was mixed and stirred for 8 hours. The subsequent production steps were the same as those of Example 3 to prepare contact lens examples 8-11.

[0098] Comparative Examples 3-7: Preparation of BR-1 Red-Green Color Blindness Contact Lenses

[0099] The preparation method was the same as that in Example 3. The photochromic compound in Comparative Example BR-1 used in this example was added in amounts of 0.1%, 0.2%, 0.5%, 0.6% and 0.8% of the total mass of the raw monomers, respectively. The mixture was mixed and stirred for 8 hours. The subsequent production steps were the same as those in Example 3 to prepare contact lenses of Comparative Examples 3-7.

[0100] Comparative Examples 8-11: Preparation of MG-1 Contact Lenses

[0101] The preparation method was the same as that of Example 3. The photochromic compound of Comparative Example MG-1 used in this example was added in amounts of 0.2%, 0.4%, 0.6% and 0.8% of the total mass of the raw material monomers. The mixture was mixed and stirred for 8 hours. The subsequent production steps were the same as those of Example 3 to prepare contact lens Comparative Examples 8-11.

[0102] Experimental Example 1: Contact Lens Appearance Observation and Stability Test

[0103] 1. Experimental Methods

[0104] The appearance of the contact lenses prepared according to Example 3-11 and Comparative Example 3-11 was observed, and the unsterilized lenses were used as controls to observe the color differences of the lenses indoors and outdoors.

[0105] 2. Experimental Results

[0106] like Figure 1-Figure 5 The contact lenses using the BR-1 compound in Examples 3-6 and Comparative Examples 3-7 (before sterilization) were colorless indoors but red when excited outdoors. The lenses in Examples 7-11 were colorless indoors but green when excited outdoors. The contact lenses in Comparative Examples 8-11, using the MG-1 compound, were colorless indoors (before sterilization) but bluish-gray when excited outdoors. This demonstrates that differences in substituent position can lead to discoloration differences.

[0107] The photochromic compounds of Examples 3-6 and 7-11 all contain polymerizable groups and can be polymerized into lenses through chemical bonds and other monomers. The polymerizable photochromic compounds can improve the appearance stability and light transmittance of the lenses. The lenses of Examples 3-6 (arranged in increasing concentration from left to right, where the first one on the left is a control lens without any color-changing compound) and Comparative Examples 3-7 are both red. The appearance and light transmittance of the lenses of Example 3 do not change before and after sterilization. According to GBT19973.2-2018, the sterilization conditions for contact lenses are 121°C and more than 20 minutes. Figure 4-Figure 5As shown, the lenses of Comparative Examples 3-7 were colorless and transparent before sterilization, but after sterilization, they became milky white, exhibiting reduced transparency and poor light transmittance. During the sterilization process, the photochromic compound BR-1 used in the comparative example escaped from the material. The lenses of Examples 7-11 (arranged from left to right in increasing concentration, with the first on the left being the control lens without any photochromic compound) showed no change in appearance or light transmittance before and after sterilization. However, the appearance and light transmittance of Comparative Examples 8-11 were similar to those of Comparative Example BR-1, exhibiting a milky white appearance. Therefore, by incorporating photochromic compounds with polymerizable groups into the material through chemical polymerization, the final material's appearance stability and light transmittance can be improved. However, non-polymerizable photochromic compounds cannot be used in contact lens products due to their poor stability.

[0108] Experimental Example 2: Light transmittance test

[0109] (1) Experimental methods

[0110] The transmittance of the lenses was tested using a UV-visible photometer. The lenses tested were divided into (1) two colors: containing type I photochromic agent (red) and type V photochromic agent (green); (2) containing different concentrations of type I or type V photochromic agent; (3) two environments: normal lenses under indoor conditions (photochromic agent inactive state) and photochromic lenses under outdoor conditions (photochromic agent inactive state), where the lens color becomes darker; and the light transmittance of BR-1 and MG-1 was tested before and after sterilization. According to GBT11417.5-2012, the light transmittance of the lenses was scanned in the 280-780 nm band (ultraviolet region 280-380 nm, visible light region 380-780 nm, blue light region 380-460 nm).

[0111] (2) Experimental results

[0112] Depend on Figure 8 It can be seen that there are three typical contact lenses: ordinary transparent lenses, lenses with 0.6% type I photochromic red-green color blindness contact lenses, and lenses with 0.6% type V photochromic red-green color blindness contact lenses. The ordinary transparent lenses do not contain any photochromic agents, ultraviolet absorbers, or blue light filtering absorbers, and their light transmittance is all above 95%.

[0113] When a 0.6% Type I photochromic red-green color blindness contact lens is added, its UVA and UVB transmittance is 44.8% and 25.9%, respectively, under indoor conditions, while its blue light transmittance is 93.2%. There is no significant change in visible light transmittance. However, under outdoor sunlight, the Type I photochromic dye in the lens is activated, causing the lens to turn from colorless to deep red. The lens's light transmittance is generally reduced, with UVA and UVB transmittances of only 8.5% and 2.2%, respectively, and blue light transmittance and visible light transmittance of only 10.6% and 46.3%, respectively.

[0114] Table 1 summarizes the light transmittance of different concentrations of type I photochromic red-green color blindness contact lenses. As the concentration increases from 0 to 0.6%, the UV transmittance of the lens decreases under indoor conditions, but its blue light and visible light transmittance do not change significantly. Under outdoor sunlight conditions, the photochromic dye in the lens is activated, and the UV transmittance, blue light and visible light transmittance all decrease significantly. The color of the lens becomes more and more obvious, and the color changes from colorless to deep red. For detailed appearance, see Figure 1 .

[0115] When 0.6% V-type photochromic red-green color blindness contact lenses were added, the UVA and UVB transmittances were 53.7% and 35.2%, respectively, and the blue light transmittance was 84.8%, with no significant change in visible light transmittance under indoor conditions. Under outdoor sunlight, the V-type photochromic dye in the lenses activated the lenses, causing them to turn from colorless to dark green. The lenses' light transmittance generally decreased, with UVA and UVB transmittances of only 1.8% and 0.6%, respectively, and blue light transmittance and visible light transmittance of only 7.8% and 47.5%, respectively. Table 2 summarizes the light transmittance of V-type photochromic red-green color blindness contact lenses at different concentrations. As the concentration increased from 0 to 0.8%, the UV transmittance decreased under indoor conditions. For type I photochromic red-green color blindness contact lenses, there was no significant change in blue light and visible light transmittance, but for V-type photochromic red-green color blindness contact lenses, both blue light and visible light transmittance decreased significantly. Under outdoor sunlight conditions, the photochromic dye in the lens is activated, and the UV transmittance, blue light and visible light transmittance are greatly reduced. The color of the lens becomes more and more obvious, and the color changes from colorless to dark green. For detailed appearance, see Figure 2 ; Figure 3 The effects of Type I and Type V photochromic red-green color blindness contact lenses worn on prosthetic eyes outdoors are demonstrated.

[0116] Combine Figure 6-7 It can be seen that by testing the light transmittance of BR-1 and MG-1 before and after sterilization, it can be found that the light transmittance of these two materials drops significantly after sterilization, and their performance drops sharply.

[0117] Table 1 Light transmittance of Examples 3-6 indoors and outdoors (Type I)

[0118]

[0119] Table 2 Light transmittance of Examples 7-11 indoors and outdoors (V-type)

[0120]

[0121] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the solution. Although the present invention has been described in detail with reference to the preferred embodiments, ordinary technicians in this field should understand and can modify or replace the technical solution of the present invention based on the understanding of this solution without departing from the purpose and scope of the technical solution of the present invention, which should be covered by the scope of the claims of the present invention.

Claims

1. A photochromic dye compound, characterized in that The chemical structure of the photochromic dye compound is shown in formula (I) or formula (V): Formula (I) is: Formula (V) is:

2. Use of the photochromic dye compound according to claim 1 in the preparation of ophthalmic products.

3. The use according to claim 2, characterized in that The ophthalmic products are contact lenses, photochromic red-green color blindness contact lenses or other implantable ophthalmic devices.

4. An ophthalmic product, characterized in that: The invention comprises the photochromic dye compound according to claim 1.

5. The ophthalmic product according to claim 4, characterized in that The amount of the photochromic dye compound used in the ophthalmic product is 0.1-5.0% of the total mass of monomers required for preparing the ophthalmic product.

6. A red-green color blindness correction contact lens, characterized in that: The invention comprises the photochromic dye compound according to claim 1 and contact lens monomers, wherein the amount of the photochromic dye compound in the red-green color blindness correction contact lens is 0.1-5.0% of the total mass of the contact lens monomers.

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