A blue light-proof photochromic resin lens

Abstract

A blue light-proof photochromic resin lens, wherein the lens substrate comprises the following components: 25 to 100 parts by weight of a thermosetting or thermoplastic optical resin, 0.6 to 3 parts by weight of a photochromic material, 0.1 to 1 parts by weight of a porphine metal complex, and 0.2 to 0.8 parts by weight of a quinophthalone compound; the porphine metal complex is selected from at least one of the following structures: type A: zinc octaethylporphine; type B: nickel octaethylporphine; type C: zinc 5,10,15,20-tetrakis(pentafluorophenyl)porphine; type D: zinc tetraphenylporphine. The lens can realize the dual functions of protecting against high-energy blue light from indoor LED light sources and protecting against ultraviolet rays after discoloration under outdoor light. The blue light absorbing material compounded by porphine metal complex and quinophthalone compound has characteristic absorption of high-energy blue light in the 400-435nm spectral region while maintaining high transmittance, and partially transmits ultraviolet light, which does not affect the color-changing function of the photochromic material under strong light and has good weather resistance.

Description

Technical Field

[0001] The invention relates to a blue light-proof photochromic resin lens, in particular to a photochromic resin lens that effectively absorbs high-energy blue light in the 400-435nm spectral region, and belongs to the technical field of resin lens manufacturing. Background Art

[0002] White light LED as a display manufacturing technology for the backlight system of display devices has become the mainstream product technology of existing electronic display technology. This type of display screen is widely used in mobile communication terminal equipment, computer equipment, home and commercial display equipment and entertainment equipment. The blue light hazards and "blue-enriched" photobiological safety issues caused by white light LED are major technical defects of this type of display screen. The light radiation hazards of white light LED are mainly manifested as short-wavelength high-energy blue light with a peak of about 435nm, which can cause retinal photochemical damage and apoptosis of epidermal cells on the pigment. Short-wave blue light has high energy and strong tissue penetration ability, and has a certain destructive effect on the biological photosensitive groups of mammals, which can cause retinal lesions. Pathological studies have confirmed that the high-energy blue light in white light LED plays a certain accelerating role in the formation mechanism of age-related macular degeneration. Because the retinal macula of children has a weak absorption capacity for blue light, the amount of blue light radiation transmitted under the same light intensity is about twice that of adults, and blue light radiation is more harmful to the retina of children. If young people in the growth and development period are exposed to high-energy blue light lighting environment for a long time, it may induce blinding eye diseases at the mildest and cause lifelong vision impairment at the worst.

[0003] Ultraviolet radiation accounts for about 7% of the total solar radiation energy. Excessive ultraviolet radiation during outdoor activities can cause photochemical reactions in biological tissues, especially damaging human skin, eyes, and immune system. The human eye is the most sensitive part to ultraviolet rays. Long-term and repeated exposure to ultraviolet rays can cause acute conjunctivitis and retinal diseases. Ultraviolet radiation is also an important cause of senile cataracts.

[0004] Therefore, functional protective lenses that protect vision and safeguard eye health have become high-profit products in the lens market. The development technology of photochromic lenses for outdoor activities in strong light environments has become mature and stable, and various types of light-colored or non-base-colored photochromic sunglasses have been sold for many years and have been recognized by the market; high-energy blue light protection glasses for indoor dim light environments have also become a hot industry in the lens market; on this basis, combined with the high-energy blue light protection needs of people who come into contact with electronic display equipment, innovative eyewear products with both outdoor photochromic and indoor high-energy blue light protection functions have emerged in recent years.

[0005] The human eye is not sensitive to blue light in the 400-440nm range for vision and color discrimination, and the light in this band has a short wavelength and high energy, which is harmful to the eyes. High-energy blue light protection lenses should maintain a low transmittance for this part of blue light; the 440-500nm range is medium and long-wave blue light, which is relatively less harmful to the human eye, and can effectively regulate the body's biological rhythm and optic nerve feedback, so that the human eye can accurately judge the color of the observed object, and a certain transmittance should be maintained for this part of blue light.

[0006] Photochromic lenses, also known as "photosensitive lenses", are based on a reversible molecular reaction mechanism of light-color interconversion. When the lens switches between indoor and outdoor light, it can quickly darken under the ultraviolet light in the outdoor light, block strong light and absorb ultraviolet light, but not absorb visible light. When it returns to the indoor low-ultraviolet or no-ultraviolet environment, the lens can quickly fade and return to a colorless and transparent state to ensure the light transmittance of the lens. Therefore, photochromic lenses can be used both indoors and outdoors, and can effectively prevent damage to the eyes from sunlight, ultraviolet light, and glare.

[0007] The main technical difficulty in combining photochromic lenses with blue light protection functions is that the various types of organic blue light absorption protection materials that are currently used most have certain spectral absorption in the ultraviolet light region, especially in the specific ultraviolet spectrum region that can cause photochromic materials to change color. Blending them with photochromic materials to produce blue light protection photochromic lenses will increase the amount of photochromic materials added by multiples, greatly increasing the manufacturing cost; and it will affect the color change and fading speed when used as a photochromic lens, resulting in low color change intensity, incomplete fading and the presence of background color, which brings consumers a poor user experience.

[0008] Therefore, under the premise of ensuring effective absorption of high-energy blue light, it is of obvious commercial value to find and develop organic blue light absorbing materials that have no absorption in the ultraviolet light region, have low industrial production and processing costs, and have high weather resistance for use in anti-blue light photochromic lenses and anti-blue light film products. Summary of the invention

[0009] In view of the above problems of the prior art, the present invention provides a blue light-proof photochromic resin lens, which realizes the dual functions of protecting against high-energy blue light from indoor LED light sources and ultraviolet light after discoloration under outdoor light. The blue light absorbing material compounded by porphine metal complex and quinophthalone compound has characteristic absorption of high-energy blue light in the 400-435nm spectral region while maintaining high light transmittance, and partially transmits ultraviolet light, which does not affect the color-changing function of the photochromic material under strong light and has good weather resistance.

[0010] To achieve the above object, the present invention includes the following technical solutions:

[0011] A blue light-proof photochromic resin lens, wherein the lens substrate comprises the following components: 25 to 100 parts by weight of a thermosetting or thermoplastic optical resin, 0.6 to 3 parts by weight of a photochromic material, 0.1 to 1 part by weight of a porphine metal complex, and 0.2 to 0.8 parts by weight of a quinophthalone compound;

[0012] The porphine metal complex is selected from at least one of the following structures: Type A: octaethylporphine zinc; Type B: octaethylporphine nickel; Type C: 5,10,15,20-tetrakis(pentafluorophenyl)porphine zinc; Type D: tetraphenylporphine zinc;

[0013]

[0014] The structural formula of the quinophthalone compound is as follows:

[0015]

[0016] As described above, the blue light blocking photochromic resin lens, preferably, the lens substrate comprises the following components: 50-100 parts by weight of thermosetting or thermoplastic optical resin material, 0.6-2.5 parts by weight of photochromic material, 0.1-1 parts by weight of porphine metal complex and 0.2-0.8 parts by weight of quinophthalone compound.

[0017] As for the blue light blocking photochromic resin lens as described above, preferably, the thermosetting or thermoplastic optical resin is selected from one or more of polymethyl methacrylate, polystyrene, and bisphenol A epoxy resin.

[0018] As described above, the anti-blue light photochromic resin lens, preferably, the monomer for preparing the thermosetting or thermoplastic optical resin is selected from one or more of isocyanate, styrene, methacrylic acid, polyethylene glycol dimethacrylate, pentaerythritol tetraacrylate, ethoxylated nonylphenol acrylate, epoxy acrylate, bisphenol A epoxy acrylate, methyl styrene, polyacrylate, ethoxylated bisphenol A diacrylate and butyl methacrylate.

[0019] As the above-mentioned blue light blocking photochromic resin lens, preferably, the photochromic material is a spiropyran and / or spirooxazine photochromic material.

[0020] As described above, the blue light protection photochromic resin lens, preferably, the photochromic material is N-(β-hydroxyethyl)-3,3-dimethyl-6-nitrospiroindolinebenzopyran, 1,3,3-trimethylindole-6-nitrobenzodihydropyranospirane and / or 1,3,3-trimethylindole-β-naphthyldihydrofuran.

[0021] In a preferred embodiment of the present invention, the blue light blocking photochromic resin lens is prepared by the following method:

[0022] I. Base material ingredients

[0023] Prepare the substrate ingredients according to the following ingredients and proportions: 25-100 parts by weight of thermosetting or thermoplastic optical resin monomer, 0-0.8 parts by weight of diluent, 0.6-3 parts by weight of photochromic material, 0.5-3 parts by weight of curing agent, 0.1-1 parts by weight of porphine metal complex and 0.2-0.8 parts by weight of quinophthalone compound (Formula I);

[0024] The porphine metal complex is selected from at least one of the following structures: Type A, octaethylporphine zinc; Type B, octaethylporphine nickel; Type C, 5,10,15,20-tetrakis(pentafluorophenyl)porphine zinc; Type D, tetraphenylporphine zinc;

[0025] II. Preparation of lens substrate mixture

[0026] a. Preparation of acrylic substrates by the following operation: accurately weigh the above-mentioned substrate ingredients except the curing agent, mix and stir until completely dissolved, add the curing agent while maintaining the temperature at 20 to 30 ° C, stir for 1 to 2 hours to make it uniformly mixed, and obtain a lens substrate mixture;

[0027] b. The following steps are used to prepare polyurethane resin substrates: accurately weigh the above-mentioned substrate ingredients except the curing agent, stir after mixing until completely dissolved, add the curing agent, seal and stir at 30-40°C, cool to 15-20°C with ice water, stir in a vacuum with a vacuum degree of -0.09MPa, stop stirring and return to room temperature to obtain the lens substrate mixture.

[0028] III. Casting

[0029] After the lens substrate mixture is degassed, the material temperature is maintained at 15-30°C, filtered through a tetrafluoroethylene filter with a pore size of <0.1μm under inert gas pressure, injected into the lens mold through a feeding device, and programmed to heat and cure in a computer-controlled temperature curing furnace. The temperature is lowered to 70-80°C and the mold is removed to obtain the lens substrate.

[0030] In the preparation method as described above, the thermosetting or thermoplastic optical resin monomer is selected from one or more of m-xylylene diisocyanate, styrene, methacrylic acid, polyethylene glycol dimethacrylate, pentaerythritol tetraacrylate, ethoxylated nonylphenol acrylate, epoxy acrylate, bisphenol A epoxy acrylate, methyl styrene, polyacrylate, ethoxylated bisphenol A diacrylate and butyl methacrylate.

[0031] In the preparation method as described above, the curing agent is selected from one or more of dibutyltin dilaurate, diisopropyl peroxydicarbonate, tert-butyl peroxy-2-ethylhexyl carbonate, 1,1′-azo(cyanocyclohexane), diisopropyl azodicarboxylate, azobisisoheptonitrile, dimethyl azobisisobutyrate, diethyl azobisisobutyrate, isopropylbenzene hydroperoxide, and tert-butyl hydroperoxide.

[0032] In the preparation method as described above, the diluent is a mixture of one or more of toluene, xylene, alkyl methacrylate, hydroxyethyl methacrylate, pentaerythritol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, n-butanol and trimethylolpropane.

[0033] The beneficial effects of the present invention are as follows:

[0034] 1. The present invention replaces conventional organic small molecule blue light absorbers such as benzophenone, benzotriazole or alkyl indole used in the prior art with a porphine complex and quinophthalone composite blue light absorbing material with absorption selectivity. The composite blue light absorbing material has a certain transmittance in the ultraviolet spectrum region, ensuring the ultraviolet radiation intensity required for photochromism, and avoiding the interference of anti-blue light materials on the color change of photochromic materials; at the same time, under the premise of maintaining high transmittance, it has characteristic absorption of high-energy blue light in the 400-435nm spectrum region, realizing the dual functions of protecting indoor LED light sources from high-energy blue light and protecting against ultraviolet rays after outdoor light discoloration.

[0035] 2. Compared with the prior art, the composite blue light absorbing material used in the present invention has a significant blue light protection effect under the condition of less addition. The average cutoff rate of blue light with a wavelength of 400-435nm reaches more than 80%, and the amount of photochromic material added is also relatively reduced by more than 50%, which reduces the production cost and has little impact on the physical properties of the lens.

[0036] 3. The anti-blue light photochromic resin lens of the present invention has strong light stability and good weather resistance. It solves the problems of low color change intensity and incomplete fading in the existing anti-blue light photochromic resin lens production technology, and can be widely used in the fields of automobile windows, optical protective glass, LED lamp protective film, mobile phone protective screen, ophthalmic protective equipment, etc., to solve the damage to human eyes caused by harmful high-energy blue light from ultraviolet rays and LED light sources. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] 1. Figure 1 This is a spectral transmittance curve of the lens prepared in Example 2.

[0038] 2. Figure 2 This is a spectral transmittance curve of the lens prepared in Comparative Example 1.

[0039] 3. Figure 3This is a spectral transmittance curve of the lens prepared in Comparative Example 2.

[0040] 4. Figure 4 This is a comparison curve of the spectral transmittance of the lenses prepared in Comparative Example 3 and Comparative Example 4.

[0041] 5. Figure 5 This is a spectral transmittance curve of the lens prepared in Comparative Example 5.

[0042] 6. Figure 6 This is a spectral transmittance curve of the lens prepared in Comparative Example 6.

[0043] 7. Figure 7 This is a spectral transmittance curve of the lens prepared in Comparative Example 7.

[0044] 8. Figure 8 This is a spectral transmittance curve of the lens prepared in Comparative Example 8.

[0045] 9. Fig. 9 This is a spectral transmittance curve of the lens prepared in Comparative Example 9. DETAILED DESCRIPTION

[0046] The content of the present invention is further described in detail below by specific examples. The raw materials, reagents or devices used in the examples and comparative examples, unless otherwise specified, can be obtained from conventional commercial sources, or can be obtained by prior art methods. Unless otherwise specified, the experiments or test methods are conventional methods in the art. The embodiments of the present invention are not limited to the following examples, and any other changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principle of the present invention should all be equivalent replacement methods, and are all included in the protection scope of the present invention.

[0047] The sources of some raw materials in the following examples are as follows:

[0048] Octaethylporphine zinc (type A): Jiangsu Shike New Materials Co., Ltd., trade name: SK408

[0049] Nickel octaethylporphine (Type B): Jiangsu Shike New Materials Co., Ltd., Trade name: SK316

[0050] 5,10,15,20-Tetrakis(pentafluorophenyl)porphine zinc (Type C): Jiangsu Shike New Materials Co., Ltd., Trade name: SK318

[0051] Tetraphenylporphine zinc (D type): Jiangsu Shike New Materials Co., Ltd., trade name: SK320

[0052] N-(β-Hydroxyethyl)-3,3-dimethyl-6-nitrospiroindolinebenzopyran: Jiangsu Shike New Materials Co., Ltd., trade name: Lan 274

[0053] 1,3,3-Trimethylindole-6-nitrobenzodihydropyranospirane: Jiangsu Shike New Materials Co., Ltd., trade name: Lan 275

[0054] 1,3,3-Trimethylindole-β-naphthyldihydrofuran: Jiangsu Shike New Materials Co., Ltd., trade name: Lan 276

[0055] The quinophthalone compound shown in formula I is prepared according to the method described in Chinese Patent No.: ZL 201710101651.3.

[0056] Example 1 Anti-blue light photochromic lens (I)

[0057] I. Preparation of Type A Anti-blue Light Color-changing Composite Resin

[0058] Weigh 1500g of polyethylene glycol dimethacrylate, then add 8g of type A porphine metal complex, 7g of quinophthalone (Formula I), 20g of N-(β-hydroxyethyl)-3,3-dimethyl-6-nitrospiroindoline benzopyran photochromic material and 0.4g of xylene diluent, add 500g of m-xylene diisocyanate (XDI) and 15g of diisopropyl azodicarboxylate curing agent, and stir for 30 minutes at a temperature of 40°C. Cool to 18°C ​​with ice water, stir in vacuum for 60 minutes, and the vacuum degree is -0.09MPa. Stop stirring and return to room temperature to obtain a photochromic composite resin containing type A blue light absorber.

[0059] II. Preparation of Blue Light-Proof Photochromic Substrate

[0060] After ultrasonic degassing of the photochromic composite resin containing type A blue light absorber, the material temperature was maintained at 20°C, filtered through a polytetrafluoroethylene filter with a pore size of 0.1 μm by nitrogen pressurization, and then injected into a lens mold, and placed in a computer-controlled temperature curing furnace for program temperature rise and curing. The thermal curing temperature curve is as follows: keep warm at 40°C for 8 hours, evenly heat to 65°C within 6 hours, continue to heat to 100°C for 4 hours and keep the temperature constant for 2 hours, cool to 70°C within 1 hour, complete curing, and obtain a (polyurethane) resin anti-blue light photochromic substrate.

[0061] Example 2 Anti-blue light photochromic lens (II)

[0062] I. Preparation of Type B Anti-blue Light Color-changing Composite Resin

[0063] Weigh 25g of methyl styrene, 25g of polyacrylate, 25g of ethoxylated bisphenol A diacrylate, and 25g of butyl methacrylate, then add 0.3g of B-type porphine metal complex, 0.25g of quinophthalone (Formula I), 1.2g of 1,3,3-trimethylindole-6-nitrobenzodihydropyran and spirane photochromic material, 0.8g of 1,3,3-trimethylindole-β-naphthyl dihydrofuran photochromic material, and 0.4g of xylene diluent, add to a conical flask and stir for 1 hour, add 2.0g of azobisisoheptanitrile curing agent and evacuate at room temperature for 30 minutes, stirring and mixing continuously during this process. Then control the temperature at 35°C, stir at a rate of 500r / min, and stand and evacuate for 90 minutes. Obtain a photochromic composite resin containing a B-type blue light absorber.

[0064] II. Preparation of Blue Light Blocking Photochromic Lens Substrate

[0065] After ultrasonic degassing of the photochromic composite resin mixture containing the type B blue light absorber, the material temperature is maintained at 20°C (specific temperature), naturally filtered through a 0.1 μm polytetrafluoroethylene filter, injected into a lens mold and sealed, and programmed to rise from room temperature to 100°C in a computer-controlled curing furnace over 20 hours. The programmed temperature rise curve is as follows: ① maintain 35°C for 0 to 4 hours; ② rise to 60°C at a constant speed for 4 to 12 hours; ③ rise to 100°C at a constant speed for 12 to 18 hours; ④ maintain 100°C for 18 to 20 hours; ⑤ open the mold after cooling to 70°C to obtain an (acrylate) resin anti-blue light photochromic substrate.

[0066] Example 3 Anti-blue light photochromic lens (III)

[0067] I. Preparation of C-type anti-blue light color-changing composite resin

[0068] Weigh 25g of methyl styrene, 25g of polyacrylate, 25g of ethoxylated bisphenol A diacrylate, and 25g of butyl methacrylate, then add 0.5g of C-type porphine metal complex, 0.35g of quinophthalone (Formula I), 1.0g of 1,3,3-trimethylindole-6-nitrobenzodihydropyran and spirane photochromic material, 0.5g of 1,3,3-trimethylindole-β-naphthyl dihydrofuran photochromic material, and 0.4g of xylene diluent into a conical flask and stir for 1 hour, add 2.0g of azobisisoheptylnitrile curing agent and evacuate at room temperature for 30 minutes, stirring and mixing continuously during this process. Then control the temperature at 35°C, stir at a rate of 500r / min, and stand and evacuate for 90 minutes. Obtain a photochromic composite resin containing a C-type blue light absorber.

[0069] II. Preparation of Blue Light Blocking Photochromic Lens Substrate

[0070] After ultrasonic degassing of the photochromic composite resin containing the C-type blue light absorber, the material temperature is maintained at 20°C (specific temperature), naturally filtered through a 0.1 μm polytetrafluoroethylene filter, injected into a lens mold and sealed, and programmed to rise from room temperature to 100°C in a computer-controlled curing furnace for 20 hours. The programmed temperature rise curve is as follows: ① maintain 35°C for 0 to 4 hours; ② rise to 60°C at a constant speed for 4 to 12 hours; ③ rise to 100°C at a constant speed for 12 to 18 hours; ④ maintain 100°C for 18 to 20 hours; ⑤ open the mold after cooling to 70°C to obtain an (acrylate) resin anti-blue light photochromic substrate, which is then cleaned and dried.

[0071] Example 4: Blue light blocking photochromic lens (IV)

[0072] I. Preparation of D-type anti-blue light color-changing composite resin

[0073] Weigh 25g of methyl styrene, 25g of polyacrylate, 25g of ethoxylated bisphenol A diacrylate, and 25g of butyl methacrylate, then add 1.0g of D-type porphine metal complex, 0.6g of quinophthalone (Formula I), 1.8g of 1,3,3-trimethylindole-6-nitrobenzodihydropyran and spirane photochromic material, 0.6g of 1,3,3-trimethylindole-β-naphthyl dihydrofuran photochromic material, and 0.4g of xylene diluent into a conical flask and stir for 1 hour, add 2.2g of azobisisoheptanitrile curing agent and evacuate at room temperature for 30 minutes, stirring and mixing continuously during this process. Then control the temperature at 35°C, stir at a rate of 500r / min, and stand and evacuate for 90 minutes. Obtain a photochromic composite resin containing a D-type blue light absorber.

[0074] II. Preparation of Blue Light Blocking Photochromic Lens Substrate

[0075] After ultrasonic degassing of the photochromic composite resin containing the D-type blue light absorber, the material temperature is maintained at 20°C (specific temperature), naturally filtered through a 0.1 μm polytetrafluoroethylene filter, injected into a lens mold and sealed, and programmed to rise from room temperature to 100°C in a computer-controlled curing furnace for 20 hours. The programmed temperature rise curve is as follows: ① maintain 35°C for 0 to 4 hours; ② rise to 60°C at a constant speed for 4 to 12 hours; ③ rise to 100°C at a constant speed for 12 to 18 hours; ④ maintain 100°C for 18 to 20 hours; ⑤ open the mold after cooling to 70°C to obtain an (acrylate) resin anti-blue light photochromic substrate, which is then cleaned and dried.

[0076] Example 5: Blue light blocking photochromic lens (V)

[0077] I. Preparation of Type A Anti-blue Light Color-changing Composite Resin

[0078] Weigh 25g of methyl styrene, 25g of polyacrylate, 25g of ethoxylated bisphenol A diacrylate, and 25g of butyl methacrylate, then add 0.8g of type A porphine metal complex, 0.5g of quinophthalone (Formula I), 0.8g of 1,3,3-trimethylindole-6-nitrobenzodihydropyran and spirane photochromic material, 0.2g of 1,3,3-trimethylindole-β-naphthyl dihydrofuran photochromic material, and 0.4g of xylene diluent into a conical flask and stir for 1 hour, add 2.2g of azobisisoheptanitrile curing agent and evacuate at room temperature for 30 minutes, stirring and mixing continuously during this process. Then control the temperature at 35°C, stir at a rate of 500r / min, and stand and evacuate for 90 minutes. Obtain a photochromic composite resin containing type A blue light absorber.

[0079] II. Preparation of Blue Light Blocking Photochromic Lens Substrate

[0080] After ultrasonic degassing of the photochromic composite resin containing type A blue light absorber, the material temperature is maintained at 20°C, and after natural filtration through a 0.1 μm polytetrafluoroethylene filter, the material is injected into a lens mold and sealed. The temperature is programmed to rise from room temperature to 100°C in a computer-controlled curing furnace for 20 hours, and the programmed temperature rise curve is as follows: ① 0 to 4 hours to maintain 35°C; ② 4 to 12 hours to uniformly increase to 60°C; ③ 12 to 18 hours to uniformly increase to 100°C; ④ 18 to 20 hours to maintain 100°C; ⑤ After cooling to 70°C, the mold is opened to obtain an acrylic resin anti-blue light photochromic substrate, which is then cleaned and dried.

[0081] Comparative Examples 1-9

[0082] Comparative Examples 1-9 respectively adopt the preparation conditions of the corresponding embodiments, except that the blue light absorber is replaced or some components are reduced. The specific formulation conditions are detailed in Table 1. The total amount of blue light absorber in each comparative example is the same as that in the corresponding embodiment, and the color-changing material in each comparative example is the same as that in the corresponding embodiment or is not added.

[0083] In contrast, the conventional blue light absorber widely sold in the market uses 4,4-(1,4-phenylene)bis(1-(4-butoxyphenyl)-1,3-propanedione (Chinese invention patent CN108191624A).

[0084] Table 1 Comparison of comparative samples prepared under different formulation conditions

[0085] sample Commercially available blue light absorbers Porphine metal complex Quinophthalone Color-changing materials Corresponding embodiment Comparative Example 1 0.3g / 0.25g √ Example 2 Comparative Example 2 / / 0.55g √ Example 2 Comparative Example 3 / 0.3g 0.25g / Example 2 Comparative Example 4 / 0.85g / / Example 3 Comparative Example 5 / 1.6g / √ Example 4 Comparative Example 6 0.5g 0.8g / √ Example 5 Comparative Example 7 15g / / √ Example 1 Comparative Example 8 / 0.85 / √ Example 3 Comparative Example 9 / / 1.3g / Example 5

[0086] Example 6: Photochromic performance test of anti-blue light photochromic lens substrate

[0087] (I) Photochromic response value test

[0088] Testing steps and methods: The ratio of the light transmittance tV(0) of the tested sample in the faded state and the light transmittance tV(1) in the discolored state after the illumination time (15min), i.e., photochromic response value = tV(0) ÷ tV(1), is used to determine the photochromic response value of the tested sample at different temperatures. After the radiation intensity of the solar simulator is attenuated by 25%, the sample is irradiated with medium light intensity. The test results are as follows: Figure 1-9 The test results are shown in Table 2.

[0089] (II) Photochromic spectral response time detection

[0090] Detection steps and methods: Place the lens substrates prepared in Examples 1-5 and Comparative Examples 1-9 into a test box respectively, turn on the solar simulator light source, and record the time required for the lens to change from colorless to colored; turn off the simulated light source after 10 minutes of irradiation, and record the time required for the lens to return to a colorless state from colored. The test results are shown in Table 2.

[0091] Table 2 Photochromic response values ​​of tested samples

[0092]

[0093] Conclusion: The optical material and lens containing the composite blue light absorbing material manufactured by the present invention have little effect on the color changing performance, and have the advantages of short photochromic response time and high photochromic response value.

[0094] Example 7: Optical performance test of blue light blocking photochromic lens substrate

[0095] The resin lens substrates prepared in Examples 1-5 and Comparative Examples 1-9 were tested for light transmittance (T / %) performance, using a UV-8000 ultraviolet-visible photometer from Shanghai Yuanxi Instrument Co., Ltd. Testing method: directly apply the resin lenses prepared in Examples 1-5 and Comparative Examples 1-8 to the prism of the ultraviolet-visible photometer to measure the light transmittance, with a wavelength range of 380 to 780 nm in the visible light region and a wavelength range of 280 to 380 nm in the ultraviolet region, using different illuminants as the light source of the instrument. Representative wavelength transmittances are listed in Table 3.

[0096] Table 3 Lens sample light transmittance test results Unit: T%

[0097]

[0098] Results and Discussion:

[0099] By comparing the above data, it can be seen that in Comparative Example 1, the porphine complex is replaced with a common blue light absorber on the market. Since the common blue light absorber also absorbs ultraviolet light, the photochromic material does not absorb enough ultraviolet light, the color change time is long, the color change effect is low, and the effect of rapid color change protection under strong light cannot be achieved;

[0100] Comparative Example 2 does not contain porphine complexes but only contains quinophthalone, and its protection in the ultraviolet region is lower than the national standard (GB10810.3-2006) requirement (≤1%), and its ultraviolet protection item is unqualified;

[0101] Comparative Example 3 does not change color because no color-changing material is added, and there is transmission in the ultraviolet region around 335nm;

[0102] Comparative Example 4 only added porphine complex, without quinophthalone and color-changing material, had higher transmittance in the ultraviolet region around 335nm, and the 435nm blue light transmittance was higher than that of Examples 1-5;

[0103] Comparative Example 5 did not add quinophthalone, and the blue light transmittance at 435 nm was higher than that of Examples 1-5;

[0104] Comparative Example 6 added some commercially available blue light absorbers but did not add quinophthalone, resulting in low color change efficiency and relatively high 435nm blue light transmission;

[0105] Comparative Example 7: The commercially available blue light absorber replaces the composite blue light absorber of the present invention, resulting in a lower color change efficiency and a higher transmittance at 435 nm;

[0106] Comparative Example 8 only added porphine complex and did not contain quinophthalone, and the 435nm blue light transmission was relatively high;

[0107] Comparative Example 9 contains only quinophthalone, without porphine complex and color-changing material, and has a higher transmittance in the ultraviolet region near 335 nm.

[0108] The porphine metal complex (AD) and quinophthalone used in the present invention are combined to effectively absorb blue light with a wavelength of 400nm-435nm, and at the same time, the photochromic performance is not affected.

Claims

1. A blue light-proof photochromic resin lens, characterized in that: The lens substrate The invention comprises the following components: 50 to 100 parts by weight of a thermosetting or thermoplastic optical resin, 0.6 to 2.5 parts by weight of a photochromic material, 0.1 to 1 part by weight of a porphine metal complex and 0.2 to 0.8 part by weight of a quinophthalone compound; The porphine metal complex is selected from at least one of the following structures: Type A: octaethylporphine zinc; Type B: octaethylporphine nickel; Type C: 5,10,15,20-tetrakis(pentafluorophenyl)porphine zinc; Type D: tetraphenylporphine zinc; The structural formula of the quinophthalone compound is as follows: The photochromic material is a spiropyran and / or spirooxazine photochromic material.

2. The blue light blocking photochromic resin lens according to claim 1, characterized in that: The thermosetting or thermoplastic optical resin is selected from one or more of polymethyl methacrylate, polystyrene, and bisphenol A epoxy resin.

3. The blue light blocking photochromic resin lens according to claim 2, characterized in that: The monomers for preparing the thermosetting or thermoplastic optical resin are selected from one or more of styrene, methacrylic acid, pentaerythritol tetraacrylate, ethoxylated nonylphenol acrylate, epoxy acrylate, bisphenol A epoxy acrylate, methyl styrene, polyacrylate, ethoxylated bisphenol A diacrylate and butyl methacrylate.

4. The blue light blocking photochromic resin lens according to any one of claims 1 to 3, characterized in that: The photochromic material is N-(β-hydroxyethyl)-3,3-dimethyl-6-nitrospiroindolinebenzopyran, 1,3,3-trimethylindole-6-nitrobenzodihydropyranospirane and / or 1,3,3-trimethylindole-β-naphthyldihydrofuran.

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