Polythiol composition, polymerizable composition for optical product and optical product

Abstract

The invention provides a polythiol composition, a polymerizable composition for an optical product and the optical product. The polythiol composition comprises a first polythiol composition and a second polythiol compound, the molecular structure of the first polythiol composition comprises at least four sulfydryl groups; the structural formula of the second polythiol compound is shown as a formula II-1, a formula II-2, a formula II-3 or a formula II-4. According to the present invention, the polymerizable composition comprising the polythiol composition and the polyisocyanate is adopted to prepare the optical product, such as the optical lens, such that the binding force between the lens and the surface plated film layer can be increased so as to increase the salt water resistance, and the refractive index of the lens is about 1.67, such that the excellent optical performance is provided.

Description

Technical Field

[0001] The present invention belongs to the technical field of optical materials, and particularly relates to a polythiol composition, a polymerizable composition for an optical product, and an optical product. Background Art

[0002] Compared with inorganic glass represented by quartz, organic optical glass materials have advantages such as high toughness, low specific gravity, convenient modification of optical fillers, and excellent processing performance. In recent years, they have developed rapidly in optical lens elements required for glasses, photography, lasers, etc. Among them, organic optical glass based on polythiol compounds has advantages such as high refractive index, high transmittance, and large Abbe number, and the lenses made thereof have higher optical application value.

[0003] In the actual use process, for organic optical glass based on polythiol compounds, a layer or multiple layers of thin films are usually required to be coated on the surface to further improve its hardness, reduce reflection, abrasion resistance, impact resistance, or dyeing performance. Therefore, the adhesion between the film layer and the lens greatly affects the weather resistance of the film layer in actual use. However, there are few reports on the research to improve the adhesion between the polythiol compound-based lens and its surface film layer, and the related mechanism also needs to be further studied. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a polythiol composition, a polymerizable composition for an optical product, and an optical product. The optical product has excellent properties that can improve the film adhesion between the lens base surface and the hardening layer, thereby enhancing its salt water resistance.

[0005] To achieve this purpose, the present invention adopts the following technical solutions:

[0006] In the first aspect, the present invention provides a polythiol composition, which includes a first polythiol composition and a second polythiol compound; the mass ratio of the second polythiol compound to the first polythiol composition is 0.001-2.0%;

[0007] The first polythiol composition includes at least 4 mercapto groups in its molecular structure;

[0008] The second polythiol compound includes one or more of the compounds shown in Formula II-1, Formula II-2, Formula II-3, and Formula II-4:

[0009]

[0010] Preferably, the mass ratio of the second polythiol compound to the first polythiol composition is 0.005-2.0%.

[0011] Preferably, the first polythiol composition comprises compounds represented by Formula I-1 to Formula I-3:

[0012]

[0013] In a second aspect, the present invention provides a polymerizable composition for an optical product, which comprises the polythiol composition and polyisocyanate involved in the above technical solution.

[0014] Preferably, the polyisocyanate comprises any one or more of tetramethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, 4,4'-diisocyanatodicyclohexylmethane, isophorone diisocyanate, norbornane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl-m-xylylene diisocyanate, dithiodipropyl diisocyanate, dithiodiethyl diisocyanate, 2,5-diisocyanatomethylthiophene, 2,5-diisocyanatomethyl-1,4-dithiane, 2,5-diisocyanate-1,4-dithiane, thiodihexyl diisocyanate, thiodipropyl diisocyanate, bis(isocyanatomethyl)adamantane, bis(isocyanatomethyl)tetrahydrothiophene, 2,6-bis(isocyanatomethyl)naphthalene, 1,5-naphthalene diisocyanate, diethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine triisocyanate, toluene diisocyanate, o-tolidine diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate or triphenylmethane triisocyanate.

[0015] Preferably, the molar ratio of -SH in the polythiol composition to -NCO in the polyisocyanate is 0.8:1 to 1.2:1.

[0016] Preferably, the polymerizable composition for an optical product further comprises a third polythiol compound.

[0017] Preferably, the third polythiol compound includes any one or more of methanedithiol, methanetrithiol, bis(2-mercaptoethyl) ether, tetrakis(mercaptomethyl)methane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane, 2,2-dimercaptopropane, 1,2-bis(2-mercaptoethoxy)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 2,3-dimercapto-1-propanol, 1,2-dimercaptoethane, 1,3-dimercapto-2-propanol, 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4-dimercaptobutane, 1,2,3-trimercaptopropane, 2-(2-mercaptoethylthio)-1,3-dimercaptopropane, 2,4-dimercaptomethyl-1,5-dimercapto-3-thiapentane, bis(2-mercaptoethyl) sulfide, ethylene glycol bis(3-mercaptopropionate), diethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(2-mercaptoacetate), 1,4-butanediol bis(2-mercaptoacetate), trimethylolpropane trimercaptopropionate, pentaerythritol tetrakis(mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), pentaerythritol tetrakis(mercaptopropionate), 1,2-dimercyclohexane, 1,1,1-tris(mercaptomethyl)propane, 1,4-butanediol bis(3-mercaptopropionate), 1,3-dimercyclohexane, trimethylolpropane trismercaptoacetate, 1,4-dimercyclohexane, 1,3-bis(mercaptomethyl)cyclohexane, 1,4-bis(mercaptomethyl)cyclohexane, bis(4-mercaptophenyl) sulfone, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-bis(2-mercaptoethylthiomethyl)-1,4-dithiane, 2,5-dimercaptomethyl-1-thiane, 2,5-dimercaptoethyl-1-thiane, 2,5-dimercaptomethylthiophene, bis(4-mercaptophenyl) sulfide, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,3-bis(mercaptomethyl)benzene, 2,5-dimercaptomethyl-1,4-dithiane, 1,4-bis(mercaptomethyl)benzene, 2,2'-dimercaptobiphenyl, bis(4-mercaptophenyl)methane, 2,2-bis(4-mercaptophenyl)propane, 4,4'-dimercaptobiphenyl, bis(4-mercaptophenyl) ether, bis(4-mercaptomethylphenyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 2,2-bis(4-mercaptomethylphenyl)propane, bis(4-mercaptomethylphenyl) ether, bis(4-mercaptomethylphenyl) sulfide, 2,5-dimercapto-1,3,4-thiadiazole, or 3,4-thiophenedithiol.

[0018] Preferably, the mass ratio of the polythiol composition to the third polythiol compound is 0.25:1 to 4:1.

[0019] In a third aspect, the present invention provides an optical product obtained by polymerizing the polymerizable composition for an optical product according to the above technical solution.

[0020] Preferably, the polymerization is carried out in the presence of an initiator.

[0021] Preferably, during the polymerization process, any one or more of a mold release agent, a toner, or an ultraviolet absorber are added.

[0022] Preferably, the optical product includes an optical lens, an optical thin film, or a display panel.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] The present invention provides a polythiol composition including a first polythiol composition and a second polythiol compound. Among them, the first polythiol composition includes at least 4 mercapto groups in its molecular structure; the second polythiol compound includes any one or more of those represented by Formulae II-1 to II-4. In the present invention, due to the polythiol composition having more active hydroxyl groups, the lens made and the coated film layer can have a higher bonding strength. At the same time, its polythio main chain structure can ensure that its optical properties such as high refractive index and transmittance are not greatly affected.

[0025] The present invention uses a polymerizable composition including the above-mentioned polythiol composition and polyisocyanate to prepare an optical product, such as an optical lens, which can enhance the bonding strength between the lens and the surface-coated film layer. Furthermore, the optical lens can have better salt water resistance, and the refractive index of the lens is about 1.67, indicating its excellent optical properties. Description of the Drawings

[0026] Figure 1 Mass spectrum of the first polythiol composition obtained in Preparation Example 1;

[0027] Figure 2 Mass spectrum of the second polythiol compound obtained in Preparation Example 2;

[0028] Figure 3 1H NMR spectrum of the polythiol compound represented by Formula II-1;

[0029] Figure 4 1H NMR spectrum of the polythiol compound represented by Formula II-2;

[0030] Figure 5 1H NMR spectrum of the polythiol compound represented by Formula II-3;

[0031] Figure 6 1H NMR spectrum of the polythiol compound represented by Formula II-4. Detailed Description of the Invention

[0032] Next, in combination with the embodiments of the present invention, the technical solutions of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts belong to the scope of protection of the present invention.

[0033] The present invention provides a polythiol composition, which includes a first polythiol composition and a second polythiol compound.

[0034] In the present invention, the first polythiol composition includes at least 4 mercapto groups in its molecular structure. Specifically, the first polythiol composition includes the compounds shown in Formula I-1 to Formula I-3:

[0035]

[0036] The present invention has no special limitation on the source of the above-mentioned first polythiol composition, and it can be directly purchased or prepared by oneself according to conventional methods. In some embodiments of the present invention, it is preferred to prepare the above-mentioned first polythiol composition according to the synthesis scheme described in CN110446696A.

[0037] In the present invention, the second polythiol compound is preferably a second polythiol compound containing at least one hydroxyl group and having a main chain longer than that of the first polythiol composition.

[0038] In some embodiments of the present invention, the molecular formula of the second polythiol compound is C 12 H 26 OS 7 , and the second polythiol compound includes one or more of the compounds shown in Formula II-1, Formula II-2, Formula II-3, and Formula II-4:

[0039]

[0040] The present invention has no special limitation on the source of the second polythiol compound having the formulas II-1 to II-4, and it can be generally commercially available or prepared by oneself. Among the second polythiol compounds shown in Formulas II-1 to II-4, Formulas II-1 to II-4 are structural isomers of each other.

[0041] In some embodiments of the present invention, the polythiol composition is obtained by mixing the first polythiol composition including any one or more of Formulas I-1 to I-3 and the second polythiol compound including any one or more of Formulas II-1 to II-4.

[0042] Upon research, the contents of the first polythiol composition and the second polythiol compound can affect the processing performance of the final optical product. Therefore, the mass percentage content of the first polythiol composition in the polythiol composition is preferably 80-99%, more preferably 80-95%; the mass percentage content of the second polythiol compound in the polythiol composition is preferably 0.001-2%, more preferably 0.005-2%.

[0043] In some embodiments of the present invention, preferably, the mass ratio of the second polythiol compound to the first polythiol composition is 0.001-2.0%; such as 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, and preferably 0.005-2.0%.

[0044] The present invention also provides a polymerizable composition for an optical product, which is the polythiol composition and polyisocyanate in the above technical solution.

[0045] In the present invention, the polyisocyanate includes any one or more of tetramethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, 4,4'-diisocyanatodicyclohexylmethane, isophorone diisocyanate, norbornane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl-m-xylylene diisocyanate, dithiobispropyl diisocyanate, dithiobisethyl diisocyanate, 2,5-diisocyanatomethylthiophene, 2,5-diisocyanatomethyl-1,4-dithiane, 2,5-diisocyanate-1,4-dithiane, thiodihexyl diisocyanate, thiodipropyl diisocyanate, bis(isocyanatomethyl)adamantane, bis(isocyanatomethyl)tetrahydrothiophene, 2,6-bis(isocyanatomethyl)naphthalene, 1,5-naphthalene diisocyanate, diethylidene diisocyanate, trimethylhexamethylene diisocyanate, lysine triisocyanate, toluene diisocyanate, o-tolidine diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate or triphenylmethane triisocyanate; preferably includes any one or more of hexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, m-xylylene diisocyanate or hydrogenated m-xylylene diisocyanate; more preferably includes any one or more of hydrogenated m-xylylene diisocyanate, norbornane diisocyanate or m-xylylene diisocyanate.

[0046] In some embodiments of the present invention, the molar ratio of -SH in the polythiol composition to -NCO of the polyisocyanate is 0.8:1 to 1.2:1, such as 0.8:1, 0.9:1, 1:1, 1.1:1 or 1.2:1, etc., and preferably 1:1.

[0047] In some preferred embodiments of the present invention, the polymerizable composition for an optical product further comprises a third polythiol compound.

[0048] Among them, the third polythiol compound includes methanedithiol, methanetrithiol, bis(2-mercaptoethyl) ether, tetrakis(mercaptomethyl)methane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane, 2,2-dimercaptopropane, 1,2-bis(2-mercaptoethoxy)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 2,3-dimercapto-1-propanol, 1,2-dimercaptoethane, 1,3-dimercapto-2-propanol, 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4-dimercaptobutane, 1,2,3-trimercaptopropane, 2-(2-mercaptoethylthio)-1,3-dimercaptopropane, 2,4-dimercaptomethyl-1,5-dimercapto-3-thiapentane, bis(2-mercaptoethyl) sulfide, ethylene glycol bis(3-mercaptopropionate), diethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(2-mercaptoacetate), 1,4-butanediol bis(2-mercaptoacetate), trimethylolpropane trimercaptopropionate, pentaerythritol tetrakis(mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), pentaerythritol tetrakis(mercaptopropionate), 1,2-dimercyclohexane, 1,1,1-tris(mercaptomethyl)propane, 1,4-butanediol bis(3-mercaptopropionate), 1,3-dimercyclohexane, trimethylolpropane trismercaptoacetate, 1,4-dimercyclohexane, 1,3-bis(mercaptomethyl)cyclohexane, 1,4-bis(mercaptomethyl)cyclohexane, bis(4-mercaptophenyl) sulfone, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-bis(2-mercaptoethylthiomethyl)-1,4-dithiane, 2,5-dimercaptomethyl-1-thiane, 2,5-dimercaptoethyl-1-thiane, 2,5-dimercaptomethylthiophene, bis(4-mercaptophenyl) sulfide, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,3-bis(mercaptomethyl)benzene, 2,5-dimercaptomethyl-1,4-dithiane, 1,4-bis(mercaptomethyl)benzene, 2,2'-dimercaptobiphenyl, bis(4-mercaptophenyl)methane, 2,2-bis(4-mercaptophenyl)propane, 4,4'-dimercaptobiphenyl, bis(4-mercaptophenyl) ether, bis(4-mercaptomethylphenyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 2,2-bis(4-mercaptomethylphenyl)propane, bis(4-mercaptomethylphenyl) ether, bis(4-mercaptomethylphenyl) sulfide, 2,5-dimercapto-1,3,4-thiadiazole, or 3,4-thiophenedithiol, or any one or more of them.

[0049] In some embodiments of the present invention, the mass ratio of the polythiol composition to the third polythiol compound is 0.25:1 to 4:1, such as 0.25:1, 0.5:1, 1:1, 1.5:1, 2.5:1, 3:1, 3.5:1, 4:1, etc., and preferably 1:1.

[0050] The present invention also provides an optical product obtained by polymerizing the above-mentioned polymerizable composition for optical products. The optical product may be an optical lens, an optical film or a display panel.

[0051] In the present invention, the polymerization is preferably carried out in the presence of an initiator, and the initiator includes any one or more of dibutyltin dilaurate, dibutyltin dichloride, dibutyltin oxide or stannous octoate, and preferably includes dibutyltin dilaurate and / or dibutyltin dichloride.

[0052] In the present invention, when the mass ratio of the initiator to the polymerizable composition for optical products is less than 0.005%, incomplete polymerization may occur, resulting in poor mechanical properties of the finally prepared optical product; while when the mass ratio of the two is greater than 0.2%, the polymerization rate may be too fast, resulting in an increase in the hue of the finally prepared optical product. Therefore, in some embodiments of the present invention, the mass ratio of the initiator to the polymerizable composition for optical products is preferably (0.005 - 0.2):100, more preferably (0.01 - 0.1):100.

[0053] In some preferred embodiments of the present invention, the raw materials for preparing the optical product further include additives, and the additives include any one or more of a release agent, a toner or an ultraviolet absorber.

[0054] In some embodiments of the present invention, when the additive is selected as a release agent, the release agent is a polyphosphate ester. The mass ratio of the release agent to the polymerizable composition for optical products is (0.005 - 0.2):100, preferably (0.01 - 0.1):100.

[0055] In some embodiments of the present invention, the optical product is an optical lens.

[0056] The present invention also provides a method for preparing an optical product with a hardening layer, comprising the following steps:

[0057] A) Stir and dissolve a polyisocyanate, a catalyst and a release agent to obtain a first mixed solution;

[0058] B) Mix the first mixed solution, the polythiol composition involved in the above technical solution and an optional third polythiol compound, and after degassing, obtain a second mixed solution;

[0059] C) Pour the second mixed solution into a mold, polymerize and cure to obtain an optical product substrate;

[0060] D) Using the dip coating method, the obtained optical product substrate is coated with a hardening solution containing silicone and nano-titanium dioxide on the substrate surface through an immersion-lifting process. Generally, after the substrate is completely immersed, the lifting speed is controlled at 2-5 mm / s. After the solvent is dried in a drying tunnel at 90-95 °C, it enters a high-temperature oven at 100 °C and is heated for 3.5-6 h for the polymerization reaction of silicone cross-linking to form a hardening layer on its surface, obtaining an optical product with a hardening layer.

[0061] In the present invention, in the above step A): the temperature for stirring and dissolving is 10-20 °C, preferably 15 °C.

[0062] In the present invention, in the above step B), it is preferably degassed using a vacuum pump, the pressure is controlled below 350 Pa, and the degassing time is 0.5-1.0 h, preferably 0.6-0.8 h.

[0063] In the present invention, in the above step C), the mold is a glass mold with a curved surface of 0° having a diameter of 80 mm and a thickness of 10 mm. The specifications of the glass mold can also be adjusted according to actual needs.

[0064] In the present invention, after the casting, it preferably further includes: laying flat in a tray.

[0065] In some embodiments of the present invention, the temperature increase program for polymerization curing includes:

[0066] Insulating at 25-35 °C for 175-185 min, increasing the temperature at a rate of 0.83-1.25 °C / 10 min to 43-47 °C, then increasing the temperature at a rate of 0.42-0.56 °C / 10 min to 48-52 °C, then increasing the temperature at a rate of 0.57-0.83 °C / 10 min to 58-62 °C, then increasing the temperature at a rate of 2.00-2.50 °C / 10 min to 115-125 °C, and then insulating at 115-125 °C for 180-240 min.

[0067] In some specific embodiments of the present invention, the temperature increase program for polymerization curing includes:

[0068] Insulating at 30 °C for 180 min, increasing the temperature at a rate of 1.25 °C / 10 min to 45 °C, then increasing the temperature at a rate of 0.56 °C / 10 min to 50 °C, then increasing the temperature at a rate of 0.83 °C / 10 min to 60 °C, then increasing the temperature at a rate of 2.50 °C / 10 min to 120 °C, and then insulating at 120 °C for 180 min.

[0069] In some other specific embodiments of the present invention, the temperature increase program for polymerization curing includes:

[0070] Keep it at 30°C for 180 min, heat it up to 45°C at a heating rate of 0.83°C / 10 min, then heat it up to 50°C at a heating rate of 0.42°C / 10 min, then heat it up to 60°C at a heating rate of 0.57°C / 10 min, then heat it up to 120°C at a heating rate of 2.00°C / 10 min, and then keep it at 120°C for 240 min.

[0071] In some embodiments of the present invention, after the polymerization and curing, it further includes: cooling down. Preferably, the present invention cools down to a temperature of 75 - 85°C, preferably 80°C; the cooling time is 115 - 125 min, preferably 120 min.

[0072] In some embodiments of the present invention, after forming the hardening layer in step D), the optical product with the hardening layer can be placed in a vacuum coating chamber for vacuum coating as needed, and successively and continuously deposit an isolation layer, an organic color-changing layer, and an anti-reflection coating layer. The organic color-changing layer is completed by flash evaporation and vacuum spraying, and finally an optical product with a multi-layer film including a hardening layer, an isolation layer, an organic color-changing layer, and an anti-reflection coating layer is obtained.

[0073] The present invention has no special restrictions on the sources of the raw materials used above, and they can be generally commercially available.

[0074] Taking the prepared optical product as an optical lens as an example, the present invention conducts tests and finds that the prepared optical lens has better salt water resistance, indicating that the polythiol composition provided by the present invention can significantly improve the film adhesion on the surface of the optical lens (i.e., the bonding force between the hardening layer and the lens), and the refractive index is about 1.67, indicating its excellent optical properties. In addition, by further defining the mass ratio of the first polythiol composition and the second polythiol compound, the present invention can significantly control the film adhesion on the surface of the optical product, while the refractive index does not decrease significantly, improving the application performance of the polythiol composition.

[0075] To further illustrate the present invention, the following detailed description is provided through the following examples. All the experimental raw materials used in the following examples of the present invention are generally commercially available products.

[0076] Preparation Example 1

[0077] In this example, the above-mentioned first polythiol composition (including any one or more of the structures shown in Formulae I-1 to I-3) was prepared by using the existing methods in the prior art. Specifically, it was prepared according to the synthesis scheme described in Patent CN110446696A, and the obtained product was analyzed by a mass spectrometer to confirm that its structure was consistent with that described in the literature.

[0078] The mass spectrum of the first polythiol composition obtained in this Preparation Example 1 is as Figure 1 shown.

[0079] Preparation Example 2

[0080] 1) Add 117.5 g (1.5 mol) of 2-mercaptoethanol into a four-necked flask equipped with a thermometer, a stirrer, and a constant-pressure dropping funnel, and dropwise add an aqueous potassium hydroxide solution with a mass fraction of 42%. The molar ratio of the 2-mercaptoethanol to potassium hydroxide is 1.4:1.5. Keep stirring and reacting at 70 °C at 200 rpm for 3 h to obtain a first mixed solution;

[0081] 2) Dropwise add bis(3-chloro-2-hydroxypropyl)sulfide (75 g, 0.344 mol, CAS: 19030-86-5) to the first mixed solution obtained in step 1). The molar ratio of the bis(3-chloro-2-hydroxypropyl)sulfide to the 2-mercaptoethanol in step 1) is 0.23:1. React at 75 °C for 3 h to obtain a first reaction solution;

[0082] 3) Dropwise add an aqueous potassium hydroxide solution with a mass fraction of 42% to 117.5 g (1.5 mol) of 2-mercaptoethanol. The molar ratio of the 2-mercaptoethanol to potassium hydroxide is 1.4:1.5. Keep stirring and reacting at 65 °C at 200 rpm for 3 h to obtain a second mixed solution;

[0083] 4) Dropwise add 1,3-dichloro-2-propanol in an equimolar amount to the bis(3-chloro-2-hydroxypropyl)sulfide in step 2) to the second mixed solution obtained in step 3). The molar ratio of the 1,3-dichloro-2-propanol to the 2-mercaptoethanol in step 3) is 0.23:1. React at 75 °C for 3 h to obtain a second reaction solution;

[0084] 5) Mix the first reaction solution in step 2) and the second reaction solution in step 4), and then add sodium sulfide. The molar ratio of the sodium sulfide to the bis(3-chloro-2-hydroxypropyl)sulfide in step 2) is 1:1. Keep stirring and reacting at 75 °C at 200 rpm for 2 h to obtain a third reaction solution;

[0085] 6) Add a hydrochloric acid solution with a mass concentration of 30% and thiourea to the third reaction solution obtained in step 5). The molar ratio of the hydrochloric acid to the sodium sulfide in step 5) is 4.7:1.0, and the molar ratio of the thiourea to the sodium sulfide in step 5) is 4.8:1.5. Carry out a reflux reaction at 115 °C for 8 h to obtain a fourth reaction solution;

[0086] 7) Add an aqueous ammonia solution with a mass concentration of 15% to the fourth reaction solution obtained in step 6). The NH in the aqueous ammonia 3The molar ratio to sodium sulfide in step 5) is 10:1, and the temperature is raised to 95 °C for reaction for 2 h to obtain a mixed product containing a second polythiol compound shown in Formula II (i.e., shown in Formula II-1 to II-4); the lower-layer crude product is transferred into a single-neck flask, and ethanol with the same mass as the crude product is added for washing. The washing is carried out 3 times, and after washing, the crude product is subjected to vacuum desolvation. The obtained product is analyzed by a mass spectrometer, and it is found that a mixture (2.5 g) of a second polythiol compound containing the structure shown in Formula II (i.e., the structure shown in Formula II-1 to II-4) is obtained. Among them, each component contained in the second polythiol compound is further separated and purified by column chromatography.

[0087] Among them, the mass spectrum of the mixture of the second polythiol compound shown in Formula II obtained in Preparation Example 2 is as Figure 2 shown. The 1H NMR spectra of the second polythiol compounds shown in Formula II-1 to II-4 are respectively as Figure 3 , Figure 4 , Figure 5 and Figure 6 shown.

[0088] Examples 1 to 10

[0089] A variety of polythiol compositions are provided. Among them, the mass ratios (denoted as mII:mI) of the mixture of the second polythiol compound shown in Formula II obtained in Preparation Example 2 to the first polythiol composition shown in Formula I are 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.3%, 0.5%, 1.0%, 1.5%, and 2.0% respectively.

[0090] Application Examples 1 to 10

[0091] 51.2 parts by mass of xylylene diisocyanate, 0.01 part by mass of a catalyst (dibutyltin dichloride), and 0.08 part by mass of a release agent (polypolyphosphate ester) are added into a batching kettle and stirred and dissolved at 15°C; 48.8 parts by mass of the polythiol composition prepared in Examples 1 to 10 are added and stirred evenly. Degassing is carried out using a vacuum pump, with the pressure controlled at 350 Pa and the degassing time being 0.5 h to prepare a mixed solution. The solution is poured into 1000 clean glass molds with a curved surface of 0°, a diameter of 80 mm, and a thickness of 10 mm. After pouring, the molds are placed flat in a tray. They are put into an oven for programmed temperature rise curing (insulating at 30°C for 180 min, rising the temperature to 45°C at a heating rate of 1.25°C / 10 min, then rising the temperature to 50°C at a heating rate of 0.56°C / 10 min, then rising the temperature to 60°C at a heating rate of 0.83°C / 10 min, then rising the temperature to 120°C at a heating rate of 2.50°C / 10 min, and then insulating at 120°C for 180 min), and then cooling to 80°C after 120 min. The molds are taken out and opened to obtain optical lens substrates. Subsequently, the obtained optical lens substrates are coated with a hardening solution containing silicone and nano-titanium dioxide on the surface of the substrates by the dip-coating method through the dipping-lifting process. Generally, after the lens substrates are completely immersed, the lifting speed is controlled at 3 mm / s. After the solvent is dried in a drying tunnel at 90°C, it enters a high-temperature oven at 120°C and is heated for 2.5 h for the polymerization reaction of silicone cross-linking to form a hardening layer on its surface, obtaining lenses with a hardening layer.

[0092] Application Examples 11 - 20

[0093] 49.5 parts by mass of hydrogenated xylylene diisocyanate is added into a batching kettle, 0.10 part by mass of a catalyst (dibutyltin dichloride) and 0.10 part by mass of a demolding agent (polypolyphosphate ester) are added, and they are stirred and dissolved at 15°C; 30.5 parts by mass of the polythiol composition prepared in Examples 1 to 10 and 20.0 parts by mass of a third polythiol compound (pentaerythritol tetrakis(mercaptoacetate)) are added and stirred evenly. Degassing is carried out using a vacuum pump, the pressure is controlled at 350 Pa, and the degassing time is 0.5 h to prepare a mixed solution. The solution is poured into a clean glass mold with a curved surface of 0° having a diameter of 80 mm and a thickness of 10 mm, and 1000 molds are poured. After pouring, they are placed flat in a tray. They are put into an oven for programmed temperature curing (held at 30°C for 180 min, heated at a heating rate of 0.83°C / 10 min to 45°C, then heated at a heating rate of 0.42°C / 10 min to 50°C, then heated at a heating rate of 0.57°C / 10 min to 60°C, then heated at a heating rate of 2.00°C / 10 min to 120°C, and then held at 120°C for 240 min), and then cooled to 80°C in 120 min. The molds are taken out and opened to obtain an optical lens substrate. Subsequently, the obtained optical lens substrate is coated with a hardening solution containing silicone and nano-titanium dioxide on the surface of the substrate by the dip-coating method through the dipping-lifting process. Generally, after the lens substrate is completely immersed, the lifting speed is controlled at 2 mm / s, and after the solvent is dried in a drying tunnel at 90°C, it enters a high-temperature oven at 100°C and is heated for 3.5 h for the polymerization reaction of silicone cross-linking to form a hardening layer on its surface, and a lens with a hardening layer is obtained.

[0094] Comparative Application Example 1

[0095] Compared with Application Example 1, the difference is only that the polythiol composition prepared in Example 1 is replaced with a first polythiol composition having the structure shown in Formula I, and the remaining parameters and steps are the same as those in Application Example 1.

[0096] Comparative Application Example 2

[0097] Compared with Application Example 1, the difference is only that the polythiol composition prepared in Example 1 is replaced with a mixture of a second polythiol compound having the structure shown in Formula II-1 and a first polythiol composition having the structure shown in Formula I, wherein the mass ratio of the second polythiol compound to the first polythiol composition is 3%, and the remaining parameters and steps are the same as those in Application Example 1.

[0098] Comparative Application Example 3

[0099] Compared with Application Example 1, the difference is that the polythiol composition prepared in Example 1 is replaced with a mixture of a second polythiol compound having the structure shown in Formula II-1 and a first polythiol composition having the structure shown in Formula I, wherein the mass ratio of the second polythiol compound to the first polythiol composition is 1.0%, and the remaining parameters and steps are the same as those in Application Example 1.

[0100] Meanwhile, after forming the hardening layer, the lens with the hardening layer is placed in a vacuum coating chamber for vacuum coating, and an isolation layer, an organic color-changing layer, and an anti-reflection coating layer are sequentially and continuously vapor-deposited. The organic color-changing layer is completed by flash evaporation and vacuum spraying, and finally a lens with a multi-layer film including a hardening layer, an isolation layer, an organic color-changing layer, and an anti-reflection coating layer is obtained.

[0101] Comparative Application Example 4

[0102] Compared with Application Example 11, the difference is only that the polythiol composition prepared in Example 1 is replaced with the first polythiol composition shown in Formula I, and the remaining parameters and steps are the same as those in Application Example 11.

[0103] Comparative Application Example 5

[0104] Compared with Application Example 11, the difference is only that the polythiol composition prepared in Example 1 is replaced with a mixture of a second polythiol compound having the structure shown in Formula II-1 and a first polythiol composition having the structure shown in Formula I, wherein the mass ratio of the second polythiol compound to the first polythiol composition is 3%, and the remaining parameters and steps are the same as those in Application Example 11.

[0105] Comparative Application Example 6

[0106] Compared with Application Example 11, the difference is that the polythiol composition prepared in Example 1 is replaced with a mixture of a second polythiol compound having the structure shown in Formula II-1 and a first polythiol composition having the structure shown in Formula I, wherein the mass ratio of the second polythiol compound to the first polythiol composition is 1.0%, and the remaining parameters and steps are the same as those in Application Example 11.

[0107] Meanwhile, after forming the hardening layer, the lens with the hardening layer is placed in a vacuum coating chamber for vacuum coating, and an isolation layer, an organic color-changing layer, and an anti-reflection coating layer are sequentially and continuously vapor-deposited. The organic color-changing layer is completed by flash evaporation and vacuum spraying, and finally a lens with a multi-layer film including a hardening layer, an isolation layer, an organic color-changing layer, and an anti-reflection coating layer is obtained.

[0108] Performance Test

[0109] For the lenses with hardening layers obtained from the above application examples and comparative application examples, a brine immersion experiment (for counting the number of squares) and a test of film adhesion are carried out;

[0110] Among them, for the brine immersion test, the method of GBT10810.4 - 2012 is adopted. The brine is a 4.5% brine solution, that is, at room temperature, 45 g of sodium chloride (analytical pure) is dissolved in 1 L of pure water; the container is a glass container and the bracket is a plastic bracket, both of which have good chemical stability to the sodium chloride solution; a new solution is used for each test experiment; during the test, the specimen (i.e., the lens with a hardening layer) is immersed in 400 mL of brine, kept at 37 °C for 7 h, the specimen is taken out, washed and wiped dry with a soft and clean cloth.

[0111] For the film adhesion test, the method of GBT10810.4 - 2012 is adopted. After the brine immersion test, count the number of squares where all the films have not peeled off, and calculate the ratio (%) of it to the total number of squares; if the film peels off in a square, the experimental result is considered unqualified, and if the number of non - peeled squares is less than 85%, the experimental result is also considered unqualified.

[0112] The test results are shown in Table 1 as follows:

[0113] Table 1

[0114]

[0115]

[0116] It can be seen from the data in Table 1 above that from Application Examples 1 - 10 and Application Examples 11 - 20, as the proportion of the mass of the second polythiol compound in the sum of the mass of the second polythiol compound and the first polythiol composition increases, the proportion of the number of film peel - offs of the lens with a hardening layer decreases significantly, indicating an improvement in its brine resistance performance. After the proportion of the second polythiol compound is greater than 1.0%, the decreasing trend tends to be gentle.

[0117] The results of Comparative Application Example 1, Comparative Application Example 2, Comparative Application Example 4 and Comparative Application Example 5 show that as the proportion of the mass of the second polythiol compound in the sum of the mass of the second polythiol compound and the first polythiol composition increases, the change in the ratio of the number of non - peeled squares of the lens to the total number of squares is not obvious, but the refractive index of the lens decreases. When the proportion of the second polythiol compound exceeds 3.0%, the refractive index is already lower than 1.6670, which cannot meet the usage requirements.

[0118] The results of Comparative Application Example 3 and Comparative Application Example 6 show that when the number of film layers coated on the lens surface is increased, the change in the ratio of the number of non - peeled squares of the lens to the total number of squares is not obvious.

[0119] The foregoing description of the disclosed embodiments enables those skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A polythiol composition, characterized in that It comprises a first polythiol composition and a second polythiol compound; the mass ratio of the second polythiol compound to the first polythiol composition is 0.001 to 2.0%; The first polythiol composition comprises a molecular structure having at least 4 thiol groups; The second polythiol compound includes one or more compounds represented by formula II-1, formula II-2, formula II-3, and formula II-4; 2. The polythiol composition according to claim 1, characterized in that The mass ratio of the second polythiol compound to the first polythiol composition is 0.005 to 2.0%.

3. The polythiol composition according to claim 1, characterized in that The first polythiol composition includes compounds represented by Formula I-1 to Formula I-3:

4. A polymerizable composition for optical products, characterized in that: The invention comprises a polythiol composition comprising a first polythiol composition and a second polythiol compound according to any one of claims 1 to 3, and a polyisocyanate.

5. The polymerizable composition for optical products according to claim 4, characterized in that: The polyisocyanate includes tetramethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, 4,4'-diisocyanate dicyclohexylmethane, isophorone diisocyanate, norbornane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl meta-xylylene diisocyanate, dipropyl disulfide, diethyl disulfide, 2,5-diisocyanatomethylthiophene, 2,5-diisocyanatomethyl-1,4-dithiane, 2,5-diisocyanatomethyl Any one or more of ester-1,4-dithiane, dihexyl thiodiisocyanate, dipropyl thiodiisocyanate, bis(isocyanatomethyl)adamantane, bis(isocyanatomethyl)tetrahydrothiophene, 2,6-bis(isocyanatomethyl)naphthalene, 1,5-naphthalene diisocyanate, diethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine triisocyanate, toluene diisocyanate, o-tolidine diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate or triphenylmethane triisocyanate.

6. The polymerizable composition for optical products according to claim 4 or 5, characterized in that: The molar ratio of -SH in the polythiol composition to -NCO of the polyisocyanate is 0.8:1 to 1.2:

1.

7. The polymerizable composition for optical products according to any one of claims 4 to 6, characterized in that: The polymerizable composition for optical products further includes a third polythiol compound; The third polythiol compound includes methanedithiol, methanetrithiol, bis(2-mercaptoethyl) ether, tetrakis(mercaptomethyl)methane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane, 2,2-dimercaptopropane, 1,2-bis(2-mercaptoethoxy)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 2,3-dimercapto-1-propanol, 1,2-dimercaptoethane, 1,3-dimercapto-2-propanol, 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4-dimercaptobutane, 1,2,3-trimercaptopropane, 2-(2-mercaptoethylthio)-1,3-dimercaptopropane, 2,4-dimercaptomethyl-1,5-dimercapto-3-thiapentane, bis(2-mercaptoethyl) sulfide, ethylene glycol bis(3-mercaptopropionate), diethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(2-mercaptoacetate), 1,4-butanediol bis(2-mercaptoacetate), trimethylolpropane trimercaptopropionate, pentaerythritol tetramercaptoacetate, diethylene glycol bis(3-mercaptopropionate), pentaerythritol tetramercaptopropionate, 1,2-dimercaptocyclohexane, 1,1,1-tris(mercaptomethyl)propane, 1,4-butanediol bis(3-mercaptopropionate esters), 1,3-dimercaptocyclohexane, trimethylolpropane trimercaptoacetate, 1,4-dimercaptocyclohexane, 1,3-bis(mercaptomethyl)cyclohexane, 1,4-bis(mercaptomethyl)cyclohexane, bis(4-mercaptophenyl)sulfone, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-bis(2-mercaptoethylthiomethyl)-1,4-dithiane, 2,5-dimercaptomethyl-1-thiane, 2,5-dimercaptoethyl-1-thiane, 2,5-dimercaptomethylthiophene, bis(4-mercaptophenyl)sulfide, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,3-bis(mercaptoethylthiomethyl)-1,4-dithiane any one or more of (4-mercaptomethyl)benzene, 2,5-dimercaptomethyl-1,4-dithiane, 1,4-bis(mercaptomethyl)benzene, 2,2'-dimercaptobiphenyl, bis(4-mercaptophenyl)methane, 2,2-bis(4-mercaptophenyl)propane, 4,4'-dimercaptobiphenyl, bis(4-mercaptophenyl)ether, bis(4-mercaptomethylphenyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 2,2-bis(4-mercaptomethylphenyl)propane, bis(4-mercaptomethylphenyl)ether, bis(4-mercaptomethylphenyl)sulfide, 2,5-dimercapto-1,3,4-thiadiazole or 3,4-thiophenedithiol.

8. An optical product, characterized in that: The optical product is obtained by polymerizing the polymerizable composition for optical products according to any one of claims 4 to 6.

9. The optical product according to claim 8, characterized in that: The polymerization is carried out in the presence of an initiator; During the polymerization, any one or more of a release agent, a toner or an ultraviolet absorber is added.

10. The optical product according to claim 8 or 9, characterized in that: The optical product includes an optical lens, an optical film or a display panel.

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