Polythiol compositions and their applications

Abstract

The present invention relates to the technical field of optical materials, and in particular to polythiol compositions and their applications. The present invention provides a polythiol composition comprising a first polythiol compound having a structure represented by Formula I and a second polythiol compound having a structure represented by Formula II. The polythiol composition provided by the present invention can be used in the production of optical materials by further limiting the mass ratio of the first polythiol compound having the structure represented by Formula I to the second polythiol compound having the structure represented by Formula II, thereby significantly reducing the material leakage rate after casting without significantly reducing the refractive index and improving polythiol application performance.

Description

[Technical Field]

[0001] The present invention relates to the technical field of optical materials, and in particular to polythiol compositions and their applications. [Background technology]

[0002] Transparent plastic materials have advantages such as light weight, toughness, and ease of dyeing, and have been widely used in recent years to produce various optical materials. For example, when used in the fields of eyeglasses and lenses, high transparency, low yellowness, high heat resistance, high strength, high refractive index, and Abbe number are required. A high refractive index allows for thinner lenses, and a high Abbe number reduces chromatic aberration in lenses.

[0003] Polythiourethane-based optical resin materials with such excellent properties are produced mainly from polythiol compounds and polyisocyanates, and have become an important research subject in recent years.

[0004] Most of the current polythiourethane-based optical resin materials are manufactured from a polythiol compound (chemical name: 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol) represented by the following formula and polyisocyanate, and the resulting resin is a thermosetting resin.

[0005] [ka]

[0006] The specific manufacturing method involves first attaching two glass molds with tape, leaving a certain distance between them. Typically, the center-to-center distance is about 2 mm. Polythiol, polyisocyanate, and additives are mixed and degassed to obtain a prepolymer. The tape on the mold is then peeled off, and the prepolymer is poured into the mold, the tape is glued in place, the prepolymer is cured, and the mold is demolded to obtain the resin material.

[0007] In actual applications, if the injected mold is left unattended, the material will leak from the injection port and onto the outer surface of the glass mold. After curing is complete, the leaked material will become a hard resin and adhere to the mold surface, making cleaning difficult and affecting production efficiency. Even more serious problems may occur. In severe cases, the material inside the mold will be exposed, allowing traces of outside air to enter the mold, resulting in air bubbles at the edge of the cured lens at the injection port, which will affect the pass rate of the lens. Summary of the Invention [Problem to be solved by the invention]

[0008] Therefore, the technical problem that the present invention aims to solve is to provide a polythiol composition that can significantly improve material leakage after casting (pouring a prepolymer into a mold) in the production of optical materials, and uses thereof. [Means for solving the problem]

[0009] The present invention provides a polythiol composition comprising a first polythiol compound having the structure shown in Formula I and a second polythiol compound having the structure shown in Formula II.

[0010] [ka]

[0011] Preferably, the mass ratio of the first polythiol compound having the structure represented by chemical formula I to the second polythiol compound having the structure represented by chemical formula II is 0.4-5.0:100.

[0012] The present invention also provides an optical material prepared from raw materials including material A and a catalyst. Material A includes a polythiol composition and a polyisocyanate. The polythiol composition is the polythiol composition described above.

[0013] Preferably, the polyisocyanate is tetramethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 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-diisocyanato-1,4-dithiane, At least one of benzene, 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-toluidine diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate, and triphenylmethane triisocyanate is selected.

[0014] Preferably, the molar ratio of —SH in the polythiol composition to —NCO of the polyisocyanate is 0.8:1 to 1.2:1.

[0015] Preferably, the material a also includes a third polythiol compound, such as 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, methanedithiol, methanetrithiol, bis(2-mercaptoethyl)ether, tetrakis(mercaptomethyl)methane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, or 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-Dimercapto Methyl-1,5-dimercapto-3-thiopentane, 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), 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(mercaptomethyl)benzene, 2,5-dimercaptomethyl-1,4-dithiane, 1,4-bis(mercaptomethyl)benzene, 2,2'-dimercaptobiphenyl, bis(4-mercaptophenyl) At least one of the following is selected: bis(4-mercaptomethylphenyl)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, and 3,4-thiophenedithiol. The mass ratio of the polythiol composition to the third polythiol compound is 0.5:1 to 2:1.

[0016] Preferably, the catalyst includes at least one of dibutyltin dilaurate, dibutyltin dichloride, dibutyltin oxide, and stannous octoate. The mass ratio of the catalyst to the raw material a is 0.005 to 0.2:100.

[0017] Preferably, the raw materials for preparing the optical material also contain an auxiliary agent, such as at least one of a release agent, an ultraviolet absorber, and a color-tuning agent. The release agent is a polyphosphate.

[0018] The present invention also provides a method for producing the above-mentioned optical material, comprising the following steps: mixing raw materials including material A and a catalyst, followed by polymerization and solidification to obtain the optical material; material A includes a polythiol composition and a polyisocyanate; and the polythiol composition is the above-mentioned polythiol composition.

[0019] Preferably, the method for producing an optical material includes the following steps: A) Stirring and dissolving a polyisocyanate, a catalyst, and a mold release agent to obtain a first mixed solution; B) Mixing the first mixed solution, a polythiol composition, and a third polythiol compound, and degassing the mixture to obtain a second mixed solution; C) Injecting the second mixed solution into a mold and polymerizing and solidifying it to obtain an optical material. The polythiol composition is the polythiol composition described above.

[0020] The present invention provides a polythiol composition comprising a first polythiol compound having a structure represented by Formula I and a second polythiol compound having a structure represented by Formula II. Compared to the second polythiol compound, the polythiol composition provided by the present invention has a longer molecular chain and higher self-viscosity, which allows it to increase the viscosity of the prepolymer. At the same time, it also has less steric hindrance in the reaction with polyisocyanate and a higher degree of polymerization of the prepolymer, thereby significantly reducing material leakage after casting in the production of optical materials. By increasing the viscosity moderately, the prepolymer is less likely to leak from the spout. At the same time, the first polythiol compound and the second polythiol compound have similar structures, so their chemical properties are relatively close, and their addition has little effect on the mechanical properties of the resin material. However, due to the low sulfur content and low refractive index of the first polythiol compound, the refractive index of the resin lens produced after adding the first polythiol compound is slightly reduced. Therefore, the amount added must be controlled to minimize leakage while maintaining the appropriate refractive index of the resin lens. DETAILED DESCRIPTION OF THE INVENTION

[0021] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are included in the scope of protection of the present invention. The present invention provides a polythiol composition comprising a first polythiol compound having a structure shown in Formula I and a second polythiol compound having a structure shown in Formula II.

[0022] [ka]

[0023] In some embodiments of the present invention, the mass ratio of the first polythiol compound having the structure shown in Formula I to the second polythiol compound having the structure shown in Formula II is 0.4 to 5.0:100, preferably 0.8 to 2.0:100, for example, 0.4%, 0.6%, 0.8%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 4.0%, or 5.0%.

[0024] The present invention is not particularly limited to the source of the first polythiol compound having the structure shown in Formula I. In a specific embodiment of the present invention, a method for preparing the first polythiol compound having the structure shown in Formula I includes the following steps: a1) adding a sodium hydroxide solution dropwise to mercaptoethanol (2-mercaptoethanol) and stirring at 30 to 40°C; a2) adding 1,2,3-trichloropropane dropwise, and then reacting at 30 to 50°C to obtain 1,2,3-trichloropropane; a3) After adding the hydrochloric acid solution and thiourea, the temperature is increased to 110°C or higher for reflux reaction; a4) The temperature is reduced to 30°C or lower, an aqueous ammonia solution is added, and the temperature is increased to 60-70°C for reaction to obtain a first polythiol compound represented by Formula I.

[0025] Step A1): The mass concentration of the sodium hydroxide solution is 30% to 35%, for example 32%, and the solvent of the sodium hydroxide solution is water. The molar ratio of mercaptoethanol to sodium hydroxide is 1-2:1-2, for example, 1.5:1.55. The stirring temperature is 45°C, and the stirring time is 20 to 40 minutes, for example, 30 minutes.

[0026] Step A2): The molar ratio of 1,2,3-trichloropropane to mercaptoethanol is 0.3 to 0.7:1 to 2, for example, 0.5:1.5. The reaction temperature is 40° C., and the reaction time is 1.5 to 2.5 hours, for example, 2 hours.

[0027] Step A3): The mass concentration of the hydrochloric acid solution is 35 to 40%, for example 37%. The molar ratio of hydrochloric acid to mercaptoethanol is 1.5 to 2.5:1 to 2, for example, 2:1.5. The molar ratio of thiourea to mercaptoethanol is 1:1 to 2:1, for example, 1.6:1.5 (ie, 1.1:1). The reflux reaction temperature is 120° C., and the reaction time is 3 to 5 hours, for example, 4 hours.

[0028] Step A4): Cool to 25°C. The mass concentration of the ammonia solution is 15 to 20%, for example 18%. The molar ratio of aqueous ammonia to mercaptoethanol is 2-3:1-2, for example, 2.5:1.5. The reaction temperature is 65°C, and the reaction time is 2 to 4 hours, for example, 3 hours. After the reaction, a separation step is also included, in which the resulting lower layer crude product is washed with ethanol and the solvent is removed under vacuum to obtain a first polythiol compound having the structure shown in Formula I. The amount of ethanol is the same as the mass of the lower layer crude product. The washing is performed three or more times, specifically three times.

[0029] In the present invention, there are no particular limitations on the source of the second polythiol compound represented by formula II, and commercially available compounds can be used. In certain embodiments of the present invention, a polythiol composition is obtained by combining a first polythiol compound having a structure represented by Formula I and a second polythiol compound having a structure represented by Formula II.

[0030] The present invention also provides an optical material prepared from raw materials including material a and a catalyst. Material a includes a polythiol composition and a polyisocyanate. The polythiol composition is the polythiol composition described above.

[0031] In certain embodiments of the present invention, the polyisocyanate may include tetramethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 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-dithian ... The solvent may include at least one of hexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, m-xylylene diisocyanate, and hydrogenated m-xylylene diisocyanate. More preferably, it contains at least one of hydrogenated m-xylylene diisocyanate, norbornane diisocyanate, and m-xylylene diisocyanate.

[0032] 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, for example, 1:1.

[0033] In some embodiments of the present invention, material a also includes a third polythiol compound. The third polythiol compounds include 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, methanedithiol, methanetrithiol, bis(2-mercaptoethyl)ether, tetrakis(mercaptomethyl)methane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, and 1,6-dimercaptomethyl. Xane, 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-thio pentane, 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-dimercapto cyclohexane, 1,1,1-tris(mercaptomethyl)propane, 1,4-butanediol bis(3-mercaptopropionate), 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(mercaptomethyl)benzene, 2,5-Dimercaptomethyl-1,4-dithiane, 1,4-Bis(mercaptomethyl)benzene, 2,2'-Dimercaptobiphenyl, Bis(4-mercaptophenyl)methane, 2,2-Bis(4 bis(4-mercaptomethylphenyl)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, and 3,4-thiophenedithiol.

[0034] In some embodiments of the present invention, the weight ratio of the polythiol composition to the third polythiol compound is from 0.5:1 to 2:1, for example, 1.8:1 or 1.1:1.

[0035] In certain embodiments of the present invention, the catalyst comprises at least one of dibutyltin dilaurate, dibutyltin dichloride, dibutyltin oxide, and stannous octoate, with dibutyltin dilaurate or dibutyltin dichloride being preferred.

[0036] In some embodiments of the present invention, the mass ratio of the catalyst to the material a is 0.005 to 0.2:100, preferably 0.01 to 0.1:100. In the present invention, if the mass ratio of the catalyst to the raw material a is less than 0.005%, the polymerization may be incomplete, resulting in a deterioration in the mechanical properties of the optical material.If the mass ratio of the catalyst to the raw material a exceeds 0.2%, the polymerization rate may be too fast, resulting in a high color tone of the optical material.

[0037] In some embodiments of the present invention, the raw materials for preparing the optical material further include an auxiliary agent, such as at least one of a mold release agent, an ultraviolet absorber, and a color toning agent.

[0038] In a specific embodiment of the present invention, the release agent is a polyphosphate. The mass ratio of the release agent to material a is 0.005 to 0.2:100, preferably 0.01 to 0.1:100.

[0039] In some embodiments of the present invention, the optical material is an optical lens. The present invention also provides a method for producing the above optical material, which comprises the following steps: After mixing the material a and the raw materials containing the catalyst, the mixture is polymerized and solidified to obtain an optical material. Material a includes a polythiol composition and a polyisocyanate. The polythiol composition is the polythiol composition described above. The raw material components and proportions used in the manufacturing method of the optical material are the same as those described above, and therefore will not be described again here.

[0040] In some embodiments of the present invention, a method for preparing an optical material comprises the steps of: A) The polyisocyanate, catalyst, and release agent are stirred and dissolved to obtain a first mixed solution. B) The first mixed solution, the polythiol composition, and the third polythiol compound are mixed and degassed to obtain a second mixed solution. C) The second mixed solution is poured into a mold and polymerized and solidified to obtain an optical material. The polythiol composition is the polythiol composition described above.

[0041] Step A): The stirring dissolution temperature is 10 to 20°C. Step B): A vacuum pump is used for degassing, the pressure is controlled to 350 Pa or less, and the degassing time is 0.5 to 1.0 hour. Step C): The mold is a glass mold with a diameter of 80 mm and a thickness of 10 mm, and has a 0° curved surface. After said casting, the method further comprises the step of arranging the molded articles flat on a tray.

[0042] In some embodiments of the present invention, the temperature ramp program for polymerization and curing includes: The temperature is maintained at 25-35°C for 175-185 minutes, then the temperature is increased to 43-47°C at a rate of 0.83-1.25°C / 10 minutes, then increased to 48-52°C at a rate of 0.42-0.56°C / 10 minutes, then increased to 58-62°C at a rate of 0.57-0.83°C / 10 minutes, then increased to 115-125°C at a rate of 2.00-2.50°C / 10 minutes, and then held at 115-125°C for 180-240 minutes.

[0043] In some embodiments, the temperature ramp program for polymerization and curing includes: The temperature is maintained at 30°C for 180 minutes, then the temperature is increased to 45°C at a rate of 1.25°C / 10 minutes, then increased to 50°C at a rate of 0.56°C / 10 minutes, increased to 60°C at a rate of 0.83°C / 10 minutes, increased to 120°C at a rate of 2.50°C / 10 minutes, and then held at 120°C for 180 minutes. or The temperature is maintained at 30°C for 180 minutes, then the temperature is increased to 45°C at a rate of 0.83°C / 10 minutes, then increased to 50°C at a rate of 0.42°C / 10 minutes, increased to 60°C at a rate of 0.57°C / 10 minutes, increased to 120°C at a rate of 2.00°C / 10 minutes, and held at 120°C for 240 minutes.

[0044] In some embodiments of the present invention, after polymerization and curing, the method further comprises a cooling step, where the temperature after cooling is 75 to 85°C, for example 80°C, and the time is 115 to 125 minutes, for example 120 minutes. In the present invention, there is no particular limitation on the source of the above raw materials, and commercially available materials can be used.

[0045] The polythiol composition provided by the present invention can be used in the production of optical materials by further limiting the mass ratio of the first polythiol compound having the structure represented by Formula I to the second polythiol compound having the structure represented by Formula II, thereby significantly reducing the material leakage rate after casting without significantly reducing the refractive index and improving the polythiol application performance.

[0046] To further illustrate the present invention, the polythiol composition provided by the present invention and its uses will be described in detail below with examples, which should not be construed as limiting the scope of the present invention.

[0047] Example 1 Preparation of a First Polythiol Compound Having the Structure Shown in Formula I: 117.5 g (1.5 mol) of mercaptoethanol was added to a four-neck flask equipped with a thermometer, a stirrer, and a constant pressure dropping funnel, and 193.8 g of a 32% mass concentration aqueous sodium hydroxide solution (the molar amount of sodium hydroxide was 1.55 mol) was added dropwise, followed by stirring at 35°C for 30 minutes. Next, 73.8 g (0.5 mol) of 1,2,3-trichloropropane was added dropwise, the temperature was controlled at 45° C. during the addition, and after the addition was completed, the reaction was carried out at 40° C. for 2 hours.

[0048] Subsequently, 197.5 g of 37.0% hydrochloric acid (the molar amount of hydrochloric acid was 2 moles) and 122.5 g (1.6 moles) of thiourea were added to the four-neck flask, and the mixture was heated to 120° C. and refluxed for 4 hours.

[0049] The mixture was cooled to 25°C, and 236 g of 18% mass concentration aqueous ammonia (2.5 moles of aqueous ammonia) was added. The temperature was raised to 65°C, and the mixture was allowed to react for 3 hours. After the reaction was completed, the mixture was separated, and the crude product in the lower layer was transferred to a single-mouth bottle and washed three times with the same mass of ethanol as the crude product. After washing, the crude product was vacuum-desolvated to obtain 132 g of a first polythiol compound having the structure shown in Formula I.

[0050] Example 2 A first polythiol compound having a structure represented by Formula I and a second polythiol compound having a structure represented by Formula II are mixed in different proportions to obtain different polythiol compositions.

[0051] The mass ratios (denoted as mI:mII) of the first polythiol compound having a structure represented by formula I to the second polythiol compound having a structure represented by formula II are 0.4%, 0.6%, 0.8%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 4.0%, and 5.0%, respectively.

[0052] (Comparative Example 1) Preparation of optical materials: 52.0 parts by weight of xylylene diisocyanate was added to a batch kettle, followed by 0.01 parts by weight of a catalyst (dibutyltin dichloride) and 0.08 parts by weight of a mold release agent (polyphosphate). The mixture was dissolved by stirring at 15°C, and 48.0 parts by weight of a second polythiol compound represented by Formula II was added and stirred uniformly. The molar ratio of -SH in the second polythiol compound to -NCO in the xylylene diisocyanate was 1:1. A vacuum pump was used to degas the mixture, controlling the pressure at 350 Pa for 0.5 hours to prepare a mixed solution. The mixed solution was poured into clean glass molds with a diameter of 80 mm and a thickness of 10 mm and a 0° curved surface, producing 1,000 molds. After casting was completed, the molds were placed flat on a tray. The mold is placed in an oven and cured at a programmed temperature (hold at 30°C for 180 minutes, then increase the temperature to 45°C at a rate of 1.25°C / 10 minutes, then increase the temperature to 50°C at a rate of 0.56°C / 10 minutes, then increase the temperature to 60°C at a rate of 0.83°C / 10 minutes, then increase the temperature to 120°C at a rate of 2.50°C / 10 minutes, and hold at 120°C for 180 minutes). The mold is then cooled to 80°C over 120 minutes, removed, and opened to obtain the optical lens.

[0053] (Application Examples 1 to 10) The second polythiol compound represented by Chemical Formula II in Comparative Example 1 was replaced with the polythiol composition in Example 2. The molar ratio of -SH in the polythiol composition to -NCO in the polyisocyanate was set to 1:1, and an optical lens was finally produced.

[0054] (Comparative Example 2) The second polythiol compound having the structure shown in Formula II in Comparative Example 1 was replaced with the first polythiol compound having the structure shown in Formula I and the second polythiol compound having the structure shown in Formula II, with a mass ratio of 10%. The molar ratio of -SH in the polythiol composition to -NCO in the polyisocyanate was 1:1, and an optical lens was finally produced.

[0055] The material leakage rate and the refractive index of the optical lens were measured for Application Examples 1 to 10 and Comparative Examples 1 and 2. The results are shown in Table 1.

[0056] Method for measuring material leakage rate: After placing the cast mold in an oven to harden at a constant temperature, remove the mold and inspect the outer surface of the mold to see if any solid resin is attached. If there is leakage, it is judged to be material leakage, and the ratio of the number of leaked material to the total number is calculated to obtain the material leakage rate. The brand name of the inspection device used for refractive index testing is ATAGO, model: NAR-4T.

[0057] [Table 1]

[0058] (Comparative Example 3) Preparation of optical materials: 49.8 parts by mass of hydrogenated xylylene diisocyanate was added to a batch kettle, followed by 0.10 parts by mass of a catalyst (dibutyltin dichloride) and 0.10 parts by mass of a release agent (polyphosphate). The mixture was stirred at 15°C to dissolve the mixture. 30.2 parts by mass of a second polythiol compound represented by Formula II and 20.0 parts by mass of a third polythiol compound (pentaerythritol tetramercaptopropionate) were then added and stirred uniformly. The molar ratio of -SH in the polythiol composition to -NCO in the polyisocyanate was 1:1. A vacuum pump was used to degas the mixture, controlling the pressure to 350 Pa for 0.5 hours to prepare a mixed solution. This mixed solution was then poured into a glass mold with a diameter of 80 mm, a thickness of 10 mm, and a 0° curved surface, producing 1,000 molds. After pouring was completed, the material leakage from the pouring port was observed, and the material leakage rate was calculated. The mold is placed in an oven and cured at a programmed temperature (hold at 30°C for 180 minutes, increase the temperature to 45°C at a rate of 0.83°C / 10 minutes, increase the temperature to 50°C at a rate of 0.42°C / 10 minutes, increase the temperature to 60°C at a rate of 0.57°C / 10 minutes, then increase the temperature to 120°C at a rate of 2.00°C / 10 minutes, and hold at 120°C for 240 minutes).The mold is then cooled to 80°C over 120 minutes, removed, and opened to obtain the optical lens.

[0059] (Application Examples 11-20) The second polythiol compound represented by Chemical Formula II in Comparative Example 3 was replaced with the polythiol composition in Example 2. The molar ratio of -SH in the polythiol composition to -NCO in the polyisocyanate was set to 1:1, and an optical lens was finally produced.

[0060] Comparative Example 4 The second polythiol compound having the structure shown in Formula II in Comparative Example 3 was replaced with the first polythiol compound having the structure shown in Formula I and the second polythiol compound having the structure shown in Formula II. The mass ratio was 10%. The molar ratio of -SH in the polythiol composition to -NCO in the polyisocyanate was 1:1. Finally, an optical lens was produced.

[0061] The material leakage rates and refractive indices of the optical lenses of Application Examples 11 to 20 and Comparative Examples 3 and 4 were measured, and the results are shown in Table 2. How to detect material leakage rate: After placing the poured mold in an oven to cure at a constant temperature, remove the mold and inspect the outer surface of the mold to see if there is any resin solids adhering to it. If there is any leakage, it is judged to be a material leak, and the ratio of the number of leaked material to the total number is calculated to find the material leakage rate.

[0062] [Table 2]

[0063] (Application Example 21) Preparation of optical materials: 22.8 parts by weight of hexamethylene diisocyanate, 10.0 parts by weight of isophorone diisocyanate, 16.0 parts by weight of hydrogenated xylylene diisocyanate, 0.15 parts by weight of a catalyst (dibutyltin dichloride), and 0.10 parts by weight of a mold release agent (polyphosphate) were added to a batch kettle. 33.0 parts by weight of a polythiol composition (a first polythiol compound having the structure shown in Formula I and a second polythiol compound having the structure shown in Formula II, in a 0.8% weight ratio) and 18.2 parts by weight of pentaerythritol tetramercaptopropionate were added and dissolved with stirring at 15°C. The molar ratio of -SH in the polythiol composition to -NCO in the polyisocyanate was 1:1. A vacuum pump was used to degas the mixture at a pressure of 350 Pa for 0.5 hours, yielding a mixed solution. The resulting mixed solution was poured into a 0° curved glass mold with a diameter of 80 mm and a thickness of 10 mm. The mixture was poured into 1,000 molds, which were then laid flat on a tray. The molds were then placed in an oven and cured at a programmed temperature (hold at 30°C for 180 minutes, then ramp to 45°C at a rate of 0.83°C / 10 minutes, then ramp to 50°C at a rate of 0.42°C / 10 minutes, then ramp to 60°C at a rate of 0.57°C / 10 minutes, then ramp to 120°C at a rate of 2.00°C / 10 minutes, and hold at 120°C for 240 minutes). The temperature was then lowered to 80°C over 120 minutes, and the molds were removed and opened to obtain the optical lenses. The measured refractive index was 1.5958, and the estimated material leakage rate was 1.0%.

[0064] (Application Example 22) 49.6 parts by weight of norbornane diisocyanate, 0.03 parts by weight of a catalyst (dibutyltin dichloride), and 0.75 parts by weight of a mold release agent (polyphosphate) were added to a batch kettle, stirred, and dissolved at 15°C. 25.5 parts by weight of a polythiol composition (a first polythiol compound having the structure shown in Formula I and a second polythiol compound having the structure shown in Formula II, in a 0.8% weight ratio) and 23.9 parts by weight of pentaerythritol tetramercaptopropionate were added and stirred uniformly. The molar ratio of -SH in the polythiol composition to -NCO in the polyisocyanate was 1:1. A vacuum pump was used to degas the mixture at a pressure of 350 Pa for 0.5 hours to obtain a mixed solution. The resulting mixed solution was poured into a 0° curved glass mold with a diameter of 80 mm and a thickness of 10 mm. 1,000 molds were poured, and upon completion of the pouring, they were placed flat on a tray. The mold is placed in an oven and cured at a programmed temperature (hold at 30°C for 180 minutes, then increase the temperature to 45°C at a rate of 0.83°C / 10 minutes, increase the temperature to 50°C at a rate of 0.42°C / 10 minutes, increase the temperature to 60°C at a rate of 0.57°C / 10 minutes, increase the temperature to 120°C at a rate of 2.00°C / 10 minutes, and hold at 120°C for 240 minutes). The mold is then cooled to 80°C over 120 minutes, removed, and opened to obtain the optical lens. The measured refractive index is 1.5960, and the statistical material leakage rate is 0.9%.

[0065] The above 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 comprising a first polythiol compound having a structure represented by Formula I and a second polythiol compound having a structure represented by Formula II. 【Chemical 1】

2. The polythiol composition according to claim 1, characterized in that the mass ratio of the first polythiol compound having a structure represented by Formula I to the second polythiol compound having a structure represented by Formula II is 0.4 to 5.0:

100.

3. An optical material prepared from material a and a catalyst, The material a includes a polythiol composition and a polyisocyanate, The polythiol composition according to claim 1 or 2, which is an optical material.

4. The polyisocyanate may be tetramethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 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-diisocyanato-1,4-dithiane, thiodihexyldiisocyanate, 2,5-diisocyanatomethyl-1,4-dithiane ...

4. The optical material according to claim 3, comprising at least one of the following: bis(isocyanatomethyl)isocyanate, 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-toluidine diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate, and triphenylmethane triisocyanate.

5. 4. The optical material according to claim 3, wherein the molar ratio of --SH in the polythiol composition to --NCO in the polyisocyanate is 0.8:1 to 1.2:

1.

6. The material a further includes a third polythiol compound, The third polythiol compound may be 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, methanedithiol, methanetrithiol, bis(2-mercaptoethyl)ether, tetrakis(mercaptomethyl)methane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercapto Hexane, 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- Thiopentane, 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-dimercapto bis(mercaptomethyl)cyclohexane, 1,1,1-tris(mercaptomethyl)propane, 1,4-butanediol bis(3-mercaptopropionate), 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(mercaptomethyl)benzene, 2,5-dimercaptomethyl-1,4-dithiane, 1,4-bis(mercaptomethyl)benzene, 2,2'-dimercaptobiphenyl, bis(4-mercaptophenyl)methane, 2,2-bis(4- at least one of 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, and 3,4-thiophenedithiol, 4. The optical material according to claim 3, wherein the mass ratio of the polythiol composition to the third polythiol compound is 0.5:1 to 2:

1.

7. the catalyst comprises at least one of dibutyltin dilaurate, dibutyltin dichloride, dibutyltin oxide, and stannous octoate; 4. The optical material according to claim 3, wherein the mass ratio of the catalyst to the material a is 0.005 to 0.2:

100.

8. The raw materials for preparing the optical material further contain an auxiliary agent, 4. The optical material according to claim 3, wherein the auxiliary agent comprises at least one of a release agent, an ultraviolet absorber, and a toning agent, and the release agent is a polyphosphate.

9. The method for producing the optical material includes a step of mixing raw materials containing material A and a catalyst, and then polymerizing and solidifying the mixture to obtain the optical material, The material a includes a polythiol composition and a polyisocyanate, The method for producing an optical material, wherein the polythiol composition is the polythiol composition according to claim 1 or 2.

10. A method for producing the optical material, comprising the following steps: A) A polyisocyanate, a catalyst, and a release agent are stirred and dissolved to obtain a first mixed solution. B) The first mixed solution, the polythiol composition, and the third polythiol compound are mixed and degassed to obtain a second mixed solution. C) The second mixed solution is poured into a mold and polymerized and solidified to obtain an optical material. The method according to claim 9 , wherein the polythiol composition is the polythiol composition according to claim 1 or 2 .

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