High-refractive-index optical resin material composition and optical resin material

Abstract

The invention relates to the technical field of optical materials, in particular to a high-refractive-index optical resin material composition and an optical resin material, and the high-refractive-index optical resin material composition comprises an episulfide compound and a catalyst; the episulfide compound comprises one or more of bis (beta-episulfide propyl) thioether and bis (beta-episulfide propyl) disulfide; the mass content of the catalyst is 0.001%-10%; the activation energy of the optical resin material composition with the high refractive index is 35 to 160 KJ.mol <-1 >. According to the method, the activation energy is calculated through simulation, the appropriate catalyst is used for polymerizing the material, the bubble problem of the high-refractive-index optical resin material is solved, the yield is greatly improved, meanwhile, the curing time is shortened, manpower and material resources are greatly saved, and the wide market application prospect is achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of optical materials, in particular to a high-refractive optical resin material composition and an optical resin material. BACKGROUND

[0002] Optical resin is an organic polymer material aiming at realizing specific optical performance, and its core characteristics include high refractive index (up to 1.630 or above), light transmittance of 84%-95%, and lightweight advantage with density only 1 / 3 to 1 / 2 of glass. The material is widely used in the manufacture of glasses.

[0003] However, the yield of optical resin material with refractive index greater than 1.70 is low at present, and the main reason is that when the refractive index exceeds 1.70, the bubble problem occurs. It is found that during the curing process of high-refractive optical resin material, the liquid prepolymer expands and shrinks with the increase of temperature, and the interface of the adhesive tape is obviously expanded with the hole, and the material shrinks greatly after reaching the gel point, which causes the sample to have a gap, which is called the bubble phenomenon. The reaction rate is fast before the gel point, and the heat release is large, which cannot be dissipated in time, and the adhesive tape is expanded with the hole, which is the inducement of the bubble phenomenon, and the low-refractive material has no such phenomenon. Or the reaction rate is slow before the gel point, although there is no bubble, but the performance of the material is obviously decreased, which cannot meet the use conditions.

[0004] The bubble phenomenon greatly reduces the yield of high-refractive optical resin material and affects the application of optical resin material. SUMMARY

[0005] Therefore, the technical problem to be solved by the present application is to provide a high-refractive optical resin material composition and an optical resin material, by controlling the activation energy of the composition, so that the prepared high-refractive optical resin material has a high yield.

[0006] To achieve the above-mentioned purpose, the present application provides a high-refractive optical resin material composition, comprising: a cyclic sulfur compound and a catalyst.

[0007] The cyclic sulfur compound includes one or more of bis(beta-cyclopropyl sulfide) and bis(beta-cyclopropyl sulfide).

[0008] The mass content of the catalyst is 0.001%-10%;

[0009] The activation energy of the high-refractive optical resin material composition is 35-160 KJ·mol -1 .

[0010] The cyclic sulfur compound in the composition can be bis(beta-cyclopropyl sulfide) and / or bis(beta-cyclopropyl sulfide).

[0011] The catalyst preferably includes one or more of an amine-based catalyst, a phosphine-based catalyst, and a quaternary phosphonium salt-based catalyst.

[0012] The amine-based catalyst preferably includes one or more of trimethylamine, triethylamine, tri-n-propylamine, tri-i-propylamine, tri-1,2-dimethylpropylamine, tri-3-methoxypropylamine, tri-n-butylamine, tri-i-butylamine, tri-s-butylamine, dicyclohexyl-ethylamine, cyclohexyl-diethylamine, N,N-dimethylhexylamine, N-methyl-di- hexylamine, N,N-dimethylcyclohexylamine, N,N-dicyclohexylmethylamine, N,N-diethyl- ethanolamine, N,N-dimethylethanolamine, N-ethyl-diethanolamine, and the like.

[0013] The phosphine-based catalyst preferably includes one or more of trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tri-i-propylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,2- bis(dimethylphosphino)ethane, and the like.

[0014] The quaternary phosphonium salt-based catalyst preferably includes one or more of tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, and the like.

[0015] Further preferably, the catalyst includes one or more of N,N-dimethylcyclohexylamine, N,N-dicyclohexylmethylamine, and tetrabutylphosphonium bromide.

[0016] In some embodiments of the present application, the catalyst is selected from N,N- dimethylcyclohexylamine and / or N,N-dicyclohexylmethylamine, or tetrabutylphosphonium bromide.

[0017] The mass content of the catalyst in the composition is preferably 0.001% to 10%, more preferably 0.001% to 5%, further preferably 0.005% to 1.5%, still further preferably 0.01% to 1.5%, yet further preferably 0.01% to 0.5%, most preferably 0.008% to 0.2%, and in some embodiments of the present application, the content of the catalyst is 0.008%, 0.01%, 0.06%, 0.07%, 0.09%, 0.1%, 0.11%, 0.12%, 0.15%, 0.2%, or a range value having any of the above values as an upper limit or a lower limit.

[0018] Preferably, the high-refractive optical resin material composition further includes a polythiol compound. The polythiol compound can increase the refractive index of the material and improve the optical properties.

[0019] The polythiol compound preferably includes:

[0020] one or more of pentaerythritol tetra(2-mercaptoacetate), pentaerythritol tetra(3- mercaptopropionate), bis(mercaptoethyl) sulfide, 1,2-bis(2-mercaptoethylthio)-3- mercaptopropane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7- dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11- dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9- trithiaundecane, 2,5-dimercaptomethyl-1,4-dithiacyclohexane, 1,1,3,3-tetrakis- (mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, 2- (2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, ethylene glycol bis(3- mercaptopropionate), and the like; more preferably 5,7-dimercaptomethyl-1,11-dimercapto- 3,6,9-trithiaundecane and / or 1,2-bis(2-mercaptoethylthio)-3-mercapto-propane.

[0021] The mass ratio of the polythiol compound and the cyclic sulfur compound is preferably 0-30:100-70, and more preferably 0-25:100-75. Preferably, the content of the polythiol compound is not 0, and more preferably 1-30:99-70, and further preferably 1-25:99-75.

[0022] That is, the amount of the cyclic sulfur compound added in the composition is 70-100 parts by weight, and the amount of the polythiol compound added is 0-30 parts by weight, and the total amount of the two is 100 parts by weight. Preferably, the amount of the cyclic sulfur compound added is 75-100 parts by weight, and the amount of the polythiol compound added is 0-25 parts by weight, and the total amount of the two is 100 parts by weight.

[0023] Preferably, the content of the polythiol compound is not 0, and the amount of the cyclic sulfur compound added is 70-99 parts by weight, and the amount of the polythiol compound added is 1-30 parts by weight, and the total amount of the two is 100 parts by weight. More preferably, the amount of the cyclic sulfur compound added is 75-99 parts by weight, and the amount of the polythiol compound added is 1-25 parts by weight, and the total amount of the two is 100 parts by weight.

[0024] In order to facilitate the demolding of the material, preferably, the high-refractive optical resin material composition further comprises a release agent.

[0025] The release agent is not particularly limited in the present application, and can be any release agent known to those skilled in the art. Preferably, the release agent is an acidic phosphate release agent, and more preferably one or more of dibutyl phosphate, polyoxyethylene ether phosphate, and the like.

[0026] In order to prevent the photo-degradation of the resin material, protect the color and performance of the material, and prolong the service life, preferably, the high-refractive optical resin material composition further comprises: an ultraviolet absorber.

[0027] The ultraviolet absorber of the present application can not be specially limited, and can be an ultraviolet absorber known to those skilled in the art, preferably a benzotriazole ultraviolet absorber, including but not limited to one or more of UV-326, UV-327, UV-329, UV-541, etc., more preferably UV-329.

[0028] The present application limits the amount of catalyst to make the activation energy of the high-refractive optical resin material composition 35-160 KJ·mol -1 , preferably, the activation energy is 40-150 KJ·mol -1 . More preferably, the activation energy is 40-130 KJ·mol -1

[0029] The activation energy can be tested by thermal analysis devices known to those skilled in the art, including but not limited to: differential scanning calorimeter, calorimeter, microcalorimeter, differential thermal analyzer, differential thermal-gravimetric simultaneous analyzer, thermal gravimetric analyzer, thermal mechanical analyzer, dynamic thermal mechanical analyzer, etc.

[0030] The present application is introduced by taking differential scanning calorimeter (DSC) as an example:

[0031] After the raw materials of the composition are uniformly mixed, the differential scanning calorimeter is used to test the curing temperature rise reaction heat with a selected dynamic temperature rise rate of 15 K / min, and the size of the activation energy (Ea) is simulated according to the reaction heat curve; the suitable catalyst process is adjusted according to the activation energy range, and the activation energy is simulated and calculated again until the activation energy is within the specified range.

[0032] The general reaction kinetics is described based on the following assumptions: the reaction rate is the change of the conversion rate per unit time, which is a function of the conversion rate:

[0033]

[0034] The temperature dependence of the reaction rate constant K can be described by the Arrhenius equation:

[0035]

[0036] Substitute k in the reaction rate equation with the Arrhenius equation to get:

[0037]

[0038] Wherein, k(T): the reaction rate constant corresponding to the temperature T; k0: the rate constant (referring to the pre-exponential factor) when the temperature is infinite; f(alpha): the mechanism function related to the reaction rate, that is, the reaction model, which is independent of the temperature; E a : activation energy; R: molar gas constant; alpha: reaction conversion rate.

[0039] The simple reaction process can be described by n-stage kinetics f(alpha)=(1-alpha)n, thereby obtaining:

[0040]

[0041] The parameters E a , k0 and n can be determined by the least square method from the data of a single dynamic temperature rising test; and the reaction rate is calculated according to the type of the test:

[0042]

[0043] Wherein, is the heat flow, and Delta H tot is the peak area (mJ); the reaction rate is proportional to the heat flow.

[0044] Through deep research, it is found that adding an appropriate amount of catalyst and controlling the activation energy can effectively solve the problem of bubbling of high refractive index optical resin materials. According to real-time infrared functional group detection, the reaction rate is faster before the gel point. The differential scanning calorimeter is used to select the dynamic temperature rising rate to test the curing temperature rising reaction heat, and the activation energy (Ea) is simulated according to the reaction heat curve. The lower the activation energy, the faster the reaction rate, and the easier the sample to bubble; the higher the activation energy, although there is no bubbling phenomenon, but the reaction rate is slower, the material after curing is not completely reacted, and the glass transition temperature is low. Adjusting the amount of catalyst to make the activation energy in a certain range can effectively solve the problem of bubbling. Through a large number of experiments, it is verified that the amount of catalyst added: 0.001%~10%, the activation energy is in the range of 35KJ·mol -1 ~160KJ·mol -1 , and the optical resin material after curing has no bubbling phenomenon and excellent performance, thereby improving the yield and being beneficial to industrial production.

[0045] The test results show that when the activation energy is controlled in the above range, the yield of the high refractive index optical resin material can reach 98%~100%, and no bubbles are generated.

[0046] The optical resin prepared by the method provided by the present application does not need to be improved by adjusting the program temperature, avoiding the problem of long time consumption and large number of parallel times in the program temperature in industrial production.

[0047] Based on the above, the present application provides a high refractive index optical resin material, which is obtained by polymerization and curing of the high refractive index optical resin material composition.

[0048] Preferably, the refractive index of the optical resin material is greater than 1.70.

[0049] The above curing parameters can not be specially limited, and can be adjusted as needed by those skilled in the art.

[0050] Preferably, the curing is programmed temperature curing.

[0051] The temperature rising procedure of the programmed temperature curing comprises primary curing and secondary curing.

[0052] The primary curing is:

[0053] The initial temperature is 15-30℃, and the temperature is kept for 2-6h, then the temperature is raised to 55-65℃ for 10-15h, raised to 75-105℃ for 2-5h, kept for 2-5h, and then the temperature is lowered to 60-75℃ for 1-3h.

[0054] The secondary curing is:

[0055] The temperature is kept at 100-120℃ for 1-4h, and then the temperature is lowered to 60-75℃ for 1-3h.

[0056] More preferably, the curing is programmed temperature curing.

[0057] The temperature rising procedure of the programmed temperature curing comprises primary curing and secondary curing.

[0058] The primary curing is:

[0059] The initial temperature is 15-30℃, and the temperature is kept for 2-4h, then the temperature is raised to 55-65℃ for 10-15h, raised to 90-100℃ for 2-5h, kept for 2-4h, and then the temperature is lowered to 60-70℃ for 1-2h.

[0060] The secondary curing is:

[0061] The temperature is kept at 100-120℃ for 1-3h, and then the temperature is lowered to 60-70℃ for 1-2h.

[0062] The secondary curing is performed after the mold is opened.

[0063] The above curing parameters can obtain the best yield of finished products.

[0064] After curing, whether there is blister is detected by naked eyes, and the yield of finished products is calculated.

[0065] Compared with the prior art, the high-refractive optical resin material composition provided by the application comprises a cyclic sulfur compound and a catalyst; the cyclic sulfur compound comprises one or more of bis(beta-cyclopropyl sulfide) and bis(beta-cyclopropyl sulfide) disulfide; the mass content of the catalyst is 0.001% to 10%; and the activation energy of the high-refractive optical resin material composition is 35 to 160 KJ·mol -1 The application solves the problem of bubbles in the high-refractive optical resin material by simulating the size of the activation energy and using a suitable catalyst polymerization material, greatly improves the yield of finished products, and has excellent performance of the prepared optical material, can meet the application requirements. The preparation process is simple and easy to industrialize, reduces the time cost increased by the optimization program temperature in the production process, and shortens the curing time, greatly saves manpower and material resources, and has a wide market application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0066] Figure 1 The high-refractive optical resin material prepared by the application is shown in the figure. DETAILED DESCRIPTION

[0067] In order to further illustrate the application, the following embodiments are described in detail. However, it should be understood that these descriptions are only to further illustrate the features and advantages of the application, and are not limitations on the claims of the application.

[0068] All raw materials of the application are not particularly limited in source, and can be purchased on the market or prepared according to conventional methods well known to those skilled in the art.

[0069] The abbreviations of the following examples are as follows:

[0070] Component A: bis(beta-cyclopropyl sulfide);

[0071] Component B: bis(beta-cyclopropyl sulfide) disulfide;

[0072] Component C: 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane;

[0073] Component D: 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane;

[0074] CAT-1: N,N-dimethylcyclohexylamine;

[0075] CAT-2: N,N-dicyclohexylmethylamine;

[0076] CAT-3: tetrabutylphosphonium bromide.

[0077] The detection method is as follows:

[0078] Refractive index (Ne): Abbe refractometer;

[0079] Glass transition temperature (Tg): DSC-II differential scanning calorimeter, heating rate 15 K / min;

[0080] Yield: 100 lenses were prepared for each formulation. Yield = (100 - number of blister lenses) / 100 * 100%.

[0081] Example 1

[0082] At 15℃, 0.01 g CAT-1, 0.1 g CAT-2 and 75 g component B, 0.08 g UV329, 0.005 g di-n-butyl phosphate were stirred uniformly, then 25 g component C was added and stirred uniformly, and then the sample was tested for curing heat of reaction by DSC at a dynamic heating rate of 15 K / min. The activation energy (Ea) was 126.54 KJ·mol -1 .

[0083] It was determined that the activation energy would not cause the lenses to produce bubbles, so the sample was vacuum-stirred degassed for 30 min, filtered through a polytetrafluoroethylene filter membrane with a pore size of 10 μm, injected into a mold, and then the mold was placed in a programmed temperature curing oven for curing to obtain a bubble-free optical material. The refractive index was 1.7326, the Tg was 81℃, and the yield was 100% in 100 pieces.

[0084] The temperature program of the programmed temperature curing oven was as follows: the initial temperature of the first curing was 30℃, and the temperature was maintained for 2 h, then the temperature was increased to 55℃ for 12 h, then the temperature was increased to 100℃ for 5 h, then the temperature was maintained for 2 h, and finally the temperature was decreased to 60℃ for 2 h. After demolding, the mold was subjected to a programmed temperature for secondary curing, and the temperature was maintained at 100℃ for 2 h, and finally the temperature was decreased to 65℃ for 1 h.

[0085] Example 2

[0086] At 15℃, 0.03 g CAT-1, 0.07 g CAT-2 and 87 g component B, 0.08 g UV329, 0.005 g di-n-butyl phosphate were stirred uniformly, then 13 g component C was added and stirred uniformly, and then the sample was tested for curing heat of reaction by DSC at a dynamic heating rate of 15 K / min. The activation energy (Ea) was 89.79 KJ·mol -1 .

[0087] It was determined that the activation energy would not cause the lenses to produce bubbles, so the sample was vacuum-stirred degassed for 30 min, filtered through a polytetrafluoroethylene filter membrane with a pore size of 10 μm, injected into a mold, and then the mold was placed in a programmed temperature curing oven for curing to obtain a bubble-free optical material. The refractive index was 1.7389, the Tg was 82℃, and the yield was 99% in 100 pieces.

[0088] The temperature program of the programmed temperature curing oven is as follows: the initial temperature of the first curing is 20℃, the temperature is kept for 4h, the temperature is raised to 55℃ for 10h, then the temperature is raised to 100℃ for 3h, the temperature is kept at 100℃ for 2h, and finally the temperature is lowered to 70℃ for 1.5h. After the mold is opened, the second curing is performed by programmed temperature rising, the temperature is kept at 120℃ for 2h, and finally the temperature is lowered to 70℃ for 1.5h.

[0089] Example 3

[0090] At 15℃, 0.02g CAT-1, 0.08g CAT-2, 10g component A and 80g component B, 0.08g UV329, 0.005g di-n-butyl phosphate are stirred uniformly, then 8g component C and 2g component D are stirred uniformly, and then a sample is taken to test the curing heat of reaction by DSC with a dynamic temperature rising rate of 15K / min. The activation energy (Ea) is 65.32KJ·mol -1 .

[0091] It is judged that the activation energy will not cause bubbles in the lens. Therefore, the sample is vacuum stirred and degassed for 30min, filtered through a polytetrafluoroethylene filter membrane with a pore size of 10μm, injected into a mold, and then the mold is placed in a programmed temperature curing oven for curing to obtain an optical material without bubbles. The refractive index is 1.7359, the Tg is 89℃, and the yield rate of 100 pieces is 100%.

[0092] The initial temperature is 20℃, the temperature is kept for 2h, then the temperature is raised to 60℃ for 15h, the temperature is raised to 100℃ for 2h, then the temperature is kept at 100℃ for 2h, and finally the temperature is lowered to 60℃ for 1h. After the mold is opened, the second curing is performed by programmed temperature rising, the temperature is kept at 100℃ for 2h, and finally the temperature is lowered to 60℃ for 1h.

[0093] Example 4

[0094] At 15℃, 0.05g CAT-1, 0.04g CAT-2 and 91g component B, 0.08g UV329, 0.005g di-n-butyl phosphate are stirred uniformly, then 9g component C is stirred uniformly, and then a sample is taken to test the curing heat of reaction by DSC with a dynamic temperature rising rate of 15K / min. The activation energy (Ea) is 63.25KJ·mol -1 .

[0095] It is judged that the activation energy will not cause bubbles in the lens. Therefore, the sample is vacuum stirred and degassed for 30min, filtered through a polytetrafluoroethylene filter membrane with a pore size of 10μm, injected into a mold, and then the mold is placed in a programmed temperature curing oven for curing to obtain an optical material without bubbles. The refractive index is 1.7359, the Tg is 89℃, and the yield rate of 100 pieces is 100%.

[0096] The initial temperature is 15°C, and the sample is kept at this temperature for 4 hours. Then the temperature is raised to 65°C in 10 hours, and then to 90°C in 2 hours. The sample is kept at 90°C for 4 hours, and then the temperature is lowered to 60°C in 1 hour. After the mold is opened, the sample is subjected to a secondary curing process, in which the temperature is raised to 110°C and kept at this temperature for 2 hours. Finally, the temperature is lowered to 70°C in 1 hour.

[0097] Example 5

[0098] At 15°C, 0.1 g of CAT-1, 88 g of component A, and 5 g of component B, 0.08 g of UV329, and 0.005 g of di-n-butyl phosphate are stirred uniformly. Then 7 g of component C is added and stirred uniformly. A sample is taken and subjected to a curing temperature rise reaction heat test using DSC with a dynamic temperature rise rate of 15 K / min. The activation energy (Ea) is 42.61 KJ·mol -1 .

[0099] It is determined that the activation energy will not cause bubbles in the lens. Therefore, the sample is vacuum-stirred and degassed for 30 minutes, filtered through a polytetrafluoroethylene filter membrane with a pore size of 10 μm, and injected into a mold. Then the mold is placed in a programmed temperature curing oven for curing to obtain an optical material without bubbles. The refractive index is 1.7126, the Tg is 92°C, and the yield rate is 99% in 100 pieces.

[0100] The temperature program of the programmed temperature curing oven is as follows: the initial temperature of the first curing is 25°C, and the sample is kept at this temperature for 3 hours. Then the temperature is raised to 55°C in 12 hours, and then to 100°C in 5 hours. The sample is kept at 100°C for 2 hours, and then the temperature is lowered to 60°C in 2 hours. After the mold is opened, the sample is subjected to a secondary curing process, in which the temperature is raised to 100°C and kept at this temperature for 2 hours. Finally, the temperature is lowered to 65°C in 1 hour.

[0101] Example 6

[0102] At 15°C, 0.07 g of CAT-3, 75 g of component A, 13 g of component B, 0.08 g of UV329, and 0.005 g of di-n-butyl phosphate are stirred uniformly. Then 12 g of component D is added and stirred uniformly. A sample is taken and subjected to a curing temperature rise reaction heat test using DSC with a dynamic temperature rise rate of 15 K / min. The activation energy (Ea) is 100.52 KJ·mol -1 .

[0103] It is determined that the activation energy will not cause bubbles in the lens. Therefore, the sample is vacuum-stirred and degassed for 30 minutes, filtered through a polytetrafluoroethylene filter membrane with a pore size of 10 μm, and injected into a mold. Then the mold is placed in a programmed temperature curing oven for curing to obtain an optical material without bubbles. The refractive index is 1.7216, the Tg is 93°C, and the yield rate is 98% in 100 pieces.

[0104] The temperature program of the programmed temperature curing oven is as follows: the initial temperature of the first curing is 20°C, and the temperature is kept for 3h, then the temperature is increased to 55°C for 12h, then the temperature is increased to 100°C for 5h, then the temperature is kept for 2h, and finally the temperature is decreased to 60°C for 2h. After the mold is opened, the second curing is performed by increasing the temperature, the temperature is kept at 110°C for 2h, and finally the temperature is decreased to 65°C for 1h.

[0105] Comparative Example 1

[0106] At 15°C, 0.05g CAT-1, 0.15g CAT-2 and 87g component A, 0.08g UV329, 0.005g di-n-butyl phosphate are stirred uniformly, then 13g component B is added and stirred uniformly, and then the sample is taken for DSC dynamic temperature rate selection of 15K / min to test the curing temperature reaction heat, and the activation energy (Ea) is 25.86KJ·mol -1 .

[0107] It is judged that the activation energy will cause bubbles in the lens, and the experimental data is further verified, and the results are as follows:

[0108] The sample is continuously vacuum stirred and degassed for 30min, filtered through a polytetrafluoroethylene filter membrane with a pore size of 10μm, and injected into a mold, and then the mold is placed in a programmed temperature curing oven for curing to obtain an optical material with bubbles. The refractive index is 1.7412, the Tg is 79°C, and the yield of 100 pieces is 8%. The yield is low.

[0109] The temperature program of the programmed temperature curing oven is as follows: the initial temperature of the first curing is 20°C, and the temperature is kept for 4h, then the temperature is increased to 55°C for 10h, then the temperature is increased to 100°C for 3h, then the temperature is kept at 100°C for 2h, and finally the temperature is decreased to 70°C for 1.5h. After the mold is opened, the second curing is performed by increasing the temperature, the temperature is kept at 120°C for 2h, and finally the temperature is decreased to 70°C for 1.5h.

[0110] Comparative Example 2

[0111] At 15°C, 0.1g CAT-1, 0.02g CAT-2, 70g component A, 0.08g UV329, 0.005g di-n-butyl phosphate are stirred uniformly, then 30g component C is added and stirred uniformly, and then the sample is taken for DSC dynamic temperature rate selection of 15K / min to test the curing temperature reaction heat, and the activation energy (Ea) is 32KJ·mol -1 .

[0112] It is judged that the activation energy will cause bubbles in the lens, and the experimental data is further verified, and the results are as follows:

[0113] The sample was vacuum-stirred and degassed for 30 min, filtered through a polytetrafluoroethylene filter membrane with a pore size of 10 pm, and injected into a mold, and then the mold was placed in a programmed temperature curing oven to obtain an optical material with bubbles. The refractive index was 1.7125, the Tg was 85°C, and the yield rate of 100 pieces was 16%. The sample had a Tg of 85°C, and the yield rate was low.

[0114] The temperature rising program of the programmed temperature curing oven was as follows: the initial temperature of the first curing was 20°C, and the temperature was kept for 4 h, then the temperature was raised to 55°C in 10 h, then the temperature was raised to 11°C in 3 h, the temperature was kept at 100°C for 2 h, and finally the temperature was lowered to 70°C in 1 h. After the mold was opened, the second curing was performed by programmed temperature rising, the temperature was kept at 110°C for 2 h, and finally the temperature was lowered to 70°C in 1.5 h.

[0115] Comparative Example 3

[0116] At 15°C, 0.008 g of CAT-1 and 91 g of component A, 0.08 g of UV329, and 0.005 g of di-n-butyl phosphate were stirred uniformly, and then 9 g of component B was added and stirred uniformly. The sample was taken for DSC to test the curing temperature reaction heat at a dynamic temperature rising rate of 15 K / min, and the activation energy (Ea) was 168.52 KJ·mol -1 .

[0117] It was judged that the activation energy would not cause bubbles in the lens, but the material performance was not up to standard and could not be further processed and used. The experimental verification results were as follows:

[0118] The sample was vacuum-stirred and degassed for 30 min, filtered through a polytetrafluoroethylene filter membrane with a pore size of 10 pm, and injected into a mold, and then the mold was placed in a programmed temperature curing oven to obtain an optical material with bubbles. The refractive index was 1.7125, the Tg was 85°C, and the yield rate of 100 pieces was 16%. The sample had a Tg of 85°C, and the yield rate was low.

[0119] The temperature rising program of the programmed temperature curing oven was as follows: the initial temperature of the first curing was 20°C, and the temperature was kept for 4 h, then the temperature was raised to 55°C in 10 h, then the temperature was raised to 11°C in 3 h, the temperature was kept at 100°C for 2 h, and finally the temperature was lowered to 70°C in 1 h. After the mold was opened, the second curing was performed by programmed temperature rising, the temperature was kept at 110°C for 2 h, and finally the temperature was lowered to 70°C in 1.5 h.

[0120] Comparative Example 4

[0121] At 15°C, 0.02 g of CAT-1, 0.04 g of CAT-2, 25 g of component A, and 46 g of component B, 0.08 g of UV329, and 0.005 g of di-n-butyl phosphate were stirred uniformly, and then 15 g of component C and 14 g of component D were added and stirred uniformly. The sample was taken for DSC to test the curing temperature reaction heat at a dynamic temperature rising rate of 15 K / min, and the activation energy (Ea) was 179.69 KJ·mol-1 .

[0122] The activation energy did not cause bubbles in the lens, and the final sample was gel-like and not fully cured.

[0123] The parameters and results of the above examples and comparative examples are summarized in Table 1:

[0124] Table 1 Test parameters and results of Examples 1-6 and Comparative Examples 1-4

[0125]

[0126] Figure 1 A diagram of the high-refractive optical resin material prepared in the present application is shown, in which the left side is the optical resin material prepared in Example 1 without bubbles, and the right side is the optical resin material prepared in Comparative Example 1 with bubbles.

[0127] The above examples are only used to help understand the method of the present application and its core idea. It should be noted that for those skilled in the art, without departing from the principles of the present application, the present application can be improved and modified in several ways, and these improvements and modifications also fall within the scope of protection of the claims of the present application.

Claims

1. A high refractive index optical resin material composition comprising: A cyclic sulfur compound and a catalyst; The cyclic sulfur compound includes one or more of bis(β-cyclotropyl) sulfide, bis(β-cyclotropyl) disulfide. The catalyst has a mass content of 0.001% to 10%. The high refractive index optical resin material composition has an activation energy of 35 to 160 KJ·mol -1 .

2. The high refractive index optical resin material composition according to claim 1, characterized by, The high refractive index optical resin material composition has an activation energy of 40-150 KJ·mol -1 .

3. The high refractive index optical resin material composition according to claim 1, characterized by, The high refractive index optical resin material composition has an activation energy of 40-130 KJ·mol -1 .

4. The high refractive index optical resin material composition according to claim 1, characterized by, Further comprising: A polysulfydryl compound.

5. The high refractive index optical resin material composition according to claim 4, characterized by, The mass ratio of the polysulfydryl compound to the cyclic sulfur compound is 0 to 30: 100 to 70.

6. The high refractive index optical resin material composition according to claim 4, characterized by, The polysulfydryl compound includes: One or more of pentaerythritol tetra(2-mercaptoacetate), pentaerythritol tetra(3-mercapto propionate), bis(mercaptoethyl) sulfide, 1,2-bis(2-mercaptoethylthio)-3-mercapto propane, 4-mercapto methyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 2,5-dimercaptomethyl-1,4-dithiacyclohexane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, ethylene glycol bis(3-mercapto propionate).

7. The high refractive index optical resin material composition according to claim 1, characterized by, The catalyst includes one or more of an amine-based catalyst, a phosphine-based catalyst, a quaternary phosphonium salt-based catalyst.

8. The high refractive index optical resin material composition according to claim 1, characterized by, The catalyst has a mass content of 0.008% to 0.2%.

9. A high refractive index optical resin material prepared from the high refractive index optical resin material composition according to any one of claims 1 to 8.

10. The high refractive index optical resin material according to claim 9, characterized by, The optical resin material has a refractive index greater than 1.70.

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