Curing Adhesive, S-Type Epoxy Compound with Binaphthyl Group, Preparation Method and Application

Abstract

The present application discloses a curing adhesive, an S-type epoxy compound with binaphthyl group, a preparation method and an application thereof. The curing adhesive includes the S-type epoxy compound with binaphthyl group, and the S-type epoxy compound with binaphthyl group includes a compound having the structure shown in Formula I. The curing adhesive has the advantages of high refractive index and low yellowness, and the optical film prepared therefrom has the remarkable advantages of high refractive index, low yellowness, high light transmittance and high heat resistance.

Description

Technical Field

[0001] The present application relates to the field of optical materials, and particularly to a curing adhesive, an S-shaped naphthyl-based epoxy compound, a preparation method and an application thereof. Background Art

[0002] In many current application fields, such as optical communication technology, spectacle lenses, lenses, display panels, and optical waveguides, high refractive index materials are required to achieve effects such as increasing the system efficiency of photon integration, increasing brightness, and protecting devices. However, the refractive indices of most organic curing materials are relatively low, generally in the range of 1.45 to 1.55, and it is difficult for the refractive index of the prepared curing adhesive to reach 1.6.

[0003] Currently, the conventional strategy for increasing the refractive index of the curing adhesive system is to introduce a certain amount of inorganic nanoparticles into the organic curing material. The more the amount of inorganic nanoparticles used, the higher the refractive index is increased. However, the incompatibility between the inorganic nanoparticles and the organic curing material makes it difficult for the inorganic nanoparticles to be stably dispersed in the organic curing material, thereby affecting the refractive index, yellowness, and light transmittance of the curing adhesive system and making it difficult to meet the market demand.

[0004] Therefore, in order to meet the market demand, it is necessary to design a brand-new all-organic curing system or an organic-inorganic curing system with good compatibility, so that the curing adhesive system has high refractive index, low yellowness, high light transmittance, and high heat resistance. Summary of the Invention

[0005] Therefore, the technical problem to be solved by the present application is to overcome the above defects in the prior art. The purpose is to provide a curing adhesive, which includes an S-shaped naphthyl-based epoxy compound. The S-shaped naphthyl-based epoxy compound has the advantages of high refractive index and low yellowness, which is beneficial to the preparation of an optical film with high refractive index, low yellowness, high light transmittance, and high heat resistance by the curing adhesive.

[0006] In the first aspect of the present application, there is provided a curing adhesive, including an S-shaped naphthyl-based epoxy compound, and the S-shaped naphthyl-based epoxy compound includes a compound having the structure shown in Formula I,

[0007] Formula I,

[0008] wherein, R1 includes at least one of substituted or unsubstituted C 1-10 alkylene, substituted or unsubstituted C 1-10 alkoxy, substituted or unsubstituted C 3-10 cycloalkoxy, and substituted or unsubstituted phenoxy.

[0009] It is found in the research of this application that due to the advantages of the S configuration, the optical film prepared by curing the curing adhesive containing the S-type epoxy compound with binaphthyl groups not only has the advantage of high refractive index, but more importantly, has the remarkable advantages of lower yellowness, higher transmittance, and better heat resistance.

[0010] In any embodiment, the curing adhesive further includes an oligomer of the S-type epoxy compound with binaphthyl groups, and the mass ratio of the oligomer of the S-type epoxy compound with binaphthyl groups to the S-type epoxy compound with binaphthyl groups is not higher than 0.055, preferably not higher than 0.05.

[0011] The introduction of the oligomer of the S-type epoxy compound with binaphthyl groups in the curing adhesive can not only avoid the influence of compatibility to the greatest extent, but more importantly, can effectively improve the refractive index of the curing adhesive, realize the design of a high refractive index system, and broaden its application window.

[0012] In any embodiment, R1 includes at least one of substituted or unsubstituted C 1-10 alkyleneoxy, substituted or unsubstituted C 3-10 cycloalkyleneoxy, and substituted or unsubstituted phenoxy.

[0013] In the second aspect of this application, a preparation method of an S-type epoxy compound with binaphthyl groups is provided, including:

[0014] Under reactable conditions, reacting raw materials including (S)-(-)-1,1'-bi-2-naphthol and epoxy haloalkane to prepare the S-type epoxy compound with binaphthyl groups;

[0015] Wherein, the epoxy haloalkane includes at least one of the compounds shown in Formula II and the compounds shown in Formula III,

[0016] Formula II, Formula III,

[0017] In the formula, R 11 , R 12 each independently includes at least one of substituted or unsubstituted C 1-10 alkylene, and Y1 and Y2 each independently include at least one of bromine, fluorine, chlorine, and iodine.

[0018] This preparation method has easily available raw materials, simple operation, and low production cost. The prepared S-type epoxy compound with binaphthyl groups has the advantages of high refractive index and low yellowness.

[0019] In any embodiment, the raw materials further include the compound shown in Formula IV,

[0020] Formula IV,

[0021] In the formula, R 13 includes at least one of substituted or unsubstituted C 1-10 alkylene, substituted or unsubstituted C 3-10 cycloalkyl, and substituted or unsubstituted phenyl, and X1 includes at least one of bromine, fluorine, chlorine, and iodine.

[0022] The introduction of the compound of the structure shown in Formula IV is beneficial to reducing the yellowness of the S-type epoxy compound having a binaphthyl group, or improving its light transmittance and refractive index.

[0023] In the third aspect of the present application, an S-type epoxy compound having a binaphthyl group is provided, which is prepared by the preparation method of the second aspect of the present application.

[0024] In the fourth aspect of the present application, an application of the curing adhesive of the second aspect of the present application in an optical device is provided. Specific Embodiments

[0025] Hereinafter, embodiments of the curing adhesive, the S-type epoxy compound having a binaphthyl group, and the preparation method and application of the present application are specifically disclosed. However, there may be cases where unnecessary detailed descriptions are omitted. For example, there are cases where detailed descriptions of well-known matters and repeated descriptions of actually identical structures are omitted. This is to avoid the following descriptions from becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art. In addition, the following descriptions are provided for those skilled in the art to fully understand the present application and are not intended to limit the subject matter recited in the claims. Any product that is the same as or similar to the present application obtained by anyone under the inspiration of the present application or by combining the features of the present application with other prior art features falls within the protection scope of the present application.

[0026] The "range" disclosed in the present application is defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a specific range. The range defined in this way can include or not include the end values, and can be combined arbitrarily, that is, any lower limit can be combined with any upper limit to form a range. For example, the numerical range "a - b" represents an abbreviated representation of any real number combination between a and b, where a and b are both real numbers. For example, the numerical range "0 - 7" means that all real numbers between "0 - 7" are fully listed herein, and "0 - 7" is only an abbreviated representation of these numerical combinations. In addition, when it is stated that a certain parameter is an integer ≥3, it is equivalent to disclosing that the parameter is, for example, the integer 3, 4, 5, 6, 7, 8, 9, 10, 11, etc.

[0027] If there is no special description, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0028] Unless otherwise specified, all technical features and optional technical features of the present application can be combined with each other to form new technical solutions.

[0029] Unless otherwise specified, all steps of the present application can be carried out sequentially or randomly, preferably sequentially. For example, the method includes steps (1) and (2), which means that the method can include steps (1) and (2) carried out sequentially, or can also include steps (2) and (1) carried out sequentially. For example, it is mentioned that the method may further include step (3), which means that step (3) can be added to the method in any order. For example, the method can include steps (1), (2) and (3), or can also include steps (1), (3) and (2), or can also include steps (3), (1) and (2), etc.

[0030] Unless otherwise specified, the "including" and "comprising" mentioned in the present application mean open-ended, and can also be closed-ended. For example, the "including" and "comprising" can mean that other components not listed can also be included or comprised, or can only include or comprise the listed components.

[0031] Unless otherwise specified, in the present application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) while B is true (or exists); or both A and B are true (or exist).

[0032] The present application provides a curing adhesive, which includes an S-type epoxy compound having a binaphthyl group. The S-type epoxy compound having a binaphthyl group includes a compound having the structure shown in Formula I.

[0033] Formula I

[0034] Wherein, R1 includes at least one of substituted or unsubstituted C 1-10 alkylene, substituted or unsubstituted C 3-10 cycloalkyl, and substituted or unsubstituted phenyl.

[0035] In this article, the term "S-type epoxy compound having a binaphthyl group" refers to an epoxy compound having a binaphthyl group with the configuration of the chiral center being S-type; the specific rotation of the epoxy compound having a binaphthyl group in the present application is obtained by testing with a polarimeter. The specific rotation of the S-type epoxy compound having a binaphthyl group is "-", and the specific rotation of the R-type epoxy compound having a binaphthyl group is "+".

[0036] In this text, the term "specific rotation" refers to the angle of rotation of the plane of polarization of light with a wavelength of 589 nm at a temperature of 20 °C after passing through a solution with a unit length (1 dm) and a unit concentration (g / ml).

[0037] In this text, the term "substituted or unsubstituted" means that at least one hydrogen of the substituent is replaced by deuterium, halogen, cyano, C 1-10 alkyl, C 1-10 cycloalkyl, C 6-20 aryl, C 2-20 heteroaryl or a combination thereof.

[0038] In this text, the curing methods of the curing adhesive include but are not limited to photocuring or thermal curing. When the curing adhesive adopts the photocuring method, the curing adhesive further includes a photoinitiator; when the curing adhesive adopts the thermal curing method, the curing adhesive does not include a photoinitiator.

[0039] It has been found that introducing phenyl into the organic curing material is beneficial to improving its refractive index. The S-type epoxy compound with binaphthyl groups in this application not only has the advantages of high refractive index and low yellowness, but more importantly, compared with the R-type epoxy compound with binaphthyl groups or the hybrid-type epoxy compound with binaphthyl groups, the configuration of the S-type epoxy compound with binaphthyl groups has more advantages in the optical field, which is beneficial to the molecular arrangement during the curing process, resulting in an optical film with a lower refractive index and a higher light transmittance, and broadening the application window of the curing adhesive.

[0040] It can be understood that due to the influence of the molecular configuration, during the curing process, compared with the curing reaction of the R-type epoxy compound with binaphthyl groups, or the curing reaction of the R-type and S-type hybrid epoxy compound with binaphthyl groups, the curing reaction of the S-type epoxy compound with binaphthyl groups is more conducive to the preparation of an optical film with lower yellowness and higher light transmittance, and the yellowness of the optical film prepared by the curing adhesive containing the S-type epoxy compound with binaphthyl groups after high-temperature storage is also significantly lower than that of the R-type epoxy compound system with binaphthyl groups (R-type epoxy compound with binaphthyl groups / S-type epoxy compound with binaphthyl groups mixed system), and it has more optical advantages.

[0041] In some embodiments, the specific rotation of the S-form naphthyl-based epoxy compound is -50 to -30 (°·ml) / (dm·g). In some embodiments, the specific rotation of the S-form naphthyl-based epoxy compound can be optionally -50 (°·ml) / (dm·g), -48 (°·ml) / (dm·g), -46 (°·ml) / (dm·g), -45 (°·ml) / (dm·g), -44 (°·ml) / (dm·g), -42 (°·ml) / (dm·g), -40 (°·ml) / (dm·g), -38 (°·ml) / (dm·g), -36 (°·ml) / (dm·g), -35 (°·ml) / (dm·g), -34 (°·ml) / (dm·g), -32 (°·ml) / (dm·g), -30 (°·ml) / (dm·g), or a value within the range formed by any two of the above values.

[0042] In this application, the optical film prepared from the curing adhesive containing the S-form naphthyl-based epoxy compound with a specific rotation of -50 to -30 (°·ml) / (dm·g) has significant advantages of high refractive index, low yellowness, high light transmittance, and high heat resistance.

[0043] In some embodiments, the epoxy value of the S-form naphthyl-based epoxy compound is 0.184 to 0.502 mol / 100g. In some embodiments, the epoxy value of the S-form naphthyl-based epoxy compound can be optionally 0.184 mol / 100g, 0.185 mol / 100g, 0.200 mol / 100g, 0.220 mol / 100g, 0.240 mol / 100g, 0.250 mol / 100g, 0.260 mol / 100g, 0.280 mol / 100g, 0.300 mol / 100g, 0.320 mol / 100g, 0.340 mol / 100g, 0.350 mol / 100g, 0.360 mol / 100g, 0.380 mol / 100g, 0.400 mol / 100g, 0.420 mol / 100g, 0.440 mol / 100g, 0.450 mol / 100g, 0.460 mol / 100g, 0.480 mol / 100g, 0.500 mol / 100g, 0.502 mol / 100g, or a value within the range formed by any two of the above values.

[0044] In this application, the epoxy value of the S-form naphthyl-based epoxy compound can be tested by any well-known method. As an example, the epoxy value of the S-form naphthyl-based epoxy compound is determined by the hydrochloric acid-acetone titration method, and the ASTM-D1652 standard can be referred to.

[0045] In some embodiments, the refractive index of the S-type epoxy compound having a binaphthyl group is 1.64 to 1.70.

[0046] In the present application, the refractive index of the S-type epoxy compound having a binaphthyl group can be measured by any known method. As an example, using an Abbe refractometer (Abbemat 300), the refractive index of the S-type epoxy compound having a binaphthyl group is measured at a test temperature of 20 °C. The S-type epoxy compound having a binaphthyl group to be tested is directly dropped on the prism of the Abbe refractometer to measure its refractive index.

[0047] The refractive index of the S-type epoxy compound having a binaphthyl group in the present application exceeds 1.6. For application requirements with a refractive index of 1.6 to 1.7, an all-organic curing adhesive can be prepared.

[0048] In some embodiments, the curing adhesive further includes an oligomer of the S-type epoxy compound having a binaphthyl group, and the mass ratio of the oligomer of the S-type epoxy compound having a binaphthyl group to the S-type epoxy compound having a binaphthyl group is not higher than 0.055. In some embodiments, the mass ratio of the oligomer of the S-type epoxy compound having a binaphthyl group to the S-type epoxy compound having a binaphthyl group can be selected from 0.0001, 0.001, 0.01, 0.02, 0.03, 0.04, 0.05, 0.055, or any value within the range formed by any two of the above.

[0049] The present application has found that the introduction of the oligomer of the S-type epoxy compound having a binaphthyl group in the curing adhesive can not only avoid the influence of compatibility to the greatest extent, but more importantly, can effectively improve the refractive index of the curing adhesive, realize the design of a high refractive index system, and broaden its application window. An excessive content of the oligomer of the S-type epoxy compound having a binaphthyl group will significantly affect the yellowness and light transmittance of the optical film prepared from the curing adhesive.

[0050] In some embodiments, R1 includes at least one of substituted or unsubstituted C 3-10 alkylene, substituted or unsubstituted C 3-10 alkoxy.

[0051] The present application has found that when R1 is selected from long-chain alkylene or alkoxy, it is further beneficial to reduce the yellowness and improve the light transmittance of the optical film prepared from the curing adhesive.

[0052] In some embodiments, R1 includes at least one of substituted or unsubstituted C 3-10 cycloalkoxy, substituted or unsubstituted phenoxy.

[0053] The present application has found that when R1 is selected from cycloalkyl or phenyl, it is further beneficial to increase the refractive index of the optical film prepared from the curing adhesive.

[0054] In some embodiments, the curable adhesive further comprises at least one of a resin, a reactive monomer, an additive, and a solvent.

[0055] The oligomer of the S-type epoxy compound having a binaphthyl group has high compatibility. Introducing a resin, a reactive monomer or an additive into the curable adhesive all has good compatibility with the oligomer of the S-type epoxy compound having a binaphthyl group, and the curable adhesives all have a high refractive index, a low yellowness, a high transmittance, and high heat resistance.

[0056] In some embodiments, the resin comprises at least one of an epoxy acrylate resin, a polyurethane acrylate resin, a polyether acrylate resin, a polyester acrylate resin, a polyurethane epoxy resin, a polyurethane resin, and a silicone resin.

[0057] In some embodiments, the reactive monomer includes at least one of epoxy monomers, acrylate monomers, and styrene monomers. The epoxy monomers include at least one of ethylene oxide, propylene oxide, butylene oxide, alkyl ethylene oxide with 3 to 20 carbon atoms in the alkyl group, styrene oxide, 1,3-butadiene diepoxide, 1,5-hexadiene diepoxide, 1,7-octadiene diepoxide, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, styrene oxide, alkyl glycidyl ether, aryl glycidyl ether, alkenyl glycidyl ether, alkynyl glycidyl ether, and cyclohexene oxide. The acrylate monomers include at least one of tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethyl diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, ethylene glycol phthalate diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol dimethacrylate, propoxylated neopentyl glycol diacrylate, dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dipropylene glycol diacrylate, ethoxylated bisphenol A dimethacrylate, tripropylene glycol diacrylate, pentaerythritol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, urethane di(meth)acrylate, bisphenol A glycerol dimethacrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, isobornyl methacrylate, isobornyl acrylate, isooctyl acrylate, isooctyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, 2-phenoxyethyl acrylate, pentaerythritol (meth)acrylate, n-butyl acrylate, isodecyl acrylate, lauryl acrylate, cyclohexyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, 4-tert-butylcyclohexyl acrylate, dicyclopentenyl acrylate, octadecyl methacrylate, butyl acrylate, isodecyl acrylate, isodecyl methacrylate, lauryl acrylate, lauryl methacrylate, glycidyl methacrylate, 2-phenoxyethyl methacrylate, isodecyl acrylate, vinyl acetate, ethoxylated dicyclopentenyl methacrylate, 4-tert-butylcyclohexyl acrylate. The styrene monomers include at least one of styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, α-butylstyrene, 4-n-butylstyrene, divinylbenzene, 2,4-dimethylstyrene, ethylstyrene, and p-tert-butylstyrene.

[0058] In some embodiments, the additives include at least one of photoinitiators, thermal curing agents, leveling agents, antioxidants, and dispersants.

[0059] In some embodiments, the photoinitiator includes at least one of diaryliodonium salts, triarylsulfonium salts, sulfonium hexafluoroantimonate salts, and aromatic diazonium salts. The photoinitiator includes at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, isopropyl thioxanthone, 2,2-dimethoxy-2-phenylethanone, α-amino-1-phenyl-1-propanone, 2-hydroxy thioxanthone, α-aminophenylacetone hydrochloride, benzoylmethylpyridinium oxalate, photoinitiator UV6992, photoinitiator UV6976, photoinitiator 819, photoinitiator 907, photoinitiator ITX, photoinitiator 1173, photoinitiator TPO, photoinitiator 184, photoinitiator 1176, and photoinitiator 6976.

[0060] In some embodiments, the thermal curing agent includes at least one of aliphatic tertiary amines, aromatic tertiary amines, quaternary ammonium salts, sulfonium salts, and guanidines. In some embodiments, the thermal curing agent includes at least one of bis(4-aminophenyl)sulfone, bis(4-aminophenyl)ether, 2,2-bis(4-aminophenyl)propane, dimethylaminopropylamine, N-methyl-4-methylpyridinium hexafluorophosphate, fluorenediamine, tetramethylguanidine, and dicyandiamide.

[0061] In some embodiments, the leveling agent includes at least one of TEGO Glide 410, BYK346, BYK333, BYK3499, BYK3455, BYK301, EFKA3777, and Evonik420.

[0062] In some embodiments, the dispersant includes at least one of BYK163, BYK191, BYK180, BYK110, EFKA4310, EFKA4010, EFKA4560, SURFYNOL 104E, Tego dispers 655, and SN-Dispersant 5027.

[0063] In some embodiments, the antioxidant includes at least one of antioxidant 1076, antioxidant 1010, and antioxidant 168.

[0064] In some embodiments, the solvent includes at least one of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, and ethanol

[0065] In some embodiments, based on the total mass of the cured adhesive, the mass content of the S-type epoxy compound with binaphthyl groups is 10% - 90%, the mass content of the solvent is 5% - 88%, the mass content of the auxiliary agent is 0.1% - 5%, the mass content of the resin is 0% - 30%, and the content of the reactive monomer is 0% - 30%. In some embodiments, based on the total mass of the cured adhesive, the mass content of the S-type epoxy compound with binaphthyl groups can be optionally 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or any value within the range formed by any two of the above, the mass content of the solvent is 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 88%, or any value within the range formed by any two of the above, the mass content of the auxiliary agent is 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, or any value within the range formed by any two of the above, the mass content of the resin is 0%, 0.001%, 0.01%, 0.1%, 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, or any value within the range formed by any two of the above, and the content of the reactive monomer is 0%, 0.001%, 0.01%, 0.1%, 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, or any value within the range formed by any two of the above.

[0066] In this application, the S-type epoxy compound with binaphthyl groups can be mixed with other resins, reactive monomers or auxiliary agents in any proportion within the range of 10wt% - 90wt% to obtain a cured adhesive, and the optical adhesives prepared from this cured adhesive all have high refractive index, low yellowness, high transmittance and high heat resistance.

[0067] In some embodiments, the cured adhesive further includes nanoparticles, and the nanoparticles include at least one of SiO2, ZnS, ZnO, CeO2, GeO2, Ta2O5, Bi4Ti3O2, Nb2O5, ITO, HfO2, SnO2, MoO3, Sb2O3, Sb2O5, Nd2O3, ZrO2, TiO2.

[0068] In some embodiments, based on the total mass of the cured adhesive, the mass content of the nanoparticles is 0% - 60%. In some embodiments, based on the total mass of the cured adhesive, the mass content of the nanoparticles can be optionally 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, or any value within the range formed by any two of the above.

[0069] It is found in the research of this application that when the mass content of nanoparticles is controlled within 60%, S-type epoxy compounds with binaphthyl groups have good compatibility with nanoparticles, which can avoid the influence on the optical properties (refractive index, yellowness, transmittance, heat resistance) of the optical film due to compatibility problems to the greatest extent. Introducing SiO2 into the curing adhesive can improve its wear resistance and mechanical strength, and introducing high-refractive-index nanoparticles such as ZrO2 and TiO2 into the curing adhesive can improve its refractive index and mechanical strength.

[0070] This application also provides a preparation method of an S-type epoxy compound with a binaphthyl group, including:

[0071] Under reactable conditions, reacting raw materials including (S)-(-)-1,1'-bi-2-naphthol and epoxy halide to prepare an S-type epoxy compound with a binaphthyl group;

[0072] Among them, the epoxy halide includes at least one of the compounds with the structure shown in Formula II and the compounds with the structure shown in Formula III,

[0073] Formula II, Formula III,

[0074] In the formula, R 11 、R 12 each independently includes at least one of substituted or unsubstituted C 1-10 alkylene, and Y1 and Y2 each independently include at least one of bromine, fluorine, chlorine, and iodine.

[0075] This preparation method has easily available raw materials, simple operation, and low production cost. The prepared S-type epoxy compound with a binaphthyl group has the advantages of high refractive index and low yellowness.

[0076] In some embodiments, the molar ratio of the epoxy halide to (S)-(-)-1,1'-bi-2-naphthol is (4 - 50):1. In some embodiments, the molar ratio of the epoxy halide to (S)-(-)-1,1'-bi-2-naphthol is 4:1, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, or any ratio within the range formed by any two of the above ratios.

[0077] In some embodiments, the reaction temperature is 40 - 110 °C, and the reaction time is 2 - 6 h. In some embodiments, the reaction temperature can be selected as 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, or any value within the range formed by any two of the above points, and the reaction time can be selected as 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, or any value within the range formed by any two of the above points.

[0078] In some embodiments, the catalyst for the reaction comprises a quaternary ammonium salt. In some embodiments, the catalyst for the reaction comprises at least one of tetrabutylammonium bromide, benzyltriethylammonium chloride, and tetramethylammonium bromide.

[0079] In some embodiments, the mass ratio of the catalyst to (S)-(-)-1,1'-binaphthol is (0.01~0.1):1. In some embodiments, the mass ratio of the catalyst to (S)-(-)-1,1'-binaphthol can be selected from 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, or any ratio within the range formed by any two of the above ratios.

[0080] Controlling appropriate reaction conditions is beneficial to the preparation of an S-type binaphthyl-containing epoxy compound with high refractive index and low yellowness.

[0081] In some embodiments, the epoxyhaloalkane comprises at least one of epichlorohydrin, 1,2-epichlorobutane, 2-(4-chlorobutyl)oxirane, (8-chlorooctyl)oxirane, epibromohydrin, epiiodohydrin, 2-(chloromethyl)-2-methyloxirane, 2-(bromomethyl)-2-methyloxirane, and 3-chloro-2-methyl-1,2-epoxypropane.

[0082] In some embodiments, the raw materials further include a compound having the structure shown in Formula IV,

[0083] Formula IV,

[0084] In the formula, R 13 comprises at least one of a substituted or unsubstituted C 1-10 alkylene, a substituted or unsubstituted C 3-10 cycloalkyl, and a substituted or unsubstituted phenyl, and X1 comprises at least one of bromine, fluorine, chlorine, and iodine.

[0085] In some embodiments, the compound having the structure shown in Formula IV comprises at least one of 2-chloroethanol, 3-bromo-1-propanol, 1-chloro-2-propanol, 4-bromo-1-butanol, 4-bromo-1-cyclohexanol, 2-chlorocyclohexanol, 3-bromocyclopentanol, 4-fluorocycloheptanol, 2-iodocyclohexanol, 2-bromocycloheptanol, m-hydroxy phenethyl bromide, and 2-iodophenol.

[0086] The introduction of the compound having the structure shown in Formula IV is beneficial to reducing the yellowness of the S-type binaphthyl-containing epoxy compound, or improving its light transmittance and refractive index.

[0087] The present application also provides an S-shaped naphthyl-based epoxy compound prepared by the preparation method in some embodiments.

[0088] The present application also provides the application of the curing glue in some embodiments in optical devices.

[0089] The optical devices include but are not limited to spectacle lenses, lens lenses, optical communication devices or display panels.

[0090] Examples

[0091] The following examples are for better further understanding of the present invention, which are not limited to the best embodiments, and do not constitute limitations on the content and protection scope of the present invention. For those examples where specific experimental steps or conditions are not indicated, the operations or conditions of the conventional experimental steps described in the literature in this field can be followed. For the reagents or instruments whose manufacturers are not indicated, they are all conventional reagent products that can be obtained through commercial purchase. Unless otherwise specified, the raw materials in the examples and comparative examples are all purchased from Sigma-Aldrich.

[0092] I. Preparation method

[0093] Example 1

[0094] Preparation of S-shaped naphthyl-based epoxy compound: Add 5.73 g of (S)-(-)-1,1'-bi-2-naphthol, 37 g of epichlorohydrin and 0.287 g of tetrabutylammonium bromide into a 100 mL three-necked flask equipped with a condenser, a magnetic stirrer and a nitrogen interface. Heat up to 105 °C and react for 3.5 h. Then stop heating and cool down to 50 °C. Use a constant pressure dropping funnel to drop 6.93 g of 30 wt% NaOH solution, and slowly drop it within 1.5 h. After reacting for 2 h, stop heating. After the reaction is completed, filter to remove the white solid, wash it with deionized water 3 - 4 times until the solution is washed to neutrality. Add anhydrous sodium sulfate to dry and remove water, filter, and then distill off epichlorohydrin under reduced pressure. Heat it in an oven at 150 °C for 16 h to obtain the S-shaped naphthyl-based epoxy compound. The yield is 92%, the epoxy value is 0.463 mol / 100 g, and the refractive index is 1.65.

[0095] Infrared spectrum: 3021 cm -1 、2982 cm -1 (benzene ring C-H bond); 2897 cm -1 (alkyl C-H bond); 1600 cm -1 、1499 cm -1 (benzene ring C=C bond); 920 cm -1 (epoxy group).

[0096] 11H NMR (400 MHz, CDCl3): δ 6.7 - 7.9 (12H, benzene ring); δ 3.9 - 4.2 (4H, -CH2- connected to epoxy group); δ 3.3 (2H, -CH- inside epoxy group); δ 2.7 - 2.8 (4H, -CH2- inside epoxy group).

[0097] Preparation of the cured adhesive: Dissolve 5 g of the above-mentioned S-type epoxy compound with binaphthyl group in 4.71 g of propylene glycol methyl ether acetate, add 0.25 g of photoinitiator UV6992 and 0.04 g of leveling agent BYK381. First, heat and mix at 120 °C for 20 min, then disperse at 600 rpm with magnetic stirring for 0.5 h to obtain the cured adhesive.

[0098] Preparation of the optical film: Place a 4-inch glass slide on a Laurell spin-coating device, and drop 4 ml of the above-mentioned cured adhesive onto the glass slide to prepare a coating. The spin-coating speed is 2000 rpm, and the spin-coating time is 1 min, and it is cured under 365 nm UV-LED with a curing energy of 3600 mJ / cm 2 , to prepare the optical film.

[0099] Example 2

[0100] The preparation methods of the S-type epoxy compound with binaphthyl group, the cured adhesive, and the optical film in Example 2 are similar to those in Example 1. The difference is that 4-bromo-1-butanol is introduced during the preparation process of the S-type epoxy compound with binaphthyl group in Example 1. The specific preparation method of the S-type epoxy compound with binaphthyl group is as follows:

[0101] Add 5.73 g of (S)-(-)-1,1'-bi-2-naphthol and 100 mL of tetrahydrofuran into a 100 mL three-necked flask equipped with a condenser, a magnetic stirrer, and a nitrogen interface. Then add 0.31 g of KOH, 0.013 g of KI, and 0.57 g of 4-bromo-1-butanol. Reflux at 85 °C for 10 h under a nitrogen atmosphere, then cool down, extract with ethyl acetate, and dry to obtain the intermediate;

[0102] The above intermediate, 37 g of epichlorohydrin, and 0.287 g of tetrabutylammonium bromide were heated to 105 °C and reacted for 3.5 h. Then, the heating was stopped, and the temperature was cooled to 50 °C. 6.93 g of 30 wt% NaOH solution was added dropwise using a constant pressure dropping funnel and slowly added dropwise within 1.5 h. After reacting for 2 h, the heating was stopped. After the reaction was completed, the white solid was removed by filtration, washed 3 - 4 times with deionized water until the solution was washed to neutrality, anhydrous sodium sulfate was added for drying to remove water, filtered, and then epichlorohydrin was removed by vacuum distillation. It was heated in an oven at 150 °C for 16 h to obtain an S-type naphthyl-based epoxy compound with a yield of 88%, an epoxy value of 0.451 mol / 100 g, and a refractive index of 1.63.

[0103] Infrared spectrum: 3035 cm -1 、2988 cm -1 (C-H bond of benzene ring); 2897 cm -1 (C-H bond of alkyl group); 1585 cm -1 、1503 cm -1 (C=C bond of benzene ring); 1189 cm -1 (C-O-C bond of aliphatic ether); 925 cm -1 (epoxy group).

[0104] 1 1H NMR (400 MHz, CDCl3): δ 6.7 - 7.7 (12H, benzene ring); δ 3.9 - 4.2 (4H, -CH2- connected to epoxy group); δ 3.3 (2H, -CH- inside epoxy group); δ 2.7 - 2.8 (4H, -CH2- inside epoxy group); δ 0.9 - 2.2 (16H, -CH2CH2CH2CH2-).

[0105] Example 3

[0106] The preparation methods of the S-type naphthyl-based epoxy compound, curing adhesive, and optical film in Example 3 are similar to those of the S-type naphthyl-based epoxy compound, curing adhesive, and optical film in Example 1, except that: During the preparation process of the S-type naphthyl-based epoxy compound in Example 1, m-hydroxy phenethyl bromide was introduced. The preparation method of the S-type naphthyl-based epoxy compound is as follows:

[0107] 5.73 g of (S)-(-)-1,1'-bi-2-naphthol and 100 mL of tetrahydrofuran were added to a 100 mL three-necked flask equipped with a condenser, magnetic stirrer, and nitrogen interface. Subsequently, 0.31 g of KOH, 0.013 g of KI, and 0.73 g of m-hydroxy phenethyl bromide were added. It was refluxed at 85 °C for 10 h under a nitrogen atmosphere, then cooled, extracted with ethyl acetate, and dried to obtain an intermediate;

[0108] The above intermediate, 37 g of epichlorohydrin, and 0.287 g of tetrabutylammonium bromide were heated to 105 °C and reacted for 3.5 h. Then, the heating was stopped and the temperature was cooled to 50 °C. 6.93 g of 30 wt% NaOH solution was added dropwise using a constant pressure dropping funnel and slowly added dropwise within 1.5 h. After reacting for 2 h, the heating was stopped. After the reaction was completed, the white solid was removed by filtration, washed 3 - 4 times with deionized water until the solution was washed to neutrality, anhydrous sodium sulfate was added for drying to remove water, filtered, and then epichlorohydrin was removed by vacuum distillation. It was heated in an oven at 150 °C for 16 h to obtain an S-type naphthyl-based epoxy compound with a yield of 89%, an epoxy value of 0.451 mol / 100 g, and a refractive index of 1.67.

[0109] Infrared spectrum: 3035 cm -1 、2988 cm -1 (C-H bond of benzene ring); 2897 cm -1 (C-H bond of alkyl group); 1593 cm -1 and 1499 cm -1 (C=C bond of benzene ring); 1183 cm -1 and 1078 cm -1 (C-O-C of ether bond); 918 cm -1 (epoxy group).

[0110] 1 1H NMR (400 MHz, CDCl3): δ 6.7 - 7.7 (12H, benzene ring); δ 3.7 - 3.9 (4H, -CH2- connected to epoxy group); δ 3.1 (2H, -CH- inside epoxy group); δ 2.8 - 2.9 (4H, -CH2- inside epoxy group); 1.8 - 2.1 (8H, -CH2CH2-).

[0111] Example 4

[0112] The preparation methods of the S-type naphthyl-based epoxy compound, curing adhesive, and optical film in Example 4 are similar to those of the S-type naphthyl-based epoxy compound, curing adhesive, and optical film in Example 1, except that: no photoinitiator was introduced into the curing adhesive in Example 1, and the curing method of the optical film was thermal curing. The preparation methods of the curing adhesive and the optical film are as follows:

[0113] Preparation of optical adhesive: 5 g of the above S-type naphthyl-based epoxy compound was dissolved in 4.6 g of propylene glycol monomethyl ether acetate, 0.4 g of curing agent dicyandiamide and 0.04 g of leveling agent BYK381 were added. First, it was heated and mixed at 100 °C for 20 min, and then dispersed at 600 rpm with magnetic stirring for 0.5 h to obtain a curing adhesive.

[0114] Preparation of the optical film: Place a 4-inch glass slide on a Laurell spin coater. Drop 4 ml of the above-mentioned curing adhesive onto the glass slide to prepare a coating. The spin coating speed is 2000 rpm, the rotation time is 1 min, and it is placed in a drying oven at 160 °C for curing. The curing time is 30 min to prepare the optical film.

[0115] Example 5

[0116] The preparation methods of the S-type epoxy compound with binaphthyl group, the curing adhesive, and the optical film in Example 5 are similar to those in Example 1 for the S-type epoxy compound with binaphthyl group, the curing adhesive, and the optical film. The difference is that: an oligomer of the S-type epoxy compound with binaphthyl group is introduced into the curing adhesive of Example 1, and the mass ratio of the oligomer of the S-type epoxy compound with binaphthyl group to the S-type epoxy compound with binaphthyl group is 0.01. The specific preparation method of the oligomer of the S-type epoxy compound with binaphthyl group is as follows:

[0117] Preparation of the oligomer of the S-type epoxy compound with binaphthyl group: Add 5.73 g of (S)-1,1'-bi-2-naphthol, 19 g of epichlorohydrin, and 0.287 g of tetrabutylammonium bromide into a 100 mL three-necked flask equipped with a condenser, a magnetic stirrer, and a nitrogen interface. Heat up to 105 °C and react for 3.5 h. Then stop heating and cool down to 50 °C. Use a constant pressure dropping funnel to drop 3.15 g of 50% NaOH solution, and slowly drop it within 1.5 h. After reacting for 2 h, stop heating. After the reaction is completed, filter to remove the white solid, wash it with deionized water 3 - 4 times until the solution is washed to neutral. Add anhydrous sodium sulfate to dry and remove water, filter, and then distill off epichlorohydrin under reduced pressure. Heat it in an oven at 150 °C for 16 h to obtain the oligomer of the S-type epoxy compound with binaphthyl group. The refractive index is 1.68, and the number average molecular weight of the oligomer of the S-type epoxy compound with binaphthyl group is 581.59 g / mol.

[0118] Examples 6 - 7

[0119] The preparation methods of the S-type epoxy compound with binaphthyl group, the curing adhesive, and the optical film in Examples 6 - 7 are similar to those in Example 5 for the S-type epoxy compound with binaphthyl group, the curing adhesive, and the optical film. The difference is that: the mass ratios of the oligomer of the S-type epoxy compound with binaphthyl group to the S-type epoxy compound with binaphthyl group in Example 5 are adjusted to 0.05 and 0.055 respectively. See Table 1-1 for details.

[0120] Examples 8 - 11

[0121] The preparation methods of the S-type epoxy compounds, curing adhesives, and optical films with binaphthyl groups in Examples 8 to 11 are similar to those of the S-type epoxy compounds, curing adhesives, and optical films with binaphthyl groups in Example 1, except that: epoxy acrylate resin CN104NS, acrylate resin CN821, polyurethane acrylate CN964, and polyester acrylate CN2270NS are respectively introduced into the curing adhesive in Example 1, and the mass ratio of these resins to the S-type epoxy compound with binaphthyl groups is 1:5. See Table 1-1 for details. (All of the above resins are purchased from Sartomer)

[0122] Example 12

[0123] The preparation methods of the S-type epoxy compounds, curing adhesives, and optical films with binaphthyl groups in Example 12 are similar to those of the S-type epoxy compounds, curing adhesives, and optical films with binaphthyl groups in Example 1, except that: nano-silica particles are introduced into the curing adhesive in Example 1, and the mass ratio of nano-silica particles to the S-type epoxy compound with binaphthyl groups is 1:5. See Table 1-2 for details.

[0124] Example 13

[0125] The preparation methods of the S-type epoxy compounds, curing adhesives, and optical films with binaphthyl groups in Example 13 are similar to those of the S-type epoxy compounds, curing adhesives, and optical films with binaphthyl groups in Example 1, except that: nano-titanium dioxide particles are introduced into the curing adhesive in Example 1, and the mass ratio of nano-titanium dioxide particles to the S-type epoxy compound with binaphthyl groups is 1:1. See Table 1-2 for details.

[0126] Example 14

[0127] The preparation methods of the S-type epoxy compounds, curing adhesives, and optical films with binaphthyl groups in Example 14 are similar to those of the S-type epoxy compounds, curing adhesives, and optical films with binaphthyl groups in Example 1, except that: the active monomer 3-phenoxybenzyl acrylate is introduced into the curing adhesive in Example 1, and the mass ratio of 3-phenoxybenzyl acrylate to the S-type epoxy compound with binaphthyl groups is 1:5. See Table 1-2 for details.

[0128] Examples 15 to 18

[0129] The preparation methods of the S-type epoxy compounds, curing adhesives, and optical films with binaphthyl groups in Examples 15 to 18 are similar to those of the S-type epoxy compounds, curing adhesives, and optical films with binaphthyl groups in Example 1, except that: by adjusting the content of the solvent, the mass content of the S-type epoxy compound with binaphthyl groups in the curing adhesive in Example 1 is adjusted to 10%, 30%, 70%, and 90% respectively. See Table 1-2 for details.

[0130] Examples 19 to 20

[0131] The preparation methods of the S-type binaphthyl-containing epoxy compounds, curing adhesives, and optical films in Examples 19 to 20 are similar to those of the S-type binaphthyl-containing epoxy compounds, curing adhesives, and optical films in Example 2, except that: by adjusting the content of the solvent, the mass contents of the S-type binaphthyl-containing epoxy compounds in the curing adhesives of Example 2 are adjusted to 20% and 80% respectively, as shown in Table 1-2 for details.

[0132] Examples 21 to 22

[0133] The preparation methods of the S-type binaphthyl-containing epoxy compounds, curing adhesives, and optical films in Examples 21 to 22 are similar to those of the S-type binaphthyl-containing epoxy compounds, curing adhesives, and optical films in Example 3, except that: by adjusting the content of the solvent, the mass contents of the S-type binaphthyl-containing epoxy compounds in the curing adhesives of Example 3 are adjusted to 20% and 80% respectively, as shown in Table 1-2 for details.

[0134] Example 23

[0135] The preparation methods of the S-type binaphthyl-containing epoxy compounds, curing adhesives, and optical films in Example 23 are similar to those of the S-type binaphthyl-containing epoxy compounds, curing adhesives, and optical films in Example 3, except that: oligomers of the S-type binaphthyl-containing epoxy compounds are introduced into the curing adhesive of Example 3, and the mass ratio of the oligomers of the S-type binaphthyl-containing epoxy compounds to the S-type binaphthyl-containing epoxy compounds is 0.05. The specific preparation method of the oligomers of the S-type binaphthyl-containing epoxy compounds can be found in Example 5, as shown in Table 1-2 for details.

[0136] Comparative Example 1

[0137] The preparation methods of the binaphthyl-containing epoxy compounds, curing adhesives, and optical films in Comparative Example 1 are similar to those of the S-type binaphthyl-containing epoxy compounds, curing adhesives, and optical films in Example 1, except that: the S-type binaphthyl-containing epoxy compound in Example 1 is adjusted to an R-type binaphthyl-containing epoxy compound. The specific preparation method of the R-type binaphthyl-containing epoxy compound is as follows:

[0138] 5.73 g of (R)-1,1'-bi-2-naphthol, 37 g of epichlorohydrin and 0.287 g of tetrabutylammonium bromide were added to a 100 mL three-necked flask equipped with a condenser, a magnetic stirrer and a nitrogen interface. The temperature was raised to 105 °C and the reaction was carried out for 3.5 h. Then the heating was stopped and the temperature was cooled to 50 °C. 6.93 g of 30% NaOH solution was added dropwise using a constant pressure dropping funnel and slowly added dropwise within 1.5 h. After reacting for 2 h, the heating was stopped. After the reaction was completed, the white solid was removed by filtration and washed 3-4 times with deionized water until the solution was washed to neutral. Anhydrous sodium sulfate was added for drying to remove water, and then filtered. Then epichlorohydrin was removed by vacuum distillation. It was heated in an oven at 150 °C for 16 h to obtain an R-type naphthyl-based epoxy compound with a yield of 91%, an epoxy value of 0.466 mol / 100 g, and a refractive index of 1.64.

[0139] Infrared spectrum: 3052 cm -1 、2937 cm -1 (C-H bond of benzene ring); 2887 cm -1 (C-H bond of alkyl group); 1600 cm -1 、1499 cm -1 (C=C bond of benzene ring); 920 cm -1 (epoxy group).

[0140] 1 1H NMR (400 MHz, CDCl3): δ 6.8 - 7.9 (12H, benzene ring); δ 3.9 - 4.2 (4H, -CH2- connected to epoxy group); δ 3.3 (2H, -CH- inside epoxy group); δ 2.7 - 2.8 (4H, -CH2- inside epoxy group).

[0141] Comparative Example 2

[0142] The preparation methods of the naphthyl-based epoxy compound, the cured adhesive and the optical film in Comparative Example 2 are similar to those of the S-type naphthyl-based epoxy compound, the cured adhesive and the optical film in Example 1, except that: the S-type naphthyl-based epoxy compound in the cured adhesive of Example 1 was adjusted to a mixture of an R-type naphthyl-based epoxy compound and an S-type naphthyl-based epoxy compound with a molar ratio of 1:1. The preparation method of the R-type naphthyl-based epoxy compound is shown in Comparative Example 1, as shown in Table 1-2 specifically.

[0143] Comparative Example 3

[0144] The preparation methods of the epoxy compound with binaphthyl group, the cured adhesive, and the optical film in Comparative Example 3 are similar to those of the S-type epoxy compound with binaphthyl group, the cured adhesive, and the optical film in Example 4, except that: the S-type epoxy compound with binaphthyl group in Example 4 is adjusted to an R-type epoxy compound with binaphthyl group. The preparation method of the R-type epoxy compound with binaphthyl group can be found in Comparative Example 1, as shown in Table 1-2 for details.

[0145] Comparative Example 4

[0146] The preparation methods of the epoxy compound with binaphthyl group, the cured adhesive, and the optical film in Comparative Example 4 are similar to those of the S-type epoxy compound with binaphthyl group, the cured adhesive, and the optical film in Example 8, except that: the S-type epoxy compound with binaphthyl group in Example 8 is adjusted to an R-type epoxy compound with binaphthyl group. The preparation method of the R-type epoxy compound with binaphthyl group can be found in Comparative Example 1, as shown in Table 1-2 for details.

[0147] Comparative Example 5

[0148] The preparation methods of the epoxy compound with binaphthyl group, the cured adhesive, and the optical film in Comparative Example 5 are similar to those of the S-type epoxy compound with binaphthyl group, the cured adhesive, and the optical film in Example 12, except that: the S-type epoxy compound with binaphthyl group in Example 12 is adjusted to an R-type epoxy compound with binaphthyl group. The preparation method of the R-type epoxy compound with binaphthyl group can be found in Comparative Example 1, as shown in Table 1-2 for details.

[0149] Table 1-1 Preparation Parameters of Examples 1 to 11

[0150]

[0151] Table 1-2 Preparation Parameters of Examples 12 to 23 and Comparative Examples 1 to 5

[0152]

[0153] II. Test Methods

[0154] 1) Specific Rotation Test of S-Type Epoxy Compound with Binaphthyl Group

[0155] The specific rotation of the S-type epoxy compound with binaphthyl group is tested with reference to the GB / T 613-2007 standard. The S-type epoxy compound with binaphthyl group to be tested is dissolved in DMSO to prepare a solution with a concentration of 1 g / 100 mL, and is placed in a polarimeter for testing. The test wavelength is 589 nm, the test temperature is 20 °C, and the model of the test equipment is KRÜSS P8000 from Germany.

[0156] 2) Yellowness and APHA Test of S-Type Epoxy Compound with Binaphthyl Group

[0157] The S-type epoxy compound with binaphthyl of the analyte was dissolved in acetone solvent and then spin-coated onto a glass substrate, followed by drying in an oven at 80 °C. Then, it was tested using a color difference meter, and the model of the testing equipment was X-Rite Ci7800 from the United States.

[0158] 3) Test of the initial decomposition temperature of the S-type epoxy compound with binaphthyl

[0159] The test of the initial decomposition temperature of the S-type epoxy compound with binaphthyl was carried out with reference to the standard of GB / T 33047.1-2016. Weigh 3 - 7 mg of the S-type epoxy compound with binaphthyl of the analyte, put it into an alumina crucible, and record the thermal degradation behavior of the analyte under a nitrogen atmosphere. The temperature range is 50 - 800 °C, and the heating rate is 10 °C / min. The model of the testing equipment is Mettler TGA2. The initial decomposition temperature T 5wt% is taken as the temperature value corresponding to the 5wt% loss point on the temperature curve.

[0160] 4) Test of the number-average molecular weight of the oligomers of the S-type epoxy compound with binaphthyl

[0161] The oligomers of the S-type epoxy compound with binaphthyl of the analyte were completely dissolved in tetrahydrofuran (THF), and the volume was fixed to 25 mL in a volumetric flask. Before injection, it was filtered with a PTFE filter head. The testing equipment was gel permeation chromatography GPC, the mobile phase was chloroform, and each sample was run at a flow rate of 1 mL / min for 30 min.

[0162] 5) Test of the refractive index of the optical film

[0163] The test of the refractive index of the optical film was carried out with reference to the standard of GB / T 6488-2008. At 20 °C, the refractive index of the optical film to be tested was measured using an ellipsometer (Semilab SE-2000).

[0164] 6) Test of the transmittance of the optical film

[0165] The test of the transmittance of the optical film was carried out with reference to the standard of GB / T 2410-2008. The transmittance of the optical film prepared on a glass substrate was measured in the range of 400 nm - 800 nm using a UV-Vis spectrophotometer, and the model of the testing equipment was Shimadzu UV-1800.

[0166] 7) Test of the yellowness value of the optical film

[0167] Test of the initial yellowness value: The yellowness value of the optical film prepared on a glass substrate was measured using a color difference meter, and the model of the testing equipment was X-Rite Ci7800 from the United States;

[0168] Yellowing value test after high-temperature storage: Place the optical film prepared with a glass substrate in an oven at 230 °C for 1 h. After taking it out, use a color difference meter to test the yellowing value. The model of the test equipment is X-Rite Ci7800 from the United States.

[0169] Table 2 Performance parameters of each example and comparative example

[0170]

[0171] III. Analysis of test results of each example and comparative example

[0172] It can be seen from Examples 1 to 23 and Comparative Examples 1 to 5 that compared with the epoxy compound with binaphthyl group of R type or the mixture of epoxy compounds with binaphthyl group of R type / S type, the cured adhesive containing the epoxy compound with binaphthyl group of S type not only has the advantages of high refractive index and low yellowing, but more importantly, this cured adhesive plays a greater advantage during the curing process, and the prepared optical film has the advantages of lower yellowing, higher light transmittance and heat resistance, broadening the application window of the cured adhesive.

[0173] It can be seen from Example 1 and Comparative Examples 1 to 2, Example 4 and Comparative Example 3, Example 8 and Comparative Example 4, and Example 12 and Comparative Example 5 that compared with the epoxy compound with binaphthyl group of R type or the mixture of epoxy compounds with binaphthyl group of R type / S type, not only the yellowing value and APHA of the epoxy compound with binaphthyl group of S type are lower, but also the yellowing value of the optical film prepared by its cured adhesive is significantly lower, the light transmittance is significantly higher, and there is a further gap in the yellowing value after high-temperature storage. The optical performance advantages of the cured adhesive containing the epoxy compound with binaphthyl group of S type are prominent.

[0174] It can be seen from Example 1 and Example 2 that the introduction of long-chain alkyl groups in the epoxy compound with binaphthyl group of S type is beneficial to reducing its yellowing value, and further reducing the yellowing value of its optical film and the yellowing value after high-temperature storage; it can be seen from Example 1 and Example 2 that the introduction of phenyl groups in the epoxy compound with binaphthyl group of S type is beneficial to increasing its refractive index, and further increasing the refractive index of its optical film.

[0175] It can be seen from Example 1 and Example 4 that both the photopolymerization and thermal curing methods can be used to prepare the cured adhesive, and the prepared optical films all have the advantages of high refractive index, low yellowing, high light transmittance and high heat resistance.

[0176] It can be seen from Example 1 and Examples 5 to 7, and Example 3 and Example 23 that introducing the oligomer of the epoxy compound with binaphthyl group of S type into the cured adhesive and controlling its content within 0.055 wt% can increase its refractive index without significantly affecting the yellowing value and light transmittance of its optical film.

[0177] As can be seen from Examples 1 and 8 to 14, the S-type epoxy compound with binaphthyl groups has excellent compatibility with resins, reactive monomers, and nanoparticles, and optical films with high refractive index, low yellowness, high light transmittance, and high heat resistance can be prepared therefrom.

[0178] As can be seen from Examples 1 and 15 to 18, Examples 2 and 19 to 20, and Examples 3 and 21 to 22, based on the total mass of the cured adhesive, when the mass content of the S-type epoxy compound with binaphthyl groups is controlled within 10% to 90%, optical films with high refractive index, low yellowness, high light transmittance, and high heat resistance can be prepared.

[0179] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application, and they should all be covered by the scope of the claims and the description of the present application. In particular, as long as there is no structural conflict, the technical features mentioned in each embodiment can be combined in any way. The present application is not limited to the specific embodiments disclosed in the text, but includes all technical solutions falling within the scope of the claims.

Claims

1. A curing adhesive, characterized in that: Including an S-type epoxy compound having a binaphthyl group, wherein the S-type epoxy compound having a binaphthyl group is a compound having a structure shown in formula I, Formula I, Wherein R1 includes substituted or unsubstituted C 1-10 Alkylene, substituted or unsubstituted C 1-10 Alkyleneoxy, substituted or unsubstituted C 3-10 At least one of a cycloalkoxy group and a substituted or unsubstituted phenoxy group; The curing adhesive does not contain an R-type epoxy compound having a binaphthyl group.

2. The curing adhesive according to claim 1, characterized in that: The curing adhesive further comprises the oligomer of the S-type epoxy compound having binaphthyl groups, and the mass ratio of the oligomer of the S-type epoxy compound having binaphthyl groups to the S-type epoxy compound having binaphthyl groups is not higher than 0.

055.

3. The curing adhesive according to claim 1, characterized in that: R1 includes substituted or unsubstituted C 1-10 Alkyleneoxy, substituted or unsubstituted C 3-10 At least one of a cycloalkoxy group and a substituted or unsubstituted phenoxy group.

4. The curing adhesive according to claim 1, characterized in that: The curing adhesive further comprises at least one of a resin, an active monomer, an auxiliary agent, and a solvent; The resin includes at least one of epoxy acrylate resin, polyurethane acrylate resin, polyether acrylate resin, polyester acrylate resin, polyurethane resin, and silicone resin; The active monomer includes at least one of epoxy monomers, acrylate monomers, and styrene monomers. The epoxy monomer includes at least one of ethylene oxide, propylene oxide, butylene oxide, alkyl ethylene oxide with alkyl carbon atoms of 3 to 20, styrene oxide, 1,3-butadiene diepoxide, 1,5-hexadiene diepoxide, 1,7-octadiene diepoxide, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, styrene oxide, alkyl glycidyl ether, aromatic glycidyl ether, alkenyl glycidyl ether, alkynyl glycidyl ether, and cyclohexene oxide. The acrylate monomer includes at least one of tricyclodecane diglycidyl ether, Methanol diacrylate, tricyclodecane dimethanol dimethyl diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, ethylene phthalate diacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol di(meth)acrylate, neopentyl glycol dimethacrylate, propoxylated neopentyl glycol diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dipropylene glycol diacrylate, ethoxylated bisphenol A dimethacrylate, tripropylene glycol di Acrylates, pentaerythritol dimethacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, urethane di(meth)acrylate, bisphenol A propylene glycol dimethacrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, isobornyl methacrylate, isobornyl acrylate, isooctyl acrylate, isooctyl methacrylate, tetrahydrofuran acrylate, tetrahydrofuran methacrylate, 2-phenoxyethyl acrylate, pentaerythritol (meth)acrylate, n-butyl acrylate, isodecyl acrylate, cyclohexyl acrylate, 3,3,5-trimethylolpropane The styrene monomer comprises at least one of styrene, vinyl toluene, α-methylstyrene, p-methylstyrene, α-butylstyrene, 4-n-butylstyrene, divinylbenzene, 2,4-dimethylstyrene, ethylstyrene and p-tert-butylstyrene; The auxiliary agent includes at least one of a photoinitiator, a leveling agent, and an antioxidant; The solvent includes at least one of propylene glycol methyl ether acetate, propylene glycol methyl ether, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, and ethanol.

5. The curing adhesive according to claim 4, characterized in that: Based on the total mass of the curing glue, the mass content of the S-type epoxy compound having a binaphthyl group is 10% to 90%, the mass content of the solvent is 5% to 88%, the mass content of the auxiliary agent is 0.1% to 5%, the mass content of the resin is 0% to 30%, and the content of the active monomer is 0% to 30%.

6. The curing adhesive according to any one of claims 1 to 5, characterized in that: The curing glue further includes nanoparticles, and the nanoparticles include at least one of SiO2, ZnS, ZnO, CeO2, GeO2, Ta2O5, Bi4Ti3O2, Nb2O5, ITO, HfO2, SnO2, MoO3, Sb2O3, Sb2O5, Nd2O3, ZrO2, and TiO2; Calculated based on the total mass of the cured adhesive, the mass content of the nanoparticles is 0% to 60%.

7. A method for preparing the S-type epoxy compound having a binaphthyl group according to any one of claims 1 to 6, comprising: Under reactive conditions, reacting raw materials including (S)-(-)-1,1'-binaphthol and epoxy halogenated alkyl to prepare the S-type epoxy compound having a binaphthyl group; Wherein, the epoxyhaloalkane comprises at least one of the compound of the structure shown in Formula II and the compound of the structure shown in Formula III, Formula II, Formula III, In the formula, R 11 , R 12 Each independently includes substituted or unsubstituted C 1-10 At least one of alkylene, Y1 and Y2 each independently include at least one of bromine, fluorine, chlorine and iodine; The raw materials also include compounds with the structure shown in formula IV, Formula IV, In the formula, R 13 Including substituted or unsubstituted C 1-10 Alkylene, substituted or unsubstituted C 3-10 At least one of cycloalkyl and substituted or unsubstituted phenyl, and X1 includes at least one of bromine, fluorine, chlorine and iodine.

8. The preparation method according to claim 7, characterized in that: The epoxyhaloalkane includes at least one of epichlorohydrin, 1,2-epoxychlorobutane, 2-(4-chlorobutyl)ethylene oxide, (8-chlorooctyl)ethylene oxide, epibromohydrin, epiiodohydrin, 2-(bromomethyl)-2-methylethylene oxide, and 3-chloro-2-methyl-1,2-epoxypropane.

9. An S-type epoxy compound having a binaphthyl group, characterized in that: Prepared by the preparation method described in claim 7 or 8.

10. Use of the curing adhesive according to any one of claims 1 to 6 in optical devices.

Images