Nanoimprint adhesive and preparation method thereof

Abstract

The invention discloses a nanoimprint adhesive and a preparation method thereof, the nanoimprint adhesive is prepared from the following raw materials: an optical monomer, an acrylate prepolymer, a modified acrylate prepolymer, nanoparticles, a photoinitiator, a coupling agent and a diluent, the structural general formula of the optical monomer is shown in the specification, R1 is methyl or hydrogen, R2 is methyl or hydrogen, and R3 is methyl or hydrogen. And the difference between the refractive index of the nanoparticles and the refractive index of the optical monomer is greater than 0.4. According to the nanoimprint adhesive provided by the invention, the optical monomer and the nanoparticles have a synergistic effect, so that the refractive index of the cured nanoimprint adhesive can reach 1.7-1.8. The optical monomer can participate in curing together with other components to form a macromolecular or cross-linked network, so that the cured colloid can realize higher structural strength, nanoimprint demoulding is facilitated, the micro-nano structure is kept intact during demoulding, and the colloid is not easy to remain; and when a reliability test is carried out, the micro-nano structure on the cured colloid can be kept relatively complete, so that the production yield can be improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of nano-imprint technology, in particular to a nano-imprint glue and a preparation method thereof. BACKGROUND

[0002] Nano-imprint technology (NIL) is a technology that transfers micro-nano structures on a template to a material to be processed by using a nano-imprint glue as an aid. In the process of imprinting, the nano-imprint glue acts as a medium for pattern transfer, and the micro-nano structures on the template are interacted with the nano-imprint glue, so that the micro-nano structures are copied on the nano-imprint glue in a proportional manner. Nano-imprint technology mainly includes thermal imprinting, ultraviolet imprinting and soft imprinting. The ultraviolet imprinting mainly uses ultraviolet nano-imprint glue which can be cured by ultraviolet light. After the glue and the template interact at room temperature, the optical material with micro-nano structures is formed by ultraviolet irradiation.

[0003] Compared with thermal imprinting, ultraviolet nano-imprint does not require high temperature and high pressure conditions, but during the ultraviolet nano-imprint process, there is a certain degree of incomplete curing, which affects the mechanical properties of the micro-nano structure. In the demolding process, damage, residual glue and other situations are prone to occur. When the optical material cured by ultraviolet light is tested for reliability, the micro-nano structure is damaged or falls off to different degrees. In addition, the content of inorganic particles is usually increased in the composition of the nano-imprint glue to increase the refractive index of the entire glue. However, a large amount of inorganic particles will reduce the flowability of the glue, so that the glue cannot interact well with the micro-nano structure of the template during the imprinting process, causing the structure size to be deformed or the parameters to change greatly, affecting the optical performance. It also affects the coatability of the nano-imprint glue, making the glue coating effect worse and reducing the production yield. SUMMARY

[0004] Therefore, the present application provides a nano-imprint glue and a preparation method thereof, which aims to solve at least one of the above technical problems, improve the structural strength of the glue after curing, and have high refractive index and convenient coating performance.

[0005] The nano-imprint glue provided by the first aspect of the present application is prepared from the following raw materials: an optical monomer, an acrylate prepolymer, a modified acrylate prepolymer, a nano-particle, a photoinitiator, a coupling agent and a diluent. The general structure of the optical monomer is

[0006] wherein R1 is methyl or hydrogen, and R2 is methyl or hydrogen. The difference between the refractive index of the nano-particle and the refractive index of the optical monomer is greater than 0.4.

[0007] It can be seen from the technical solution that the nanoimprint glue provided by the first aspect of the present application provides a certain material basis for the nanoimprint glue to have a high refractive index by using the optical monomer with a specific symmetrical structure, a phenyl sulfide group and nanoparticles, and the optical monomer has a (meth) acrylate group, thereby having two or more functionalities, being able to well participate in curing together with other components to form a macromolecule or a crosslinking network, enabling the glue after curing to achieve a high structural strength, being conducive to nanoimprint demolding, and the micro-nano structure being kept intact and not easily remaining glue during demolding; the micro-nano structure on the glue after curing can also be kept relatively complete when reliability testing is performed; the difference between the refractive index of the nanoparticles and the optical monomer is greater than 0.4, the refractive index of the optical monomer itself is 1.63-1.67, and then the refractive index of the nanoparticles is greater than 2.03; in the present application, a large amount of nanoparticles does not need to be added, and the refractive index of the nanoimprint glue after curing can reach 1.7-1.8; due to the need for only a certain amount of nanoparticles, the entire nanoimprint glue can maintain good fluidity and coatability, the glue has good coating effect and is easy to fill into a mold for imprinting, and the production yield is improved.

[0008] The preparation method of the nanoimprint glue of the foregoing embodiment provided by the second aspect of the present application includes the following steps: adding a diluent into a container, adding an optical monomer, an acrylate prepolymer and a modified acrylate prepolymer in a protective gas, stirring and mixing to form a uniform first solution; stirring the first solution and adding a coupling agent and a photoinitiator, continuing to stir to form a uniform second solution; adding nanoparticles into the second solution and continuing to stir to be uniform, and then standing; and using pressure filtration packaging to obtain the nanoimprint glue.

[0009] It can be seen from the technical solution that the preparation method of the nanoimprint glue provided by the second aspect of the present application, the nanoimprint glue prepared by the above method is fully mixed between various components, is not prone to agglomeration, can form a relatively uniform coating glue, is convenient for later coating and imprinting, and the prepared nanoimprint glue is convenient to use and ensures to have the performance of the foregoing nanoimprint glue.

[0010] It should be understood that the foregoing general description and the following detailed description are only exemplary and explanatory, and cannot limit the disclosure of the embodiments of the present application. BRIEF DESCRIPTION OF DRAWINGS

[0011] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced below. Obviously, the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creating labor.

[0012] Figure 1 is a flowchart of a preparation method of an optical monomer according to some embodiments of the present application;

[0013] Figure 2 is a chemical reaction equation involved in step S110 in the preparation of the optical monomer according to some embodiments of the present application;

[0014] Figure 3 is a chemical reaction equation involved in step S120 in the preparation of the optical monomer according to some embodiments of the present application;

[0015] Figure 4 is a chemical reaction equation involved in step S130 in the preparation of the optical monomer according to some embodiments of the present application;

[0016] Figure 5 is a flowchart of a preparation method of a nanoimprint glue according to some embodiments of the present application. DETAILED DESCRIPTION

[0017] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are some but not all of the embodiments of the present application. Based on the embodiments in the present application, any other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0018] In the related art, the structural strength of the ultraviolet nanoimprint glue is weak, and in the ultraviolet nanoimprint process, the ultraviolet nanoimprint glue with micro-nano structure is prone to adhesion to the template, resulting in easy damage to the ultraviolet nanoimprint glue with micro-nano structure after the imprinting is completed, and thus reducing the production yield. Meanwhile, the residual glue adhered to the mold pollutes the template, which is not convenient for the next use of the template.

[0019] In the related art, the monomer main component of the ultraviolet nanoimprint glue itself has a low refractive index, and a large amount of inorganic particles need to be added to improve the refractive index of the entire glue. The large amount of inorganic particles reduces the flowability of the glue, making the glue inconvenient to coat, and also making the glue not interact well with the micro-nano structure of the template in the imprinting process, so that the optical material with micro-nano structure cannot be prepared with good performance.

[0020] In view of this, the present application provides a nanoimprint glue, which has a high refractive index after curing, is convenient to use, has high structural strength, is convenient for imprinting and demolding, and greatly reduces the probability of residual glue on the template.

[0021] In the case of no conflict, the embodiments and features in the embodiments described below can be combined with each other.

[0022] The nanoimprint glue of the present application will be described below.

[0023] The nanoimprint glue is prepared from the following raw materials: an optical monomer, an acrylate prepolymer, a modified acrylate prepolymer, nanoparticles, a photoinitiator, a coupling agent and a diluent, and the general structure of the optical monomer is

[0024] wherein R1 is methyl or hydrogen, R2 is methyl or hydrogen, and the difference between the refractive index of the nanoparticles and the refractive index of the optical monomer is greater than 0.4.

[0025] As can be seen from the above, the nanoimprint glue provided by the application has certain folding and flexibility due to the use of the optical monomer with the specific symmetrical structure, and has certain toughness; the optical monomer has benzene sulfide groups, unsaturated aromatic groups, S atoms, (methyl) acrylate groups and other groups, the unsaturated aromatic groups have a conjugation effect, have a high molar refractive index and a low molar volume, and thus the refractive index of the optical monomer can be improved; the S atoms have a high polarizability and thus have a relatively high refractive index; the benzene sulfide groups have the structures of S atoms and benzene rings, and have the conjugation effect of the benzene rings and the high polarizability of the S atoms, and thus the refractive index of the optical monomer can be effectively ensured; the (methyl) acrylate groups have a high refractive index and a low volume shrinkage, and thus the optical monomer has a relatively high refractive index, and the measured refractive index is 1.63-1.67; the nanoparticles have a refractive index higher than 2.0 and a difference between the refractive index and the refractive index of the optical monomer greater than 0.4, and the raw materials having the two components provide a certain material basis for the nanoimprint glue to have a relatively high refractive index.

[0026] In addition, the acrylate groups of the application have C=C double bonds, the unsaturated bonds are relatively active, the optical monomer has a functional degree of 2 or more, can well participate in curing together with other components to form a macromolecule or a crosslinking network, the cured glue can have a relatively high structural strength, is beneficial to nanoimprint demolding, and the micro-nano structure is not easy to be damaged and residual glue during demolding; when reliability testing is performed, the micro-nano structure on the cured glue can also be kept relatively complete.

[0027] The refractive index of the optical monomer itself is 1.63-1.67, the difference between the refractive index of the nano-particle and the optical monomer is greater than 0.4, the refractive index of the nano-particle used in the application is greater than 2.03, the refractive index of the optical monomer and the nano-particle is high, and in the application, a large amount of nano-particle does not need to be added, and the refractive index of the cured nano-imprint glue can reach 1.7-1.8; since only a certain amount of nano-particle needs to be added, the refractive index and flowability of the nano-imprint glue are considered, the entire nano-imprint glue can maintain good flowability and coating properties, the coating effect of the glue is good, and the glue can be filled into the mold for imprinting in the imprinting process, especially the nano-imprint glue can be fully filled in the micro-nano structure of the mold, so that the nano-imprint glue has a complete micro-nano structure, the precision during imprinting is improved, and the production yield of the nano-imprint glue with a micro-nano structure is improved.

[0028] In the application, the addition of the acrylate prepolymer can serve as a skeleton, so that other components can form a crosslinked network on the skeleton to provide the required mechanical strength of the cured nano-imprint glue and improve the thermal stability. The modified acrylate prepolymer can improve the wear resistance and leveling property of the nano-imprint glue, and different properties can be improved depending on the specific type of addition. The addition of a photoinitiator can absorb ultraviolet light to generate free radicals or cations, triggering the curing of the acrylate monomer and the prepolymer, so that the entire system can easily undergo a photocuring reaction under the irradiation of ultraviolet light, improving the curing efficiency. The addition of a coupling agent can improve the adhesion of the nano-imprint glue to the substrate, effectively reducing the probability of the cured nano-imprint glue being peeled off from the substrate during demolding. The addition of a diluent can make the components of the entire glue system uniformly dispersed, have moderate concentration and viscosity, be easy to coat, and be easy to fill into the micro-nano structure of the mold during the imprinting process.

[0029] It can be understood that, compared with the ultraviolet nano-imprint glue in the related art, the ultraviolet nano-imprint glue is prone to adhesion to the mold during the ultraviolet nano-imprint process, resulting in damage to the ultraviolet nano-imprint glue with a micro-nano structure after imprinting, and thus reducing the production yield; at the same time, the residual glue adhered to the mold contaminates the mold, making it inconvenient to use the mold next time; the nano-imprint glue has high structural strength, the formed micro-nano structure is not damaged during demolding, can guarantee a certain production yield, and can reduce the residual glue on the mold, facilitating repeated use of the mold.

[0030] Compared with the monomer main component of the ultraviolet nanoimprint glue in the related art, the refractive index is not high, more inorganic particles need to be added to improve the refractive index of the whole glue, and the content of the inorganic particles reduces the flowability of the glue, so that the glue is not convenient to coat, and the glue cannot interact well with the micro-nano structure of the template in the process of imprinting, so that the optical material with the micro-nano structure cannot be prepared.

[0031] In some embodiments of the present application, the weight parts of each component in the raw material of the nanoimprint glue are as follows, in weight parts:

[0032] The first component is an optical monomer, and the weight parts of the optical monomer are 10 parts to 20 parts, for example, 10 parts, 11 parts, 14 parts, 15 parts, 17 parts, 19 parts, 20 parts, etc.

[0033] The second component is an acrylate prepolymer, and the weight parts of the acrylate prepolymer are 5 parts to 10 parts, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.

[0034] The third component is a modified acrylate prepolymer, and the weight parts of the modified acrylate prepolymer are 5 parts to 10 parts, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.

[0035] The fourth component is a nano particle, and the weight parts of the nano particle are 20 parts to 35 parts, for example, 20 parts, 21 parts, 23 parts, 25 parts, 26 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, etc.

[0036] The fifth component is a photoinitiator, and the weight parts of the photoinitiator are 3 parts to 5 parts, for example, 3.0 parts, 3.2 parts, 3.3 parts, 3.5 parts, 3.6 parts, 3.8 parts, 3.9 parts, 4.0 parts, 4.2 parts, 4.5 parts, 4.6 parts, 5.0 parts, etc.

[0037] The sixth component is a coupling agent, and the weight parts of the coupling agent are 1 part to 5 parts, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 3.7 parts, 4 parts, 4.5 parts, 5 parts, etc.

[0038] The seventh component is a diluent, and the weight parts of the diluent are 15 parts to 55 parts, for example, 15 parts, 20 parts, 32.2 parts, 33 parts, 39 parts, 40 parts, 52 parts, 53 parts, 55 parts, etc.

[0039] Since the nanoimprint glue needs a high refractive index, and the main components that bring high refractive index are optical monomers and nanoparticles, the contents of these two components need to be high. In addition, since the flowability of the nanoimprint glue needs to be considered, the addition amount of nanoparticles cannot be higher than 35 parts, for example, in some specific embodiments, the addition amount of nanoparticles is 25 parts. Since the diluent is used to improve the viscosity and flowability of the entire colloidal system, its amount is also high. Since the acrylate prepolymer and the modified acrylate prepolymer play a role in the curing skeleton of the nanoimprint glue and the wear resistance and leveling properties after curing, a reasonable amount needs to be added. The photo initiator and the coupling agent mainly have auxiliary effects, so a small amount is appropriate.

[0040] In some specific embodiments, the optical monomer in the raw materials in the nanoimprint glue is 15 parts, the acrylate prepolymer is 8 parts, the modified acrylate prepolymer is 8 parts, the nanoparticles are 25 parts, the photo initiator is 3 parts, the coupling agent is 1 part, and the diluent is 40 parts by weight.

[0041] In some specific embodiments, the optical monomer in the raw materials in the nanoimprint glue is 10 parts, the acrylate prepolymer is 5 parts, the modified acrylate prepolymer is 5 parts, the nanoparticles are 30 parts, the photo initiator is 4 parts, the coupling agent is 5 parts, and the diluent is 41 parts by weight.

[0042] In some specific embodiments, the optical monomer in the raw materials in the nanoimprint glue is 20 parts, the acrylate prepolymer is 10 parts, the modified acrylate prepolymer is 10 parts, the nanoparticles are 35 parts, the photo initiator is 5 parts, the coupling agent is 5 parts, and the diluent is 15 parts by weight.

[0043] In some specific embodiments, the optical monomer in the raw materials in the nanoimprint glue is 12 parts, the acrylate prepolymer is 6 parts, the modified acrylate prepolymer is 6 parts, the nanoparticles are 21 parts, the photo initiator is 3.3 parts, the coupling agent is 3.7 parts, and the diluent is 48 parts by weight.

[0044] In some specific embodiments, the optical monomer in the raw materials in the nanoimprint glue is 17 parts, the acrylate prepolymer is 9 parts, the modified acrylate prepolymer is 7 parts, the nanoparticles are 29 parts, the photo initiator is 3.8 parts, the coupling agent is 2 parts, and the diluent is 32.2 parts by weight.

[0045] The addition amount of each component can also be other parts within the addition range, which is not described here.

[0046] The structure and preparation method of the first component of the nanoimprint glue of the present application will be described below.

[0047] In some embodiments of the present application, the optical monomer comprises the following four structural formulas of monomers:

[0048] Monomer one, Monomer two,

[0049] Monomer three, Monomer four,

[0050] The preparation method of the optical monomer prepared in the present application will be described below. Since the preparation methods of the four monomers are similar, the preparation method of monomer one will be mainly described, monomer two only needs to replace the epichlorohydrin in step S110 with methyl epichlorohydrin; monomer three only needs to replace the acryloyl chloride in step S130 with methacryloyl chloride; monomer four only needs to replace the epichlorohydrin in step S110 with methyl epichlorohydrin, and replace the acryloyl chloride in step S130 with methacryloyl chloride, and the relevant products are changed accordingly, which will not be described here.

[0051] In some examples of the present application, referring to Figure 1 It is shown that monomer one in the optical monomer is prepared by the following steps: step S110, step S120 and step S130.

[0052] Step S110: referring to Figure 2 It is shown that 4-methylthiophenyl mercaptan, a first catalyst and a first solvent are uniformly mixed, and epichlorohydrin is added to generate a first product by reaction, and the first product is 1-(4-methylthiophenyl mercaptan)-3-chloro-2-propanol.

[0053] In this step, a nucleophilic substitution reaction mainly occurs, and 4-methylthiophenyl mercaptan attacks the terminal carbon of the epoxide ring of epichlorohydrin under the action of the first catalyst to generate the first product 1-(4-methylthiophenyl mercaptan)-3-chloro-2-propanol by ring opening.

[0054] It should be noted that when methyl epichlorohydrin reacts with 4-methylthiophenyl mercaptan, the first product is 1-(4-methylthiophenyl mercaptan)-3-chloro-2-methyl-2-propanol.

[0055] Step S120, referring to Figure 3 It is shown that 4'4-dimercaptodiphenyl sulfide, a second catalyst and a second solvent are uniformly mixed, and the first product is added to generate a second product by catalytic reaction, and the molar ratio of the first product to 4'4-dimercaptodiphenyl sulfide is (2-2.4):1, and the second product is 4-4'-thiobis(1-(4-methylthiophenyl mercaptan)-2-propanol) phenyl sulfide.

[0056] In this step, under the action of the second catalyst, two molecules of mercapto of 4'4-dimercaptodiphenyl sulfide attack the chlorine atoms in a certain amount of the first product, thereby generating the second product with a symmetrical structure.

[0057] It should be noted that if step S110 uses methyl epichlorohydrin to generate the first product, then the second product is 4-4' thio-bis(1-(4-methylthio phenyl mercaptan)-2-methyl-2-propanol) phenyl sulfide. It should also be noted that the molar ratio of the first product to 4'4-dimercaptodiphenyl sulfide is (2-2.4):1, which can be 2:1, 2.2:1, 2.4:1, etc., so that both molar amounts of mercapto groups can be fully reacted to generate a second product with a more symmetrical structure.

[0058] Step S130, referring to Figure 4 The second product, the auxiliary agent, the stabilizer are added into the third solvent and mixed uniformly; the solution is cooled, and acryloyl chloride and the third catalyst are added under the action of gas protection to react to generate an optical monomer (monomer one) with the structural formula The molar ratio of acryloyl chloride to the second product is (2-2.4):1, for example, which can be 2:1, 2.2:1, 2.4:1, etc., so that both molar amounts of alcohol hydroxyl groups can be fully reacted to generate a third product with a more symmetrical structure, which is the optical monomer of the present application.

[0059] In this step, an acylation reaction mainly occurs, in which the second product with alcohol hydroxyl groups attacks the carbonyl carbon of acryloyl chloride under the action of the auxiliary agent, the third catalyst and the stabilizer, and forms a side chain acrylate group after eliminating chlorine.

[0060] It should be noted that if step S110 uses methyl epichlorohydrin to generate the first product, then the second product is 4-4' thio-bis(1-(4-methylthio phenyl mercaptan)-2-methyl-2-propanol) phenyl sulfide, and if step S130 uses acryloyl chloride, monomer two with the aforementioned structural formula can be obtained. If step S130 uses methacryloyl chloride, monomer three with the aforementioned structural formula can be obtained. If step S110 uses methyl epichlorohydrin to generate the first product, then the second product is 4-4' thio-bis(1-(4-methylthio phenyl mercaptan)-2-methyl-2-propanol) phenyl sulfide, and if step S130 uses methacryloyl chloride, monomer four with the aforementioned structural formula can be obtained.

[0061] In some embodiments of the present application, the first catalyst and the second catalyst are selected from at least one of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU for short), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN for short) and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD for short), all of which can promote the nucleophilic reaction, specifically, in step S110, the protons of the mercapto groups can be abstracted to generate highly reactive thiolate ions to improve the nucleophilicity, and the thiolate ions selectively attack the less hindered terminal carbon of the epoxide in the epichlorohydrin to generate a chlorohydrin intermediate (the first product). Specifically, in step S120, the protons of the two mercapto groups can be abstracted to generate highly reactive dithiolate ions and improve the nucleophilicity, and the dithiolate ions attack the carbon atom of the halide to generate a sulfide bond. The DBU is inexpensive and easy to obtain, and can perform a mild ring-opening reaction on the epoxide substrate.

[0062] In some embodiments of the present application, the first solvent and the second solvent are selected from at least one of toluene, dimethyl sulfoxide, N,N-dimethylformamide and acetonitrile. The first solvent needs to be able to fully dissolve 4-methylthio phenyl mercaptan, the first catalyst and epichlorohydrin (or methyl epichlorohydrin), so that the three can be fully mixed and react in the reaction system, which is conducive to the reaction to be more complete and promote the reaction to be efficient. Similarly, the second solvent needs to be able to fully dissolve the first product, 4',4'-dimercaptodiphenyl sulfide and the second catalyst, so that the three can be fully mixed and react in the reaction system, which is conducive to the reaction in step S120 to be more complete and promote the reaction to be efficient.

[0063] In some embodiments of the present application, the auxiliary agent is selected from triethylamine (TEA for short) or 1,8-diazabicycloundec-7-ene (DBU for short). The auxiliary agent can enhance the deprotonation activity of the alcohol hydroxyl group of the second product, so as to facilitate the attack on acryloyl chloride (or methacryloyl chloride) to generate a positive tetrahedral intermediate, and then release chlorine to form the optical monomer of the present application.

[0064] In some embodiments of the present application, the stabilizer is selected from at least one of dibutylhydroxytoluene (BHT for short), butylated hydroxyanisole (BHA for short) and tertiary butyl hydroquinone (TBHQ for short). These stabilizers can effectively prevent the self-polymerization of acryloyl chloride, keep acryloyl chloride stable in the reaction, reduce side reactions, and keep the properties of the acrylate group generated after the reaction of acryloyl chloride stable and not easy to be oxidized, thereby ensuring the properties of the nanoimprint glue made by using the optical monomer as one of the components to be stable. In particular, the BHT is relatively easy to obtain, which can control the reaction cost.

[0065] In some embodiments of the present application, the third solvent is selected from dichloromethane or tetrahydrofuran, and the third solvent can make the second product, the auxiliary agent, the stabilizer, the acryloyl chloride (or the methacryloyl chloride) and the third catalyst be uniformly mixed, so that the reaction system is relatively uniform, which is conducive to improving the reaction efficiency and making the reaction more complete.

[0066] In some embodiments of the present application, the third catalyst is 4-dimethylaminopyridine (DMAP), and the DMAP can make the reaction proceed rapidly under mild conditions, avoid side reactions caused by high temperature, and improve the reaction purity.

[0067] In some embodiments of the present application, the molar ratio of 4-methylthiophenylthiol, the first catalyst, the first solvent and epichlorohydrin is 100:(70-90):(1317-1505):(100-120), for example, the specific ratio is 100:70:1317:100, 100:80:1410:110 or 100:90:1505:120, etc. Similarly, the molar ratio of 4-methylthiophenylthiol, the first catalyst, the first solvent and methyl epichlorohydrin is 100:(70-90):(1317-1505):(100-120), for example, the specific ratio is 100:70:1317:100, 100:80:1410:110 or 100:90:1505:120, etc. Thus, the reaction in step S110 can be relatively complete and rapid, the nucleophilic substitution reaction is more complete, and the by-products are reduced.

[0068] In some embodiments of the present application, the reaction temperature of 4-methylthiophenylthiol and epichlorohydrin or methyl epichlorohydrin is room temperature, and the reaction time is 14-18 hours, for example, which can be 14 hours, 15 hours, 16 hours, 17 hours or 18 hours, etc. The nucleophilic reaction occurring at room temperature can effectively reduce the generation of by-products and reduce the decomposition of heat-sensitive compounds.

[0069] In some embodiments of the present application, the molar ratio of 4'4-dimercaptodiphenyl sulfide, the second catalyst, the second solvent and the first product is 50:(50-55):(847-1035):(100-120), for example, which can be 50:53.5:941:100, 50:53.5:941:110, 50:53.5:941:120, 50:50:847:100, 50:55:1035:120, etc. Thus, the nucleophilic reaction in step S120 can be more complete and rapid, the nucleophilic substitution reaction is more complete, the by-products are reduced, and the bis-thio product can be generated.

[0070] In some embodiments of the present application, the reaction temperature of 4'4- dimercaptodiphenyl sulfide and the first product is room temperature, and the reaction time is 18h-22h, such as 18h, 19h, 20h, 21h or 22h, etc., which is not limited here. The nucleophilic reaction occurring at room temperature can effectively reduce the generation of by-products and reduce the decomposition of heat-sensitive compounds.

[0071] In some embodiments of the present application, the molar ratio of the second product, the auxiliary agent, the stabilizer, the third solvent, acryloyl chloride and the third catalyst is 35:(144-187.2):(1.5-2.0):(1714-2026):(70-84):(3.0-4.0), such as 35:175:1.75:1870:70:3.5, 35:175:1.75:1870:77:3.5, 35:175:1.75:1870:84:3.5, 35:144:1.5:1870:70:3.0, 35:187.2:2.0:2026:87:4.0; or the molar ratio of the second product, the auxiliary agent, the stabilizer, the third solvent, methacryloyl chloride and the third catalyst is 35:(144-187.2):(1.5-2.0):(1714-2026):(70-84):(3.0-4.0), such as 35:175:1.75:1870:70:3.5, 35:175:1.75:1870:77:3.5, 35:175:1.75:1870:84:3.5, 35:144:1.5:1870:70:3.0, 35:187.2:2.0:2026:87:4.0. Thus, the acylation reaction in step S130 can be more complete, faster, reduce by-products, and generate two molecular weight acrylate groups.

[0072] In some embodiments of the present application, the reaction temperature of the second product and acryloyl chloride or methacryloyl chloride is 0°C or ice bath conditions, and the reaction is carried out in a protective atmosphere with nitrogen or inert gas, which can effectively avoid the decomposition of acryloyl chloride (or methacryloyl chloride) and make the reaction less likely to generate by-products.

[0073] In some specific embodiments, the reaction steps of Figures 2 to 4 , and the steps S110-S130 shown in Figure 1 The specific operation of the foregoing monomer one prepared by the steps S110-S130 is as follows:

[0074] To a 250 mL round bottom flask equipped with a magnetic stir bar was added 4- methylthiophenylthiol (100 mmol) and 8 mL of DBU (80 mmol) in 150 mL of toluene (1.41 mol) and stirred for 30 minutes. Subsequently, 8.6 mL of epichlorohydrin (110 mmol) was added dropwise. The reaction vessel was stirred at room temperature for 16 hours. After which time, the volatiles were removed under reduced pressure, the residue was then diluted with DCM and washed sequentially with 1 M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The combined organic extracts were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography using a mixture of 20% ethyl acetate (EtOAc) in hexanes as eluent to yield a colorless, low viscosity liquid containing 1-(4-methylthiophenylthiol)-3-chloro-2-propanol.

[0075] To a 250 mL round bottom flask equipped with a magnetic stir bar was added 4- methylthiophenylthiol (100 mmol) and 8 mL of DBU (80 mmol) in 150 mL of toluene (1.41 mol) and stirred for 30 minutes. Subsequently, 8.6 mL of epichlorohydrin (110 mmol) was added dropwise. The reaction vessel was stirred at room temperature for 16 hours. After which time, the volatiles were removed under reduced pressure, the residue was then diluted with DCM and washed sequentially with 1 M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The combined organic extracts were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography using a mixture of 20% ethyl acetate (EtOAc) in hexanes as eluent to yield a colorless, low viscosity liquid containing 1-(4-methylthiophenylthiol)-3-chloro-2-propanol.

[0076] To a 250 mL round bottom flask equipped with a magnetic stir bar, 4-4' thio-bis(1-(4- methylthiophenylthiol)-2-propanol) (35 mmol), 24.3 mL of triethylamine (175 mmol), and 0.4 g of butylated hydroxytoluene (BHT) (1.75 mmol) were added, diluted with 120 mL of dichloromethane, and stirred under argon for 30 minutes. After cooling the solution to 0 °C, 6.3 mL of acryloyl chloride (77 mmol) was added dropwise, followed by the addition of 0.4 g of 4-dimethylaminopyridine (DMAP) (3.5 mmol). The reaction mixture was stirred at room temperature for 20 hours. After this time, the volatiles were removed under reduced pressure, the residue was diluted with 250 mL of dichloromethane, and washed sequentially with 1 M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The combined organic extracts were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography using 20% ethyl acetate (hexanes) as eluent, and the target compound was obtained as a colorless to slightly yellow viscous liquid, which is monomer one of the present application.

[0077] In some specific embodiments, the specific procedure for preparing the aforementioned monomer two is as follows: the procedure is substantially the same as that for monomer one, except that the epichlorohydrin is replaced by methyl epichlorohydrin: 4-methylthiophenylthiol (100 mmol) was mixed with 12 mL of DBU (80 mmol) in 150 mL of toluene (1.41 mol), added to a 250 mL round bottom flask equipped with a magnetic stir bar, and stirred for 30 minutes. Subsequently, 10.7 mL of methyl epichlorohydrin (110 mmol) was added dropwise. The reaction vessel was stirred at room temperature for 16 hours. After this time, the volatiles were removed under reduced pressure, the residue was then diluted with DCM, and washed sequentially with 1 M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The combined organic extracts were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography using 20% ethyl acetate (i.e., EtOAc) in hexanes as eluent, and the target compound was obtained as a colorless, low viscosity liquid, which is a liquid containing 1-(4-methylthiophenylthiol)-3-chloro-2-methyl-2-propanol.

[0078] To a 250 mL round bottom flask equipped with a magnetic stir bar, was added 4,4'- dimercaptodiphenyl sulfide (50 mmol) and 8 mL of DBU (53.5 mmol) in 100 mL of toluene (941 mmol) and stirred for 30 minutes. Subsequently, 9.1 mL of l-(4- methylthiophenylthiol)-3-chloro-2-methyl-2-propanol (110 mmol) was added dropwise. The reaction vessel was stirred at room temperature for 20 hours. After which, the volatiles were removed under reduced pressure, the residue was then diluted with DCM and washed sequentially with 1 M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The combined organic extracts were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography using a mixture of 20% ethyl acetate (EtOAc) in hexanes as eluent to yield the target compound as a yellowish viscous liquid, 4-4' thio-bis(l-(4-methylthiophenylthiol)-2-methyl-2-propanol) phenyl sulfide.

[0079] To a 250 mL round bottom flask equipped with a magnetic stir bar, was added 4-4' thio-bis(l-(4-methylthiophenylthiol)-2-methyl-2-propanol) phenyl sulfide (35 mmol), 24.3 mL of triethylamine (175 mmol) and 0.4 g of butylated hydroxytoluene (BHT) (1.75 mmol) was diluted with 120 mL (1870 mmol) of dichloromethane and stirred for 30 minutes under argon. The solution was cooled to 0 °C and 6.3 mL of acryloyl chloride (77 mmol) was added dropwise followed by the addition of 0.4 g of 4-dimethylaminopyridine (DMAP) (3.5 mmol) under argon. The reaction mixture was stirred at room temperature for 20 hours. After which, the volatiles were removed under reduced pressure, the residue was diluted with 250 mL of dichloromethane and washed sequentially with 1 Molar hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The combined organic extracts were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography using 20% ethyl acetate (hexanes) as eluent to yield the target compound as a colorless to yellowish viscous liquid, which is the monomer di of the present application. The overall synthesis of each step can be represented by the following chemical reaction equation:

[0080]

[0081] In some specific embodiments, the specific procedure for preparing the aforementioned monomer three is as follows: substantially the same as the method for preparing monomer one, except that acryloyl chloride is replaced by methacryloyl chloride: 4-methylthiophenylthiol (100 mmol) is mixed with 12 mL of DBU (80 mmol) in 150 mL of toluene (1.41 mol), added to a 250 mL round bottom flask equipped with a magnetic stir bar, and stirred for 30 minutes. Subsequently, 8.6 mL of epichlorohydrin (110 mmol) is added dropwise. The reaction vessel is stirred at room temperature for 16 hours. After that, the volatiles are removed under reduced pressure, then the residue is diluted with DCM and washed sequentially with 1 M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The combined organic extracts are dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product is purified by silica gel column chromatography using a mixture of 20% ethyl acetate (EtOAc) in hexanes as eluent, resulting in a colorless, low-viscosity liquid containing 1-(4-methylthiophenylthiol)-3-chloro-2-propanol.

[0082] 4,4'-dimercaptodiphenyl sulfide (50 mmol) is mixed with 8 mL of DBU (53.5 mmol) in 100 mL of toluene (941 mmol), added to a 250 mL round bottom flask equipped with a magnetic stir bar, and stirred for 30 minutes. Subsequently, 8.2 mL of 1-(4-methylthiophenylthiol)-3-chloro-2-propanol (110 mmol) is added dropwise. The reaction vessel is stirred at room temperature for 20 hours. After that, the volatiles are removed under reduced pressure, then the residue is diluted with DCM and washed sequentially with 1 M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The combined organic extracts are dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product is purified by silica gel column chromatography using a mixture of 20% ethyl acetate (EtOAc) in hexanes as eluent, resulting in a slightly yellow viscous liquid containing 4-4' thio-bis(1-(4-methylthiophenylthiol)-2-propanol) phenyl sulfide.

[0083] To a 250 mL round bottom flask equipped with a magnetic stir bar, 4-4' thio-bis(1-(4- methylthiophenylthiol)-2-propanol) (35 mmol), 24.3 mL of triethylamine (175 mmol), and 0.4 g of butylated hydroxytoluene (BHT) (1.75 mmol) were added, diluted with 120 mL of dichloromethane, and stirred under argon for 30 minutes. After the solution was cooled to 0 °C, 7.5 mL of methacryloyl chloride (77 mmol) was added dropwise under argon, followed by the addition of 0.4 g of 4-dimethylaminopyridine (DMAP) (3.5 mmol). The reaction mixture was stirred at room temperature for 20 hours. After this time, the volatiles were removed under reduced pressure, the residue was diluted with 250 mL of dichloromethane, and washed sequentially with 1 M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The combined organic extracts were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography using 20% ethyl acetate (hexanes) as eluent to yield the target compound as a colorless to slightly yellow viscous liquid, which is the monomer three of the present application. The overall synthesis of each step is represented by the following chemical reaction equation:

[0084]

[0085] In some specific embodiments, the specific procedure for preparing the aforementioned monomer four is as follows: the procedure is substantially the same as that for the preparation of monomer one, except that the epichlorohydrin is replaced with methyl epichlorohydrin and the acryloyl chloride is replaced with methacryloyl chloride. 4-Methylthiophenylthiol (100 mmol) was mixed with 12 mL of DBU (80 mmol) in 150 mL of toluene (1.41 mol), added to a 250 mL round bottom flask equipped with a magnetic stir bar, and stirred for 30 minutes. Subsequently, 10.7 mL of methyl epichlorohydrin (110 mmol) was added dropwise. The reaction vessel was stirred at room temperature for 16 hours. After this time, the volatiles were removed under reduced pressure, the residue was diluted with DCM, and washed sequentially with 1 M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The combined organic extracts were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography using 20% ethyl acetate (EtOAc) in hexanes as eluent to yield a colorless, low viscosity liquid containing 1-(4-methylthiophenylthiol)-3-chloro-2-methyl-2-propanol.

[0086] To a 250 mL round bottom flask equipped with a magnetic stir bar, was added 4,4'- dimercaptodiphenyl sulfide (50 mmol) and 8 mL of DBU (53.5 mmol) in 100 mL of toluene (941 mmol) and stirred for 30 minutes. Subsequently, 9.1 mL of l-(4- methylthiophenylthiol)-3-chloro-2-methyl-2-propanol (110 mmol) was added dropwise. The reaction vessel was stirred at room temperature for 20 hours. After which, the volatiles were removed under reduced pressure, the residue was then diluted with DCM and washed sequentially with 1 M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The combined organic extracts were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography using a mixture of 20% ethyl acetate (EtOAc) in hexanes as eluent to yield the target compound as a yellowish viscous liquid, 4-4' thio-bis(l-(4-methylthiophenylthiol)-2-methyl-2-propanol) phenyl sulfide.

[0087] To a 250 mL round bottom flask equipped with a magnetic stir bar, was added 4-4' thio-bis(l-(4-methylthiophenylthiol)-2-methyl-2-propanol) phenyl sulfide (35 mmol), 24.3 mL of triethylamine (175 mmol) and 0.4 g of butylated hydroxytoluene (BHT) (1.75 mmol) was diluted with 120 mL (1870 mmol) of dichloromethane and stirred for 30 minutes under argon. The solution was cooled to 0 °C and 7.5 mL of methacryloyl chloride (77 mmol) was added dropwise followed by the addition of 0.4 g of 4-dimethylaminopyridine (DMAP) (3.5 mmol) under argon. The reaction mixture was stirred at room temperature for 20 hours. After which, the volatiles were removed under reduced pressure, the residue was diluted with 250 mL of dichloromethane and washed sequentially with 1 Molar hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The combined organic extracts were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography using 20% ethyl acetate (hexanes) as eluent to yield the target compound as a colorless to yellowish viscous liquid, monomer four of the present application. The overall synthesis of each step is represented by the following chemical reaction equation:

[0088]

[0089] Test the refractive index: disperse monomer one, monomer two, monomer three, monomer four and OPPEA (also known as o-phenylphenoxyethyl acrylate, CAS number 91442-24-9) in a solvent such as tetrachloroethane, then spin-coat on a silicon wafer by spin coating method, and test the refractive index by ellipsometer after baking. The measured refractive index is: the refractive index of monomer one is 1.665, the refractive index of monomer two is 1.643, the refractive index of monomer three is 1.645, the refractive index of monomer four is 1.638; the refractive index of OPPEA is 1.575. The refractive index of the optical monomer of the present application is greater than 1.63, and the refractive index of monomer one is as high as 1.665, and the refractive index of each optical monomer is significantly improved compared with the refractive index of the comparative example OPPEA.

[0090] Glass transition temperature (Tg) test. Using TA Instruments Japan 2910 differential scanning calorimeter, test monomer one, monomer two, monomer three, monomer four and OPPEA at a temperature rising rate of 10℃ / min. The measured Tg is monomer one 118℃, monomer two 113℃, monomer three 112℃, monomer four 108℃; OPPEA 35℃. The Tg of the optical monomer of the first component in the present application is greater than 108℃, which has a higher glass transition temperature than OPPEA, indicating that the optical monomer of the present application has good heat resistance and better stability.

[0091] The following describes the types and sources of the second component of the nanoimprint glue of the present application.

[0092] In some embodiments of the present application, the acrylate prepolymer is selected from at least one of 9537 (specifically available from Kunshan Castor High Polymer Material Co., Ltd.); Changxing Material 6151, Changxing Material DR-U084, Changxing Material DR-U299, Changxing Material DR-U379, ETERCURE DR-U384, Changxing Material DR-U388, ETERCURE 6371, ETERCURE 6372 (specifically available from Changxing Material Co., Ltd.); Meiyuan HR6100, Meiyuan HR6200, Meiyuan PS4500, Meiyuan PS4040, Meiyuan PS610 (specifically available from Meiyuan Special Chemical Industry Co., Ltd.); and at least one of Sartomer CN2254NS, CN2303, CN293, CN750, CN790, CN8008NS, CN8201NS, CN983NS, CN996NS (specifically available from Sartomer).

[0093] Exemplarily, some of the above-mentioned materials are ultraviolet light curing resins with excellent adhesion, which can be quickly cured under ultraviolet light irradiation; some are multifunctional acrylates, which can quickly react to form a skeleton structure in a photo-curing reaction.

[0094] The kind and source of the third component of the nanoimprint glue of the present application will be described below.

[0095] In some embodiments of the present application, the modified acrylate prepolymer is selected from at least one of Huihui New Material CR91000, Huihui New Material CR91093, Huihui New Material CR90223, Huihui New Material HU280 (specifically purchased from Guangdong Huihui New Material Co., Ltd.); Bluestar L-6902X, Bluestar L-6901 and Bluestar L-6902 (specifically purchased from Guangdong Bluestar New Material Co., Ltd.).

[0096] Illustratively, the modified acrylate prepolymer described above is a nano-hybrid modified polyurethane acrylate, and has multiple functionalities, which improves the ability of the nanoimprint glue to rapidly solidify; is a special functional group acrylate, has high leveling property, yellowing resistance and water resistance, and good toughness, as a component of the nanoimprint glue, can improve the coating convenience of the nanoimprint glue and prevent yellowing; is an inorganic hybrid polyurethane acrylate resin, the product has high reactivity, high crosslinking density, low shrinkage, good scratch resistance and wear resistance, high hardness, and as a component of the nanoimprint glue, can improve the wear resistance of the nanoimprint glue after solidification.

[0097] The kind and source of the fourth component of the nanoimprint glue of the present application will be described below.

[0098] In some embodiments of the present application, the nano-particles are metal oxide nano-particles. The metal oxide nano-particles can improve the structural stability of the nanoimprint glue after imprinting, so that the steps of demolding and etching are not prone to collapse.

[0099] In some embodiments of the present application, the particle size range of the nano-particles is 10 nm to 20 nm, for example, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 18 nm and 20 nm, etc. The nano-particles within the above range not only can be quickly dispersed in the solution, reduce the entanglement between the polymers, and keep the viscosity within a certain range, so that the whole glue is easy to coat; the nano-particles can also be embedded in the crosslinking network of the optical monomer, which can increase the hardness of the whole solidified nanoimprint glue, and is beneficial to improve the Young's modulus, so as to avoid the collapse of the micro-nano structure on the nanoimprint glue during demolding.

[0100] In some embodiments of the present application, the nano-particles are metal oxide nano-particles and the particle size range of the nano-particles is 10 nm to 20 nm. The specific technical effects can be referred to the foregoing description, which will not be repeated here.

[0101] In further embodiments, the nanoparticles are titanium oxide nanoparticles or zirconium oxide nanoparticles, wherein the titanium oxide can absorb ultraviolet light, protect the stability of the imprinting glue in ultraviolet curing, the refractive index of the titanium oxide is 2.2-2.6, and can significantly improve the refractive index of the nanoimprint glue with a small amount of addition. The zirconium oxide has high stability, and the refractive index is 2.1-2.3, and can also quickly improve the refractive index of the nanoimprint glue with a certain amount of addition.

[0102] In specific embodiments, the nanoparticles are selected from one or more of PixClear Zirconia 10nm, PixClear Titania 20nm, and core-shell 20nm, without limitation.

[0103] The following describes the types and sources of the fifth component of the nanoimprint glue of the present application.

[0104] In some embodiments of the present application, the photoinitiator is selected from at least one of photoinitiator 1173 (i.e., 2-hydroxy-2-methyl-1-phenyl-1-propanone), photoinitiator 1176, photoinitiator 184 (i.e., 1-hydroxy-cyclohexyl-phenyl ketone), TPO (i.e., (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide), TPO-L (i.e., 2,4,6-trimethylbenzoyl phosphonic acid ethyl ester), photoinitiator 127 (i.e., 2-hydroxy-1-(4-(2-hydroxy-2-methylpropionyl phenyl) benzyl)-2-methyl-1-propanone), photoinitiator 369, ITX, BDK (i.e., benzoin dimethyl ether), photoinitiator 819 (i.e., phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide), photoinitiator 754, photoinitiator 380, BMF, ANTHRACURE TM UVS-1331, ANTHRACURE TM UVS-1101, Easepi 6992, Easepi 1176, Easepi 250.

[0105] Exemplarily, the light initiators provided above can all play a role in adjusting the curing rate and curing degree of the nanoimprint glue. By selecting different light initiators, the nanoimprint glue can be cured under light of different wavelengths. For example, (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide (also known as TPO) has an absorption wavelength of 350 nm-400 nm, and after irradiation, benzoyl and phosphoryl radicals can be generated, both of which can initiate polymerization, and the light curing speed is fast, has low volatility, no yellowing of the coating, low polymerization effect, no residue, and can be used for transparent layer structures. 2,4,6-trimethylbenzoyl ethyl phosphonate (also known as light initiator TPO-L) has an absorption wavelength of 270 nm-370 nm. 2-hydroxy-2-methyl-1-phenyl-1-propanone (also known as light initiator 1173) has an absorption wavelength of 244 nm, is a liquid product, is easy to blend, and is also easy to use in combination with other light initiators, is efficient, has low yellowing, and has a certain volatility at high temperatures. Benzoin dimethyl ether (also known as light initiator BDK) has an absorption wavelength of 205 nm-253 nm. It is a high-efficiency and stable light initiator, has stronger absorption performance than 1173 and 184, and thus can more effectively promote the crosslinking reaction of double bonds. 2-hydroxy-1-(4-(2-hydroxy-2-methylpropionyl) phenyl) benzyl)-2-methyl-1-propanone (also known as light initiator 127) has an absorption wavelength of 259 nm, has low sensitivity to oxygen, has good surface curing effect, low volatility, and low odor of itself and light decomposition products.

[0106] The types and sources of the sixth component of the nanoimprint glue of the present application will be described below.

[0107] In some embodiments of the present application, the coupling agent is at least one of γ-(methacryloyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriethoxysilane, γ-(methacryloyloxy)propyltriethoxysilane, methacryloyloxymethyltriethoxysilane, 3-methacryloyloxypropyltris(methoxyethoxy)silane, methacryloyloxypropyltris(dimethylsiloxy)silane, γ-(acryloyloxy)propyltrimethoxysilane, γ-(acryloyloxy)propyltriethoxysilane, allyl-tris(trimethylsiloxy)silane, 1,3-bis(3-methacryloyloxypropyl)tetra(trimethylsiloxy)disiloxane, and N-(3-acryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane.

[0108] Exemplarily, the organosilanes provided above can all promote adhesion to the substrate, avoid separation of the glue film from the substrate during the imprinting process, avoid migration of free coupling agents, and effectively reduce the probability of peeling of the cured nanoimprint glue from the substrate during demolding.

[0109] The kind and source of the seventh component of the nanoimprint glue of the present application will be described below.

[0110] In some embodiments of the present application, the diluent is at least one of propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, ethyl acetate, N,N-dimethylformamide, methyl ethyl ketone, dimethyl sulfoxide, and butyl acetate.

[0111] Exemplarily, the above-mentioned diluents are all organic solvents, which can uniformly disperse each component, and can also adjust the viscosity and volatilization rate of the nanoimprint glue, so as to facilitate the control of the thickness and surface flatness of the film layer in the spin coating process.

[0112] The preparation method of the nanoimprint glue in the foregoing embodiments of the present application will be described below.

[0113] According to the present application, a preparation method of the nanoimprint glue based on the foregoing embodiments is provided, as shown in the following formula (I): Figure 5 The preparation method comprises the following steps:

[0114] In step S210, the diluent is added to the container, and the optical monomer, the acrylate prepolymer, and the modified acrylate prepolymer are added in the protective gas, and then stirred and mixed to form a uniform first solution. The kind and mass ratio of the optical monomer, the acrylate prepolymer, the modified acrylate prepolymer, and the diluent can refer to the description above, and will not be repeated here.

[0115] In step S210 of some embodiments, the first stirring speed can be 400 r / min to 600 r / min, for example, 400 r / min, 450 r / min, 500 r / min, and 600 r / min, etc. In this way, each component can be slowly mixed to prevent agglomeration and to make each component disperse uniformly faster.

[0116] In step S210 of some embodiments, the temperature in the container is 21℃ to 25℃, for example, 21℃, 22℃, 23℃, 24℃, and 25℃, etc. In this way, each component can be mixed more gently and less likely to decompose.

[0117] In step S210 of some embodiments, the stirring time is 20 min to 40 min, for example, 20 min, 30 min, and 40 min, etc. In this way, each component can be fully mixed and uniformly dispersed.

[0118] In step S210 of some embodiments, during the stirring and mixing process, nitrogen, argon, or helium gas can be introduced into the container to reduce the oxygen concentration in the container. The specific gas can be selected according to the actual situation.

[0119] Step S220, stirring the first solution and adding coupling agent and photoinitiator, and continuing to stir to form a uniform second solution. The types and amounts of the coupling agent and photoinitiator added and the effects thereof can be referred to the foregoing description, and will not be repeated here.

[0120] In step S220 of some embodiments, the first stirring speed can be 700 r / min to 900 r / min, such as 700 r / min, 750 r / min, 800 r / min, 850 r / min, 900 r / min, etc. In this way, the coupling agent and the photoinitiator can be dispersed more quickly and uniformly.

[0121] In step S220 of some embodiments, the temperature in the container is 21℃ to 25℃, such as 21℃, 22℃, 23℃, 24℃, 25℃, etc. In this way, the process of continuing to add components is relatively gentle and decomposition is less likely to occur.

[0122] In step S220 of some embodiments, the stirring time is 20 min to 40 min, such as 20 min, 30 min, 40 min, etc. In this way, the components can be mixed sufficiently and uniformly.

[0123] In step S220 of some embodiments, during the process of stirring and mixing uniformly, nitrogen, helium or argon gas can be introduced into the container to reduce the oxygen concentration in the container. The specific gas can be selected according to the actual situation.

[0124] Step S230, adding nanoparticles to the second solution and continuing to stir uniformly and then standing. The types, particle sizes and effects of the nanoparticles can be referred to the foregoing description, and will not be repeated here.

[0125] In step S230 of some embodiments, the temperature in the container is 21℃ to 25℃, such as 21℃, 22℃, 23℃, 24℃, 25℃, etc. In this way, the process of continuing to add nanoparticles is relatively gentle, and the temperature before and after the mixing is consistent.

[0126] In step S230 of some embodiments, the stirring time is 10 h to 14 h, such as 10 h, 11 h, 12 h, 13 h, 14 h, etc. In this way, the nanoparticles can be dispersed sufficiently in the system.

[0127] In step S230 of some embodiments, the standing time is 20 min to 40 min, such as 20 min, 30 min, 40 min, etc.

[0128] Step S240, encapsulating the nanoimprint glue by pressure filtration.

[0129] In some embodiments of the present application, the pressure filtration package employs an organic filter membrane of 0.22 μm to filter out impurities, thereby obtaining the nanoimprint glue of the present application.

[0130] As can be seen from the above, the preparation method of the nanoimprint glue provided by the present application, the nanoimprint glue prepared by the above method, the components are mixed sufficiently, are not prone to agglomeration, can form a relatively uniform coating glue, is convenient for later coating and imprinting, and the prepared nanoimprint glue is convenient to use and ensures the performance of the aforementioned nanoimprint glue.

[0131] The preparation method of the nanoimprint glue of the present application and the performance test of the prepared nanoimprint glue will be described below in combination with specific examples.

[0132] Example 1

[0133] 40 g of propylene glycol methyl ether acetate (PGMEA) was added to a container, nitrogen protection was performed, and stirring was started at a speed of 500 r / min, then 15 g of optical monomer, 8 g of HR6200 acrylate prepolymer and 8 g of CR91000 modified acrylate prepolymer were slowly added, stirring was performed for 30 minutes to make the system completely dispersed and dissolved to obtain a uniform first solution, and the liquid temperature in the container was maintained at 23 ℃ during the process.

[0134] The speed was adjusted to 800 r / min, then 1 g of γ-(methacryloyloxy) propyl trimethoxysilane coupling agent and 3 g of TPO photoinitiator were slowly added, and stirring was continued for 30 minutes to make the system completely dispersed and dissolved to obtain a uniform second solution, and the liquid temperature in the container was maintained at 23 ℃ during the process.

[0135] 25 g of PixClear Zirconia 10 nm nanoparticle dispersion liquid was slowly added, and stirring was continued for 12 hours, and the liquid temperature in the container was maintained at 23 ℃ during the process. After stirring was completed, the system was left to stand for 30 minutes.

[0136] The nanoimprint glue was obtained by pressure filtration package using an organic filter membrane of 0.22 μm.

[0137] Example 2

[0138] The preparation method was substantially the same as that of Example 1, except that the optical monomer was replaced by monomer two with the structural formula to obtain the nanoimprint glue.

[0139] Example 3

[0140] The preparation method was substantially the same as that of Example 1, except that the optical monomer was replaced by monomer two with the structural formula monomer three, to obtain the nanoimprint glue.

[0141] Example 4

[0142] The preparation method is substantially the same as that of Example 1, except that the optical monomer is replaced by monomer four with the structural formula to obtain the nanoimprint glue.

[0143] Comparative Example 1

[0144] The preparation steps are substantially the same as those of Example 1, except that the optical monomer in Example 1 is replaced by o-phenylphenoxyethyl acrylate (OPPEA) to prepare the ultraviolet nanoimprint glue, wherein the OPPEA monomer does not have the phenyl sulfide group of the present application, nor does it have the S atom of the present application.

[0145] Test Example

[0146] The nanoimprint glues prepared in Examples 1-4 and the ultraviolet nanoimprint glue prepared in Comparative Example 1 are subjected to the following performance tests, and the test methods are as follows:

[0147] 1. Appearance test

[0148] A certain amount of the nanoimprint glues prepared in Examples 1-4 and the ultraviolet nanoimprint glue prepared in Comparative Example 1 are respectively poured into colorless transparent glass bottles, and the glue appearance characteristics are observed visually under a white light lamp or natural light.

[0149] 2. Viscosity test

[0150] The nanoimprint glues prepared in Examples 1-4 and the ultraviolet nanoimprint glue prepared in Comparative Example 1 are tested for their refractive index at 20°C on a Brookfield rheometer.

[0151] 3. Solid content test

[0152] The nanoimprint glues prepared in Examples 1-4 and the ultraviolet nanoimprint glue prepared in Comparative Example 1 are weighed on an analytical balance, then baked at 120°C for 2 hours in a forced air oven, weighed after baking, and the solid content is calculated.

[0153] 4. Hardness test

[0154] The nanoimprint glues prepared in Examples 1-4 and the ultraviolet nanoimprint glue prepared in Comparative Example 1 are spin-coated on silicon wafers according to certain parameters, baked, and then exposed and imprinted on an imprinting device to form a uniform film layer with a thickness of 1-3 μm, and the hardness is tested using a nanoindentation tester.

[0155] 5. Young's modulus test

[0156] The nanoimprint glue prepared in Examples 1-4 and the UV nanoimprint glue prepared in Comparative Example 1 were spin-coated on a silicon wafer according to certain parameters, and after baking, exposed and imprinted on an imprinting device to form a uniform film layer with a thickness of 1-3 μm. The Young's modulus was tested by a nanoindentation tester.

[0157] 6. Surface water drop angle test

[0158] The nanoimprint glue prepared in Examples 1-4 and the UV nanoimprint glue prepared in Comparative Example 1 were spin-coated on a silicon wafer according to certain parameters, and after baking, exposed and imprinted on an imprinting device to form a uniform film layer with a thickness of 1-3 μm. The surface water drop angle was tested by a water drop angle tester.

[0159] 7. Refractive index test

[0160] The nanoimprint glue prepared in Examples 1-4 and the UV nanoimprint glue prepared in Comparative Example 1 were spin-coated on a silicon wafer according to certain parameters, and after baking, exposed and imprinted on an imprinting device to form a uniform film layer with a thickness of 1-3 μm. The refractive index was tested by an ellipsometer.

[0161] The finally measured performance parameters are shown in Table 1 below.

[0162] Table 1 Performance test results of Examples 1-4 and Comparative Example 1

[0163]

[0164] From the measured performance data, it can be seen that the nanoimprint glue prepared by using the optical monomer has a higher refractive index than the UV nanoimprint glue prepared by using OPPEA. The refractive index of the optical monomer is higher than that of OPPEA. Compared with the UV nanoimprint glue prepared by using OPPEA under the same preparation conditions, the nanoimprint glue prepared by using the optical monomer has a higher refractive index after curing. Therefore, under the condition of adding the same amount of nanoparticles, the present application can obtain a higher refractive index. However, in Comparative Example 1, more nanoparticles must be used to obtain the same refractive index as the present application. Therefore, under the premise of ensuring that the nanoimprint glue has a high refractive index after curing, the nanoimprint glue with the optical monomer component of the present application can control the amount of nanoparticles added within a suitable range, so that the nanoparticles are added in an appropriate amount, and the nanoimprint glue has good flowability and is easy to coat.

[0165] Compared with the UV nanoimprint glue of Comparative Example 1, the Young's modulus of the nanoimprint glue of the present application is significantly improved, indicating that the nanoimprint glue with the optical monomer component of the present application can significantly improve the structural strength of itself. In the process of imprint demolding, the formed micro-nano structure is not easy to be damaged, which can ensure a certain production yield and reduce the residual glue on the mold, facilitating the repeated use of the mold.

[0166] At the same time, the viscosity of the nanoimprint glue of the application is slightly higher than that of the comparative example 1, but the overall viscosity is lower, the nanoimprint glue of the application has good flowability and is easy to coat, which is conducive to filling the micro-nano structure to form a high-precision pattern; and the glue is easy to adhere to the substrate and is not easy to peel off from the substrate during demolding, which is convenient for processing operation and use, matches the efficient imprint process, improves the efficiency, and is convenient for large-scale production.

[0167] The water drop angle of the nanoimprint glue of the application is smaller than that of the ultraviolet nanoimprint glue of the comparative example, indicating that the nanoimprint glue of the application is easier to spread and is easier to coat, has good wetting and leveling properties on the substrate, has excellent glue uniformity, is more uniform after coating, has high appearance yield after imprinting, and the hydrophilic contaminants on the surface of the glue are easier to remove.

[0168] The above is only a specific embodiment of the application, but the protection scope of the application is not limited thereto, and any person skilled in the art can easily think of various equivalent modifications or replacements within the technical range disclosed by the application, and these modifications or replacements should be covered within the protection scope of the application. Therefore, the protection scope of the application should be subject to the protection scope of the claims.

Claims

1. A nanoimprint glue, characterized by, The nano-imprinting glue is prepared from the following raw materials: optical monomer, acrylate prepolymer, modified acrylate prepolymer, nanoparticles, photoinitiator, coupling agent and diluent, the structural general formula of the optical monomer is wherein R1 is methyl or hydrogen, R2 is methyl or hydrogen, and the difference between the refractive index of the nanoparticle and the refractive index of the optical monomer is greater than 0.

4.

2. The nanoimprint resin according to claim 1, wherein The weight parts of each component in the raw materials are as follows, in weight parts: The optical monomer is 10-20 parts; The acrylate prepolymer is 5-10 parts; The modified acrylate prepolymer is 5-10 parts; The nanoparticles are 20-35 parts; The photoinitiator is 3-5 parts; The coupling agent is 1-5 parts; The diluent is 15-55 parts.

3. The nanoimprint glue according to claim 1 or 2, wherein The optical monomer is prepared by the following steps: The 4-methylthio phenyl mercaptan, the first catalyst and the first solvent are uniformly mixed, and the epichlorohydrin or the methyl epichlorohydrin is added to generate the first product, which is 1-(4-methylthio phenyl mercaptan)-3-chloro-2-propanol or 1-(4-methylthio phenyl mercaptan)-3-chloro-2-methyl-2-propanol; The 4'-4-dimercaptodiphenyl sulfide, the second catalyst and the second solvent are uniformly mixed, and the first product is added to generate the second product by catalytic reaction, wherein the molar ratio of the first product to the 4'-4-dimercaptodiphenyl sulfide is (2-2.4):1, and the second product is 4-4'-thiobis(1-(4-methylthio phenyl mercaptan)-2-propanol) phenyl sulfide or 4-4'-thiobis(1-(4-methylthio phenyl mercaptan)-2-methyl-2-propanol) phenyl sulfide; The second product, the auxiliary agent, and the stabilizer are added into the third solvent and mixed uniformly; the solution is cooled, and the acryloyl chloride or methacryloyl chloride is added under the protection of the gas and reacts with the third catalyst to generate the optical monomer with the general structure of , wherein the molar ratio of the acryloyl chloride or methacryloyl chloride to the second product is (2-2.4):

1.

4. The nanoimprint resin according to claim 3, wherein The first catalyst and the second catalyst are selected from at least one of 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene; The first solvent and the second solvent are selected from at least one of toluene, dimethyl sulfoxide, N,N-dimethylformamide and acetonitrile; The auxiliary agent is selected from triethylamine or 1,8-diazabicycloundec-7-ene; The stabilizer is selected from at least one of dibutylhydroxytoluene, butylhydroxyanisole and tertiary butyl hydroquinone; The third solvent is selected from dichloromethane or tetrahydrofuran; The third catalyst is 4-dimethylaminopyridine.

5. The nanoimprint resin of claim 3, wherein The molar ratio of the 4-methylthio phenyl mercaptan, the first catalyst, the first solvent and the epichlorohydrin is 100:(70-90):(1317-1505):(100-120); or the molar ratio of the 4-methylthio phenyl mercaptan, the first catalyst, the first solvent and the methyl epichlorohydrin is 100:(70-90):(1317-1505):(100-120); The reaction temperature of the 4-methylthio phenyl mercaptan and the epichlorohydrin or the methyl epichlorohydrin is room temperature, and the reaction time is 14-18 hours; The molar ratio of the 4'-4-dimercaptodiphenyl sulfide, the second catalyst, the second solvent and the first product is 50:(50-55):(847-1035):(100-120); The reaction temperature of the 4'-4-dimercaptodiphenyl sulfide and the first product is room temperature, and the reaction time is 18-22 hours; The molar ratio of the second product, the auxiliary agent, the stabilizer, the third solvent, the acryloyl chloride or the methacryloyl chloride, and the third catalyst is 35:(144-187.2):(1.5-2.0):(1714-2026):(70-84):(3.0-4.0). The reaction temperature of the second product and the acryloyl chloride or the methacryloyl chloride is 0°C or ice bath condition, and the reaction is carried out under a protective atmosphere of nitrogen or inert gas.

6. The nanoimprint paste according to claim 1 or 2, wherein The acrylate prepolymer is at least one of 9537 of Kunshan Kast, 6151, DR-U084, DR-U299, DR-U379, DR-U384, DR-U388, 6371, 6372 of Changxing Material, HR6100, HR6200, PS4500, PS4040, PS610 of Meiyuan, CN2254NS, CN2303, CN293, CN750, CN790, CN8008NS, CN8201NS, CN983NS, CN996NS of Sartomer. The modified acrylate prepolymer is at least one of CR91000, CR91093, CR90223, HU280 of Haohui New Material, L-6902X, L-6901, and L-6902 of Lanxess.

7. The nanoimprint resin according to claim 1 or 2, wherein The nanoparticle is a metal oxide nanoparticle, and / or the particle size of the nanoparticle ranges from 10 nm to 20 nm.

8. The nanoimprint resin according to claim 1 or 2, wherein The nanoparticle is a titanium oxide nanoparticle or a zirconium oxide nanoparticle.

9. The nanoimprint resin of claim 8, wherein The coupling agent is at least one of γ-(methacryloyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriethoxysilane, γ-(methacryloyloxy)propyltriethoxysilane, methacryloyloxymethyltriethoxysilane, 3-methacryloyloxypropyltris(methoxyethoxy)silane, methacryloyloxypropyltris(dimethylsiloxy)silane, γ-(acryloyloxy)propyltrimethoxysilane, γ-(acryloyloxy)propyltriethoxysilane, allyltris(trimethylsiloxy)silane, 1,3-bis(3-methacryloyloxypropyl)tetra(trimethylsiloxy)disiloxane, N-(3-acryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane.

10. The nanoimprint resin according to claim 1 or 2, wherein The photoinitiator is selected from the group consisting of Darocur® 1173, Darocur® 1176, Irgacure® 184, TPO, TPO-L, Irgacure® 127, Irgacure® 369, ITX, BDK, Irgacure® 819, Irgacure® 754, Irgacure® 380, BMF, ANTHRACURE TM UVS-1331, ANTHRACURE TM UVS-1101, Easepi 6992, Easepi 1176, Easepi 250.

11. The nanoimprint resin according to claim 1 or 2, wherein The diluent is at least one of propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, ethyl acetate, N,N-dimethylformamide, methyl ethyl ketone, dimethyl sulfoxide, butyl acetate.

12. The nanoimprint resin according to claim 1 or 2, wherein ​ 13. A method for producing the nanoimprint glue according to any one of claims 1 to 12, characterized by, The method comprises the following steps: adding diluent into a container, adding optical monomer, acrylate prepolymer and modified acrylate prepolymer in a protective gas, stirring and mixing to form a uniform first solution; Stirring the first solution, adding coupling agent and photoinitiator, and continuously stirring to form a uniform second solution; After adding nanoparticles in the second solution and continuously stirring to be uniform, standing; Nanometer imprinting glue is obtained by pressure filtration packaging.

14. The method for preparing a nanoimprint glue according to claim 13, wherein During the reaction, the temperature in the container is 21-25 DEG C; the pressure filtration packaging adopts 0.22 mu m organic filter membrane.

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