Nanoimprint glue and preparation method thereof

Abstract

The application discloses a nano-imprint glue and a preparation method thereof, wherein the nano-imprint glue is prepared from the following raw materials: an optical monomer, an acrylate prepolymer, a reactive diluent, nanoparticles, a photoinitiator, a coupling agent and an organic solvent; the general structure formula of the optical monomer is wherein R1 is a substituted or unsubstituted aromatic group or a substituted or unsubstituted naphthyl group, 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. The nano-imprint glue can make the refractive index of the cured nano-imprint glue reach 1.7-1.8 through the synergistic effect of the optical monomer and the nanoparticles. The optical monomer can participate in curing together with other components to form macromolecules or crosslinking networks, and the cured glue can realize high structural strength, is beneficial to nano-imprint demolding, and is not prone to residual glue during demolding; and the glue is not prone to breakage during reliability testing.

Description

Technical Field

[0001] This invention relates to the field of nanoimprint technology, and more particularly to nanoimprint adhesives and their preparation methods. Background Technology

[0002] Nano-imprint lithography (NIL) is a technique that uses nanoimprint lithography adhesives to transfer micro- and nano-structures from a template onto a material to be processed. During the imprinting process, the nanoimprint lithography adhesive acts as a "medium" for pattern transfer. The micro- and nano-structures on the template interact with the nanoimprint lithography adhesive, thus replicating the micro- and nano-structures proportionally onto the adhesive. Nanoimprint lithography mainly includes thermal imprinting, ultraviolet (UV) imprinting, and soft imprinting. UV imprinting primarily uses UV-curable UV nanoimprint lithography adhesives. After the colloid interacts with the template at room temperature, it is cured by UV light to form an optical material with micro- and nano-structures.

[0003] While UV nanoimprinting does not require the high temperature and pressure conditions of thermal imprinting, it suffers from incomplete curing, affecting the mechanical properties of the micro / nano structures. This can lead to breakage and residual adhesive during demolding, hindering template reuse. Furthermore, reliability testing of UV-cured optical materials reveals poor high-temperature resistance; micro / nano structures may collapse after high-temperature baking or reliability testing, resulting in varying degrees of damage or detachment. Additionally, while nanoimprinting adhesives typically incorporate a higher proportion of inorganic particles to increase refractive index, this reduces fluidity, hindering interaction with the template's micro / nano structures during imprinting. This can cause dimensional deformation or significant parameter variations, impacting optical performance. It also affects the coatability of the nanoimprinting adhesive, leading to poor coating results and reduced production yield. Summary of the Invention

[0004] In view of this, the present invention proposes a nanoimprint adhesive and its preparation method, aiming to solve at least one of the aforementioned technical problems, improve the structural strength of the adhesive after curing, and have a high refractive index and easy coating properties.

[0005] The nanoimprinting adhesive proposed in the first aspect of this invention is prepared from the following raw materials: optical monomers, acrylate prepolymers, reactive diluents, nanoparticles, photoinitiators, coupling agents, and organic solvents, wherein the general structural formula of the optical monomers is as follows:

[0006] Wherein, R1 is a substituted or unsubstituted aromatic group or a substituted or unsubstituted naphthyl group, R2 is methyl or hydrogen, R3 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.

[0007] As can be seen from the above technical solutions, the nanoimprint adhesive proposed in the first aspect of this invention uses an optical monomer with three acrylate groups. These acrylate groups have C=C double bonds, which are relatively active unsaturated bonds, allowing the optical monomer to effectively participate in curing with other components to form macromolecules or cross-linked networks. This results in a high structural strength in the cured adhesive, which is beneficial for nanoimprint demolding. Furthermore, the micro-nano structure remains intact during demolding, and there is little residue. During reliability testing, the micro-nano structure on the cured adhesive also remains relatively intact. The difference in refractive index between the nanoparticles and the optical monomer in this application is greater than 0.4. Because the optical monomer used in this application has a high refractive index, other components that need to increase the refractive index, such as nanoparticles, can be relatively reduced in the prepared nanoimprint adhesive. This helps to reduce the preparation cost of the nanoimprint adhesive and minimizes the problems of poor flowability and coating properties caused by adding too many nanoparticles, thereby improving the imprinting accuracy during the nanoimprinting process. The preparation method of the nanoimprint adhesive of the aforementioned embodiment proposed in the second aspect of the present invention includes the following steps: adding an organic solvent to a container, adding an optical monomer, an acrylate prepolymer and a reactive diluent 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 to the second solution and continuing to stir until uniform, then allowing it to stand; and encapsulating by pressure filtration to obtain the nanoimprint adhesive.

[0008] As can be seen from the above technical solutions, the preparation method of the nanoimprint adhesive proposed in the second aspect of the present invention ensures that the components are fully mixed, do not easily agglomerate, and can form a relatively uniform coating adhesive, which is convenient for subsequent coating and imprinting. The prepared nanoimprint adhesive is easy to use and ensures that it has the aforementioned properties of the nanoimprint adhesive.

[0009] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and do not limit the disclosure of the embodiments of the present invention. Attached Figure Description

[0010] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the following description of the embodiments will be briefly introduced. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0011] Figure 1 This is a schematic flowchart of a method for preparing optical monomers according to some embodiments of the present invention;

[0012] Figure 2This is a schematic flowchart of the preparation method of nanoimprint adhesive proposed in some embodiments of the present invention. Detailed Implementation

[0013] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention.

[0014] In related technologies, the UV nanoimprint adhesive used has a relatively weak structural strength. During the UV nanoimprinting process, it is easy to stick to the template, which makes the UV nanoimprint adhesive with micro-nano structure easily damaged after imprinting, thus reducing the production yield. At the same time, the residual adhesive adhering to the mold contaminates the template and makes it inconvenient for the template to be used again.

[0015] In related technologies, the refractive index of the monomer main component of the ultraviolet nanoimprint adhesive is not high. It is necessary to add more inorganic particles to increase the refractive index of the entire adhesive. The high content of inorganic particles reduces the fluidity of the adhesive, making it difficult to coat. It also prevents the adhesive from interacting well with the micro-nano structure of the template during the imprinting process, thus making it impossible to produce high-performance optical materials with micro-nano structures.

[0016] In view of this, the present invention proposes a nano-imprinting adhesive, which has a high refractive index after curing, is easy to apply and use, has high structural strength, facilitates imprinting and demolding, and greatly reduces the probability of residual adhesive on the template.

[0017] Where there is no conflict, the following embodiments and features can be combined with each other.

[0018] The nanoimprint adhesive of this application will now be described.

[0019] According to the present invention, a nanoimprinting adhesive is prepared from the following raw materials: optical monomers, acrylate prepolymers, reactive diluents, nanoparticles, photoinitiators, coupling agents, and organic solvents. The general structural formula of the optical monomers is as follows:

[0020] Wherein, R1 is a substituted or unsubstituted aromatic group or a substituted or unsubstituted naphthyl group, R2 is methyl or hydrogen, R3 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.

[0021] As can be seen from the above, the nanoimprint adhesive proposed in this invention, by using an optical monomer with a triazine structure as the central structure and three branches, gives the optical monomer of this application a certain rigidity, a certain steric hindrance, and a certain toughness, thereby improving the processability of the optical monomer and its compounding effect with other components.

[0022] Furthermore, the high refractive index groups, such as triazine groups, unsaturated aromatic groups, sulfur atoms, and (meth)acrylate groups, specifically the triazine group, have a high electron density and a highly delocalized electron cloud within the ring, resulting in high molecular polarizability and thus a high refractive index. The nitrogen atom in the triazine group has strong electron-withdrawing properties, causing uneven distribution of the electron cloud within the molecule and enhancing the molecule's ability to refract light, thereby contributing to an increase in the refractive index of the optical monomer. Unsaturated aromatic groups have a conjugation effect, exhibiting high molar refractive index and low molar volume, thus increasing the refractive index of the optical monomer. Sulfur atoms can achieve high polarizability and therefore possess a high refractive index. (Meth)acrylate groups have high refractive index and low volume shrinkage properties. Therefore, the optical monomer of this application has a high refractive index, measured to be 1.67–1.7. Nanoparticles with a refractive index difference greater than 0.4 from the optical monomer have a refractive index higher than 2.07. The raw materials containing these two components provide a certain material basis for the overall high refractive index of the nanoimprint adhesive.

[0023] Furthermore, since each mole of optical monomer in this application contains three moles of (meth)acrylate groups, and the (meth)acrylate groups themselves have C=C double bonds, these unsaturated bonds are relatively active and have high reactivity. The optical monomer has three or more functional groups, which can effectively participate in curing with other components to form macromolecules or cross-linked networks. This allows the cured colloid to achieve high structural strength, which is beneficial for nanoimprint demolding. Moreover, the micro-nano structure remains intact during demolding and is not prone to leaving colloid residue. During reliability testing, the micro-nano structure on the cured colloid also remains relatively intact.

[0024] Since the refractive index of the optical monomer with the above-mentioned structure in this application is 1.67 to 1.7, and the difference between the refractive index of the nanoparticles and the optical monomer is greater than 0.4, the refractive index of the nanoparticles in this application is at least 2.07. Both the optical monomer and the nanoparticles have high refractive indices, so this application does not need to add too many nanoparticles to achieve a refractive index of 1.7 to 1.8 after curing. Since only a certain amount of nanoparticles are added, the refractive index and flowability of the nanoimprint adhesive are taken into account, so that the entire nanoimprint adhesive can maintain good flowability and coating properties, resulting in good coating effect of the adhesive and easy filling into the mold for imprinting during the imprinting process. In particular, it can fully fill the micro-nano structure of the mold, so that the nanoimprint adhesive has a complete micro-nano structure, improving the accuracy of imprinting and improving the production yield of nanoimprint adhesive with micro-nano structure.

[0025] In this application, the addition of acrylate prepolymer serves as a framework, facilitating the formation of a cross-linked network on the framework by other components. This provides the necessary mechanical strength and improves thermal stability for the cured nanoimprint adhesive. Reactive diluents enhance the abrasion resistance, leveling properties, substrate adhesion, and environmental friendliness of the nanoimprint adhesive, with different properties improved depending on the specific type added. The addition of photoinitiators absorbs ultraviolet light to generate free radicals or cations, triggering the curing of acrylate monomers and prepolymers. This facilitates photocuring under ultraviolet light, improving curing efficiency. The addition of coupling agents improves the adhesion of the nanoimprint adhesive to the substrate, effectively reducing the probability of the cured nanoimprint adhesive being peeled off during demolding. The addition of organic solvents ensures uniform dispersion, appropriate concentration, and suitable viscosity of all components in the colloidal system, facilitating coating and filling into the micro / nano structures within the template during the imprinting process.

[0026] Understandably, compared to related technologies where UV nanoimprinting adhesives tend to adhere to the template during UV nanoimprinting, leading to easy damage to the micro-nano structured adhesive and reduced production yield, this invention offers a superior solution. Furthermore, residual adhesive on the mold contaminates the template, hindering its reuse. The nanoimprinting adhesive of this invention boasts high structural strength, ensuring the formed micro-nano structure remains intact during demolding and maintaining a certain production yield. It also reduces residual adhesive on the mold, facilitating mold reuse.

[0027] Compared to related technologies where the main monomer component of the UV nanoimprint adhesive has a low refractive index, requiring the addition of a large number of inorganic particles to increase the overall refractive index of the adhesive, the high content of inorganic particles reduces the fluidity of the adhesive, making it difficult to coat and hindering its interaction with the micro-nano structure of the template during the imprinting process, thus preventing the fabrication of high-performance optical materials with micro-nano structures. The nanoimprint adhesive of this invention has a high refractive index, and the amount of inorganic particles added can be reduced. The adhesive is easy to coat and can easily fill the micro-nano structure of the entire mold during the imprinting process.

[0028] In some embodiments of this application, the weight parts of each component in the raw material of the nanoimprint adhesive are as follows:

[0029] Component 1: 20-30 parts of optical monomer, for example, 20, 21, 24, 25, 27, 29, and 30 parts. Component 2: 3-5 parts of acrylate prepolymer, for example, 3, 3.5, 4, 4.5, 4.8, and 5 parts. Component 3: 5-10 parts of reactive diluent, for example, 5, 6, 7, 8, 9, and 10 parts.

[0030] Fourth component: 10 to 15 parts of nanoparticles, for example, 10, 11, 12, 13, 14, and 15 parts, etc.

[0031] Fifth component: 1 to 5 parts of photoinitiator, for example, 1.0, 1.6, 2.0, 2.2, 2.7, 3.0, 3.2, 3.3, 3.5, 3.6, 3.8, 3.9, 4.0, 4.2, 4.5, 4.6 and 5.0 parts, etc.

[0032] Component 6: 1 to 5 parts of coupling agent, 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 and 5 parts, etc.

[0033] Component 7: 30 to 60 parts of organic solvent, for example, 30, 35, 40, 42, 47, 50, 52, 55 and 60 parts, etc.

[0034] Because nanoimprinting adhesives require a high refractive index, and the main components contributing to this high refractive index are optical monomers and nanoparticles, the content of these two components needs to be relatively high. Furthermore, to maintain the fluidity of the nanoimprinting adhesive, the amount of nanoparticles added cannot exceed 15 parts; for example, in some specific embodiments, the amount of nanoparticles added is 13 parts. Since organic solvents are used to improve the viscosity and fluidity of the entire colloidal system, their usage is also relatively high. Because acrylate prepolymers and reactive diluents play a role in the curing framework of the nanoimprinting adhesive, as well as its cured properties such as abrasion resistance, leveling, and adhesion to the substrate, their usage needs to be appropriate. Photoinitiators and coupling agents mainly play an auxiliary role, so only a small amount is needed.

[0035] In some specific embodiments, by weight, the raw materials in the nanoimprint adhesive include 20 parts of optical monomer, 8 parts of acrylate prepolymer, 5 parts of reactive diluent, 15 parts of nanoparticles, 1 part of photoinitiator, 1 part of coupling agent, and 50 parts of organic solvent.

[0036] In some specific embodiments, by weight, the raw materials in the nanoimprint adhesive contain 22 parts of optical monomer, 5 parts of acrylate prepolymer, 3 parts of reactive diluent, 10 parts of nanoparticles, 4 parts of photoinitiator, 5 parts of coupling agent, and 51 parts of organic solvent.

[0037] In some specific embodiments, by weight, the raw materials in the nanoimprint adhesive contain 23 parts of optical monomer, 10 parts of acrylate prepolymer, 4 parts of reactive diluent, 12 parts of nanoparticles, 5 parts of photoinitiator, 4 parts of coupling agent, and 42 parts of organic solvent.

[0038] In some specific embodiments, by weight, the raw materials in the nanoimprint adhesive contain 24 parts of optical monomer, 6 parts of acrylate prepolymer, 3 parts of reactive diluent, 13 parts of nanoparticles, 3.3 parts of photoinitiator, 3.7 parts of coupling agent, and 47 parts of organic solvent.

[0039] In some specific embodiments, by weight, the raw materials in the nanoimprint adhesive contain 30 parts of optical monomer, 10 parts of acrylate prepolymer, 5 parts of reactive diluent, 15 parts of nanoparticles, 5 parts of photoinitiator, 5 parts of coupling agent, and 30 parts of organic solvent.

[0040] The amount of each component added can also be any other number of parts within the range of addition, which will not be elaborated here.

[0041] The structure and preparation method of the first component of the nanoimprint adhesive of this application are described below.

[0042] In some embodiments of this application, the optical monomer comprises monomers with the following four structural formulas:

[0043] First optical unit, Second optical unit,

[0044] Third optical unit Fourth optical unit,

[0045] In the first optical monomer, when R1 is a thiophene group, R2 is hydrogen, and R3 is hydrogen, the side chains of this structure contain acrylate groups, thiophene groups, and sulfur atoms.

[0046] In the second optical monomer, when R1 is phenyl, R2 is hydrogen, and R3 is hydrogen, the side chains of this structure contain phenyl, sulfur atoms, and acrylate groups.

[0047] In the third optical monomer, when R1 is methylthiophenyl, R2 is hydrogen, and R3 is hydrogen, the side chains of this structure contain methylthiophenyl, sulfur atoms, and acrylate groups.

[0048] In the fourth optical monomer, when R1 is naphthyl, R2 is hydrogen, and R3 is hydrogen, the side chains of this structure contain naphthyl, sulfur atoms, and acrylate groups.

[0049] Four optical monomers were dispersed in a solvent, such as tetrachloroethane, and then spin-coated onto a silicon wafer. After baking, their refractive indices were measured using an ellipsometer. The refractive indices of the first optical monomer were found to be 1.675, the second optical monomer 1.672, the third optical monomer 1.684, and the fourth optical monomer 1.698, respectively. The refractive indices of the optical monomers in this application are all not less than 1.67, with the third and fourth optical monomers having even higher refractive indices of 1.684 and 1.698, respectively. Furthermore, each optical monomer possesses three functionalities.

[0050] The optical monomers of this application are not limited to the four specific optical monomers mentioned above. In other embodiments, when R1 and R3 have the same groups as the four monomers mentioned above, and R2 is methyl, optical monomers with methacrylate groups in their side chains are obtained. These optical monomers are equivalent in properties to the aforementioned optical monomers with acrylate groups in their side chains, and those skilled in the art will understand that these optical monomers also fall within the scope of protection of this application. In still other embodiments, the aforementioned R1 is not limited to thiophene, phenyl, methylthiophenyl, and naphthyl. R1 can also be other groups, such as benzonitrile, benzaldehyde, acetophenone, methyl 2-naphthyl ester, etc., as long as R1 is within the scope of the definition of substituted or unsubstituted aromatic groups or substituted or unsubstituted naphthyl groups in this application. For example, when R1 and R2 have the same groups as the four monomers mentioned above, and R3 is methyl, optical monomers with more methyl chains in their side chains can be obtained. These optical monomers are all within the scope of protection of this application.

[0051] According to the present invention, a method for preparing an optical monomer is provided, such as... Figure 1 As shown, the process includes the following steps: step S110, step S120, and step S130:

[0052] Step S110: Mix compound P1, the first catalyst, and the first solvent thoroughly, and add epichlorohydrin or methyl epichlorohydrin to react and generate the first product. Compound P1 is a compound containing a thiol and an aromatic group, or compound P1 is a compound containing a thiol and a naphthyl group; that is, compound P1 is a compound containing R1 and a thiol group. The reaction equation can be represented as follows:

[0053] In this step, a nucleophilic substitution reaction mainly occurs. Compound P1, under the action of a first catalyst, attacks the terminal carbon on the epoxy ring of epichlorohydrin / methylepoxychlorohydrin, resulting in ring-opening to generate the first product. It should be noted that the reaction of compound P1 in this application is mainly described in terms of a compound containing a one-mole equivalent of a thiol group.

[0054] In this step, the structure of the first product varies depending on the types of R1 and R3. The types of R1 and R3 are described above and will not be repeated here.

[0055] In some specific embodiments, when R1 is thiophene and R3 is hydrogen, compound P1 is 2-mercaptothiophene, and the first product is 1-(2-mercaptothiophene)-3-chloro-2-propanol.

[0056] In some specific embodiments, when R1 is phenyl and R3 is hydrogen, compound P1 is thiophenol and the first product is 1-benzylthiol-3-chloro-2-propanol.

[0057] In some specific embodiments, when R1 is methylthiophenyl and R3 is hydrogen, compound P1 is 4-methylthiophenylthiophenol and the first product is 1-(4-methylthiophenylthiool)-3-chloro-2-propanol.

[0058] In some specific embodiments, when R1 is naphthyl and R3 is hydrogen, compound P1 is 2-mercaptonaphthalene and the first product is 1-(2-naphthyl thioether)-3-chloro-2-propanol.

[0059] Step S120: Mix 2,4,6-trimercapto-1,3,5-triazine, the second catalyst, and the second solvent evenly, and add the first product to carry out a catalytic reaction to generate the second product, wherein the molar ratio of the first product to 2,4,6-trimercapto-1,3,5-triazine is (3-4):1.

[0060]

[0061] In this step, under the action of a second catalyst, the three-molecular-weight thiol groups of 2,4,6-trimercapto-1,3,5-triazine attack an equivalent amount of chlorine atoms in the first product, thereby generating a second product with a three-branched structure.

[0062] In this step, depending on the structure of the first product, the structure of the second product obtained after the reaction in step S120 will also be different. It should be noted that this application mainly describes the reaction of compounds in which the first product contains an equivalent amount of chlorine.

[0063] In some specific embodiments, when the first product is 1-(2-mercaptothiophene)-3-chloro-2-propanol, the second product is 2,4,6-tris(1-(2-thiophene sulfide)-2-propanol)-1,3,5-triazine sulfide.

[0064] In some specific embodiments, when the first product is 1-phenylthiol-3-chloro-2-propanol, the second product is 2,4,6-tris(1-phenylthion-2-propanol)-1,3,5-triazine thioether.

[0065] In some specific embodiments, when the first product is 1-(4-methylthiophenylthiol)-3-chloro-2-propanol, the second product is 2,4,6-tris(1-(4-methylthiophenylthiol)-2-propanol)-1,3,5-triazine sulfide.

[0066] In some specific embodiments, when the first product is 1-(2-naphthyl thion)-3-chloro-2-propanol, the second product is 2,4,6-tris(1-(2-naphthyl thion)-2-propanol)-1,3,5-triazine thion.

[0067] It should be noted that the molar ratio of the first product to 2,4,6-trimercapto-1,3,5-triazine is (3-4):1, which can be 3:1, 3.1:1, 3.2:1, 3.5:1, 3.7:1 or 4:1, etc., so that all three moles of thiol groups can be fully reacted to generate the second product with three branches.

[0068] Step S130: Add the second product, auxiliaries, and stabilizers to the third solvent and mix them evenly; cool the solution, and under gas protection, add acryloyl chloride or methacryloyl chloride to react with the third catalyst to generate the optical monomer of the above embodiment, wherein the molar ratio of acryloyl chloride or methacryloyl chloride to the second product is (3-4):1.

[0069]

[0070] In this step, the acylation reaction mainly occurs, in which the second product having an alcoholic hydroxyl group attacks the carbonyl carbon of acryloyl chloride / methacryloyl chloride in the presence of an auxiliary agent, a third catalyst, and a stabilizer, and forms an acrylate group on the side chain after the elimination of chlorine. It should be noted that this application mainly describes the reaction of compounds in which the second product has a three-molecular-equivalent hydroxyl group.

[0071] In this step, depending on the structure of the second product and the different values ​​of R2, the structure of the third product obtained after the reaction in step S130 will also be different. When R2 is hydrogen, the side chain of the third product includes acrylate groups; when R2 is methyl, the side chain of the third product includes methacrylate groups.

[0072] In some specific embodiments, when the second product is 2,4,6-tris(1-(2-thiophene sulfide)-2-propanol)-1,3,5-triazine sulfide and the reactant is acryloyl chloride, the third product is 2,4,6-tris(1-(2-thiophene sulfide)-2-propylacrylate)-1,3,5-triazine sulfide, which is the aforementioned first optical monomer.

[0073] In some specific embodiments, when the second product is 2,4,6-tris(1-phenyl sulfide-2-propanol)-1,3,5-triazine sulfide and the reactant is acryloyl chloride, the third product is 2,4,6-tris(1-phenyl sulfide-2-propyl acrylate)-1,3,5-triazine sulfide, which is the aforementioned second optical monomer.

[0074] In some specific embodiments, when the second product is 2,4,6-tris(1-(4-methylthiophenylthiol)-2-propanol)-1,3,5-triazine sulfide and the reactant is acryloyl chloride, the third product is 2,4,6-tris(1-(4-methylthiophenylthiol)-2-propylacrylate)-1,3,5-triazine sulfide.

[0075] In some specific embodiments, when the second product is 2,4,6-tris(1-(2-naphthyl thion)-2-propanol)-1,3,5-triazine thion and the reactant is acryloyl chloride, the third product is 2,4,6-tris(1-(2-naphthyl thion)-2-propylacrylate)-1,3,5-triazine thion.

[0076] It should also be noted that the molar ratio of acryloyl chloride or methacryloyl chloride to the second product is (3-4):1, for example, it can be 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, etc., so that all three moles of alcohol hydroxyl groups can be fully reacted to generate a third product with three branches, which is the structure with the aforementioned general formula of this application:

[0077] Optical unit.

[0078] As can be seen from the above, the method for preparing the optical monomer proposed in this invention obtains the aforementioned optical monomer through a three-step main reaction, enabling the optical monomer to be obtained through relevant synthesis and to be manufactured according to the required amount. Each reaction step can achieve high reaction efficiency under the action of a catalyst. The beneficial effects of the optical monomer can be referred to above and will not be repeated here.

[0079] In some embodiments of this 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), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD). These types of catalysts can promote nucleophilic reactions. Specifically, in step S110, a proton can be abstracted from the thiol group to generate a highly reactive thiol anion, which enhances the nucleophilicity. The thiol anion selectively attacks the less sterically hindered terminal carbon of the epoxy group in epichlorohydrin / methyl epichlorohydrin to generate a chloroalcohol intermediate (the first product). Specifically, in step S120, a proton can be abstracted from three thiol groups to generate a highly reactive dithiol anion, which enhances the nucleophilicity. The dithiol anion attacks the carbon atom of the halide to generate a thioether bond. DBU is inexpensive and readily available, and can perform mild ring-opening reactions on epoxy substrates.

[0080] In some embodiments of this 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 compound P1, the first catalyst, and epichlorohydrin (or methyl epichlorohydrin), so that all three can be fully mixed and reacted in the reaction system, which is beneficial for a more complete reaction and promotes efficient reaction. Similarly, the second solvent needs to be able to fully dissolve the first product, 2,4,6-trimercapto-1,3,5-triazine, and the second catalyst, so that all three can be fully mixed and reacted in the reaction system, which is beneficial for a more complete reaction in step S120 and promotes efficient reaction.

[0081] In some embodiments of this application, the additive is selected from triethylamine (TEA) or 1,8-diazabicycloundec-7-ene (DBU). The additive here can enhance the deprotonation activity of the alcohol hydroxyl group of the second product, thereby facilitating the attack on acryloyl chloride (or methacryloyl chloride) to generate a tetrahedral intermediate, and then release chlorine to form the optical monomer of this application.

[0082] In some embodiments of this application, the stabilizer is selected from at least one of butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), and tert-butylhydroquinone (TBHQ). These stabilizers effectively prevent the self-polymerization of acryloyl chloride, keeping it stable during the reaction, reducing side reactions, and ensuring the stability of the acrylate groups generated after the reaction of propyl acryloyl chloride, making them less susceptible to oxidation. This guarantees the stability of the nanoimprint adhesive made using optical monomers as a component. In particular, BHT is readily available, allowing for controllable reaction costs.

[0083] In some embodiments of this application, the third solvent is selected from dichloromethane or tetrahydrofuran. The third solvent can make the second product, auxiliaries, stabilizers, acryloyl chloride (or methacryloyl chloride) and the third catalyst mix evenly, making the reaction system more homogeneous, which is beneficial to improving the reaction efficiency and making the reaction more complete.

[0084] In some embodiments of this application, the third catalyst is 4-dimethylaminopyridine (DMAP). DMAP enables the reaction to proceed rapidly under mild conditions, avoids side reactions caused by high temperatures, and improves the purity of the reaction.

[0085] In some embodiments of this application, the molar ratio of compound P1, the first catalyst, the first solvent, and epichlorohydrin is 100:(70-90):(1317-1505):(100-120), for example, specific ratios are 100:70:1317:100, 100:80:1410:110, or 100:90:1505:120. Similarly, the molar ratio of compound P1, the first catalyst, the first solvent, and methyl epichlorohydrin is 100:(70-90):(1317-1505):(100-120), for example, specific ratios are 100:70:1317:100, 100:80:1410:110, or 100:90:1505:120. This allows the reaction in step S110 to be more complete and faster, the nucleophilic substitution reaction to be more thorough, and the byproducts to be reduced.

[0086] In some embodiments of this application, the reaction temperature of compound P1 with epichlorohydrin or methyl epichlorohydrin is room temperature, and the reaction time is 14h to 18h, for example, 14h, 15h, 16h, 17h, or 18h, etc., without limitation. Nucleophilic reactions occurring at room temperature can effectively reduce the generation of byproducts and decrease the decomposition of heat-sensitive compounds.

[0087] In some embodiments of this application, after the reaction generates the first product, a post-treatment step is included. Specifically, the post-treatment step involves removing volatiles under reduced pressure, then diluting the residue with dichloromethane (DCM), and washing sequentially with 1M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The mixed organic extract is 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 hexane as the eluent. The resulting colorless, low-viscosity liquid is the liquid containing the first product of this application, and the purity of the first product can be greatly improved.

[0088] In some embodiments of this application, the molar ratio of 2,4,6-trimercapto-1,3,5-triazine, the second catalyst, the second solvent, and the first product is 50:(50-55):(847-1035):(150-200), for example, 50:53.5:941:150, 50:53.5:941:160, 50:53.5:941:170, 50:50:847:150, 50:55:1035:200, etc. This allows the nucleophilic reaction in step S120 to be more complete and faster, the nucleophilic substitution reaction to be more thorough, byproducts to be reduced, and a dithiolated product to be generated.

[0089] In some embodiments of this application, the reaction temperature of 2,4,6-trimercapto-1,3,5-triazine with the first product is room temperature, and the reaction time is 18h to 22h, for example, 18h, 19h, 20h, 21h, or 22h, etc., which are not limited here. Nucleophilic reactions occurring at room temperature can effectively reduce the generation of byproducts and reduce the decomposition of heat-sensitive compounds.

[0090] In some embodiments of this application, after the first product is added and catalytically reacted to generate the second product, a post-processing step is performed. This post-processing step includes: removing volatiles under reduced pressure, then diluting the residue with DCM (dichloromethane), and washing sequentially with 1M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The mixed organic extract is dried on 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 hexane as the eluent, ultimately yielding a pale yellow viscous liquid, which is the liquid containing the second product of this application. The purity of the second product can be greatly improved.

[0091] In some embodiments of this application, the molar ratio of the second product, auxiliaries, stabilizers, third solvent, acryloyl chloride, and third catalyst is 35:(200-300):(2.5-2.8):(1714-2026):(105-140):(5.0-6.0), for example, 35:250:2.65:1870:116:5.3, 35:250:2.5:1870:105:3.0, 35:250:2.65:1870:120:5.5, 35:280:2.75:1714:130:5.8, and 35:300:2.8:2026:140:6.0. Alternatively, the molar ratio of the second product, auxiliaries, stabilizers, third solvent, methacrylamide chloride, and third catalyst can be 35:(200–300):(2.5–2.8):(1714–2026):(105–140):(5.0–6.0), for example, 35:250:2.65:1870:116:5.3, 35:250:2.5:1870:105:3.0, 35:250:2.65:1870:120:5.5, 35:280:2.75:1714:130:5.8, or 35:300:2.8:2026:140:6.0. This allows the acylation reaction in step S130 to be more complete and faster, reduces byproducts, and generates acrylate groups with a molecular weight of two.

[0092] In some embodiments of this application, the reaction temperature of the second product with acryloyl chloride or methacryloyl chloride is 0°C or under ice bath conditions, and the reaction is carried out under a protective atmosphere with nitrogen or inert gas, which can effectively prevent the decomposition of acryloyl chloride (or methacryloyl chloride) and make the reaction less likely to generate byproducts.

[0093] In some embodiments, after generating the optical monomer, a post-processing step is further included. Specifically, the post-processing step involves removing volatile substances under reduced pressure, diluting the residue with 250 mL of dichloromethane, and washing sequentially with 1 mol / L hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The mixed organic extract is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product is purified by silica gel column chromatography using 20% ​​ethyl acetate (hexane) as eluent, ultimately yielding the target compound as a colorless to slightly yellow viscous liquid. Therefore, the post-processing step can significantly improve the purity of the optical monomer of this application.

[0094] In some specific embodiments, reference is made to Figure 1 The specific operations for preparing the aforementioned first optical monomer in steps S110 to S130 are as follows:

[0095] Compound P1, 2-mercaptothiophene (100 mmol), was mixed with 12 mL of DBU (80 mmol) in 150 mL of toluene (1.41 mol) and added to a 250 mL round-bottom flask equipped with a magnetic stir bar. The mixture was stirred for 30 minutes. Subsequently, 8.6 mL of epichlorohydrin (110 mmol) was slowly added dropwise. The reaction vessel was stirred at room temperature for 16 hours. Afterward, volatiles were removed under reduced pressure, and the residue was diluted with DCM and washed successively with 1 M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The mixed organic extract was 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 hexane as eluent, ultimately yielding a colorless, low-viscosity liquid containing 1-(2-mercaptothiophene)-3-chloro-2-propanol.

[0096] 50 mmol of 2,4,6-trimercapto-1,3,5-triazine was mixed with 8 mL of DBU (53.5 mmol) in 100 mL of toluene (941 mmol) and added to a 250 mL round-bottom flask equipped with a magnetic stir bar. The mixture was stirred for 30 minutes. Subsequently, 13.5 mL of 1-(2-mercaptothiophene)-3-chloro-2-propanol (175 mmol) was slowly added dropwise. The reaction vessel was stirred at room temperature for 20 hours. Afterward, volatiles were removed under reduced pressure, and the residue was diluted with DCM and washed successively with 1 M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The mixed organic extract was 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 hexane as the eluent, ultimately yielding a pale yellow viscous liquid containing 2,4,6-tris(1-(2-thiophene thioether)-2-propanol)-1,3,5-triazine thioether.

[0097] 35 mmol of 2,4,6-tris(1-(2-thiophene thioether)-2-propanol)-1,3,5-triazine thioether, 250 mmol of triethylamine, and 2.65 mmol of butylated hydroxytoluene (BHT) were added to a 250 mL round-bottom flask equipped with a magnetic stir bar. The solution was diluted with 120 mL of dichloromethane and stirred for 30 minutes under argon protection. After cooling the solution to 0 °C, 116 mmol of acryloyl chloride was added dropwise under argon protection, followed by 5.3 mmol of 4-dimethylaminopyridine (DMAP). The reaction mixture was stirred at room temperature for 20 hours. Volatile substances were then removed under reduced pressure. The residue was diluted with 250 mL of dichloromethane and washed successively with 100 mL of 1 mol / L hydrochloric acid, 100 mL of distilled water, and 50 mL of brine. The mixed organic extract was 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 (hexane) as eluent, finally yielding the target compound as a colorless to slightly yellow viscous liquid, which is the first optical monomer of this application—2,4,6-tris(1-(2-thiophene thioether)-2-propylacrylate)-1,3,5-triazine thioether. The overall synthesis steps can be represented by the following chemical reaction equations:

[0098]

[0099] In some specific embodiments, the preparation of the aforementioned second optical monomer is carried out as follows: The preparation method is largely the same as that of the first optical monomer, except that compound P1 is changed from 2-mercaptothiophene to thiophene, resulting in changes to the first, second, and third products:

[0100] Compound P1, 100 mmol of thiophenol, was mixed with 12 mL of DBU (80 mmol) in 150 mL of toluene (1.41 mol) and added to a 250 mL round-bottom flask equipped with a magnetic stir bar. The mixture was stirred for 30 minutes. Subsequently, 8.6 mL of epichlorohydrin (110 mmol) was slowly added dropwise. The reaction vessel was stirred at room temperature for 16 hours. Afterward, the volatiles were removed under reduced pressure, and the residue was diluted with DCM and washed successively with 1 M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The mixed organic extract was 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 hexane as the eluent, ultimately yielding a colorless, low-viscosity liquid containing 1-benzylthiol-3-chloro-2-propanol.

[0101] 50 mmol of 2,4,6-trimercapto-1,3,5-triazine was mixed with 8 mL of DBU (53.5 mmol) in 100 mL of toluene (941 mmol) and added to a 250 mL round-bottom flask equipped with a magnetic stir bar. The mixture was stirred for 30 minutes. Subsequently, 12.3 mL of 1-benzylthiol-3-chloro-2-propanol (175 mmol) was slowly added dropwise. The reaction vessel was stirred at room temperature for 20 hours. Afterward, volatiles were removed under reduced pressure, and the residue was diluted with DCM and washed successively with 1 M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The mixed organic extract was 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 hexane as the eluent, ultimately yielding a pale yellow viscous liquid, which is 2,4,6-tris(1-phenyl sulfide-2-propanol)-1,3,5-triazine sulfide.

[0102] 35 mmol of 2,4,6-tris(1-phenylsulfide-2-propanol)-1,3,5-triazine sulfide, 250 mmol of triethylamine, and 2.65 mmol of butylated hydroxytoluene (BHT) were added to a 250 mL round-bottom flask equipped with a magnetic stir bar. The solution was diluted with 120 mL (1870 mmol) of dichloromethane and stirred for 30 minutes under argon protection. After cooling the solution to 0 °C, 116 mmol of acryloyl chloride was added dropwise under argon protection, followed by 5.3 mmol of 4-dimethylaminopyridine (DMAP). The reaction mixture was stirred at room temperature for 20 hours. Volatile substances were then removed under reduced pressure. The residue was diluted with 250 mL of dichloromethane and washed successively with 100 mL of 1 mol / L hydrochloric acid, 100 mL of distilled water, and 50 mL of brine. The mixed organic extract was 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 (hexane) as eluent, finally yielding the target compound as a colorless to slightly yellow viscous liquid, thus obtaining the second optical monomer of this application—2,4,6-tris(1-phenyl sulfide-2-propylacrylate)-1,3,5-triazine sulfide. The overall synthesis steps can be represented by the following chemical reaction equations:

[0103]

[0104] In some specific embodiments, the preparation of the aforementioned third optical monomer is carried out as follows: the preparation method is roughly the same as that of the first optical monomer, except that compound P1 is changed from 2-mercaptothiophene to 4-methylthiophenethiophenol, and the first product, the second product and the third product are changed accordingly.

[0105] Compound P1 was selected. 100 mmol of 4-methylthiobenzylthiophenol was mixed with 12 mL of DBU (80 mmol) in 150 mL of toluene (1.41 mol) and added to a 250 mL round-bottom flask equipped with a magnetic stir bar. The mixture was stirred for 30 min. Subsequently, 8.6 mL of epichlorohydrin (110 mmol) was slowly added dropwise. The reaction vessel was stirred at room temperature for 16 h. Afterward, the volatiles were removed under reduced pressure, and the residue was diluted with DCM and washed successively with 1 M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The mixed organic extract was 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 hexane as the eluent, finally yielding a colorless, low-viscosity liquid containing 1-(4-methylthiobenzylthiophenol)-3-chloro-2-propanol.

[0106] 50 mmol of 2,4,6-trimercapto-1,3,5-triazine was mixed with 8 mL of DBU (53.5 mmol) in 100 mL of toluene (941 mmol) and added to a 250 mL round-bottom flask equipped with a magnetic stir bar. The mixture was stirred for 30 minutes. Subsequently, 15.8 mL of 1-(4-methylthiophenylthiol)-3-chloro-2-propanol (175 mmol) was slowly added dropwise. The reaction vessel was stirred at room temperature for 20 hours. Afterward, volatiles were removed under reduced pressure, and the residue was diluted with DCM and washed successively with 1 M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The mixed organic extract was 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 hexane as the eluent, ultimately yielding a pale yellow viscous liquid containing 2,4,6-tris(1-(4-methylthiophenylthiol)-2-propanol)-1,3,5-triazine thioether.

[0107] 35 mmol of 2,4,6-tris(1-(4-methylthiophenylthiol)-2-propanol)-1,3,5-triazine sulfide, 250 mmol of triethylamine, and 2.65 mmol of butylated hydroxytoluene (BHT) were added to a 250 mL round-bottom flask equipped with a magnetic stir bar. The solution was diluted with 120 mL of dichloromethane and stirred for 30 minutes under argon protection. After cooling the solution to 0 °C, 116 mmol of acryloyl chloride was added dropwise under argon protection, followed by 5.3 mmol of 4-dimethylaminopyridine (DMAP). The reaction mixture was stirred at room temperature for 20 hours. Volatile substances were then removed under reduced pressure. The residue was diluted with 250 mL of dichloromethane and washed successively with 100 mL of 1 mol / L hydrochloric acid, 100 mL of distilled water, and 50 mL of brine. The mixed organic extract was 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 (hexane) as eluent, finally yielding the target compound as a colorless to slightly yellow viscous liquid, which is the third optical monomer of this application—2,4,6-tris(1-(4-methylthiophenylthiol)-2-propylacrylate)-1,3,5-triazine sulfide. The overall synthesis steps can be represented by the following chemical reaction equations:

[0108]

[0109] In some specific embodiments, the preparation of the aforementioned fourth optical monomer is carried out as follows: the preparation method is roughly the same as that of the first optical monomer, except that compound P1 is changed from 2-mercaptothiophene to 2-mercaptonaphthalene, and the first product, the second product and the third product are changed accordingly.

[0110] Compound P1, 2-mercaptonaphthalene (100 mmol), was mixed with 12 mL of DBU (80 mmol) in 150 mL of toluene (1.41 mol) and added to a 250 mL round-bottom flask equipped with a magnetic stir bar. The mixture was stirred for 30 minutes. Subsequently, 10.7 mL of epichlorohydrin (110 mmol) was slowly added dropwise. The reaction vessel was stirred at room temperature for 16 hours. Afterward, volatiles were removed under reduced pressure, and the residue was diluted with DCM and washed successively with 1 M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The mixed organic extract was 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 hexane as eluent, ultimately yielding a colorless, low-viscosity liquid containing 1-(2-naphthylthion)-3-chloro-2-propanol.

[0111] 50 mmol of 2,4,6-trimercapto-1,3,5-triazine was mixed with 8 mL of DBU (53.5 mmol) in 100 mL of toluene (941 mmol) and added to a 250 mL round-bottom flask equipped with a magnetic stir bar. The mixture was stirred for 30 minutes. Subsequently, 19.7 mL of 1-(2-naphthylthion)-3-chloro-2-propanol (175 mmol) was slowly added dropwise. The reaction vessel was stirred at room temperature for 20 hours. Afterward, volatiles were removed under reduced pressure, and the residue was diluted with DCM and washed successively with 1 M hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The mixed organic extract was 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 hexane as the eluent, ultimately yielding a pale yellow viscous liquid, which was the second product 2,4,6-tris(1-(2-naphthylthion)-2-propanol)-1,3,5-triazine thioether.

[0112] The second product, 2,4,6-tris(1-(2-naphthylthion)-2-propanol)-1,3,5-triazine thioether (35 mmol), 36.5 mL of triethylamine (250 mmol), and 0.6 g of butylated hydroxytoluene (BHT) (2.65 mmol) were added to a 250 mL round-bottom flask equipped with a magnetic stir bar. The solution was diluted with 120 mL of dichloromethane and stirred for 30 minutes under argon protection. After cooling the solution to 0 °C, 9.5 mL of acryloyl chloride (116 mmol) was added dropwise under argon protection, followed by 0.6 g of 4-dimethylaminopyridine (DMAP) (5.3 mmol). The reaction mixture was stirred at room temperature for 20 hours. Volatile substances were then removed under reduced pressure. The residue was diluted with 250 mL of dichloromethane and washed successively with 1 mol / L hydrochloric acid (100 mL), distilled water (100 mL), and brine (50 mL). The mixed organic extract was 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 (hexane) as eluent, finally yielding the target compound as a colorless to slightly yellow viscous liquid, which is the fourth optical monomer of this application—2,4,6-tris(1-(2-naphthyl thione)-2-propylacrylate)-1,3,5-triazine thione. The overall synthesis steps can be represented by the following chemical reaction equations:

[0113]

[0114] Refractive index testing: The first, second, third, and fourth optical monomers, along with OPPEA (also known as o-phenylphenoxyethyl acrylate, CAS No. 91442-24-9), were dispersed in a solvent such as tetrachloroethane. The mixture was then spin-coated onto a silicon wafer, baked, and its refractive index was measured using an ellipsometer. The measured refractive indices were as follows: 1.675 for the first optical monomer, 1.672 for the second, 1.684 for the third, and 1.698 for the fourth; the refractive index of OPPEA was 1.575. The optical monomers of this application have refractive indices greater than 1.67, and the fourth optical monomer has a refractive index as high as 1.698. The refractive indices of each optical monomer are significantly improved compared to the comparative example OPPEA.

[0115] Glass transition temperature (Tg) testing. A TA Instruments Japan 2910 differential scanning calorimeter was used to test the first, second, third, and fourth optical monomers and OPPEA at a heating rate of 10℃ / min. The measured Tg values ​​were 112℃ for the first optical monomer, 116℃ for the second, 113℃ for the third, and 126℃ for the fourth; OPPEA was 35℃. The Tg values ​​of the optical monomers in the first component of this application are all greater than 112℃, exhibiting a higher glass transition temperature than OPPEA, indicating that the optical monomers of this application have better heat resistance and stability.

[0116] The types and sources of the second component of the nanoimprint adhesive of this application are described below.

[0117] In some embodiments of this application, the acrylate prepolymer is selected from Kunshan Castel 9537 (specifically purchased from Kunshan Castel Polymer Materials Co., Ltd.); Changxing Materials 6151, Changxing Materials DR-U084, Changxing Materials DR-U299, Changxing Materials DR-U379, ETERCURE DR-U384, Changxing Materials DR-U388, ETERCURE 6371, ETERCURE 6372 (specifically purchased from Changxing Materials Co., Ltd.); Meiyuan HR6100, Meiyuan HR6200, Meiyuan PS4500, Meiyuan PS4040, Meiyuan PS610 (specifically purchased from Meiyuan Special Chemicals Co., Ltd.); at least one of Sartoma CN2254NS, CN2303, CN293, CN750, CN790, CN8008NS, CN8201NS, CN983NS, CN996NS (specifically purchased from Sartoma).

[0118] For example, some of the above materials are UV-curable resins with excellent adhesion, which can be rapidly cured under UV light irradiation; others are multifunctional acrylates, which are convenient for rapid reaction in the photocuring reaction to form a skeleton structure.

[0119] The type and source of the third component of the nanoimprint adhesive of this application are described below.

[0120] In some embodiments of this application, the reactive diluent is selected from at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, 1,6-hexanediol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), propoxylated neopentyl glycol diacrylate (2PO-NPGDA), propoxylated glycerol triacrylate (GPTA), ethoxylated trimethylolpropane triacrylate (TMP3EOTA), cyclotrimethylolpropane methyl acetal acrylate (CTFA), 4-hydroxybutyl acrylate (4-HBA), dicyclopentadiene methacrylate (DPCMA), tetrahydrofuran methacrylate (THFMA), tetrahydrofuran acrylate (THFA), 4-tert-butylcyclohexyl acrylate (TBCHA), 4-acryloylmorpholine (ACMO), trimethylcyclohexyl acrylate (TMCHA), trimethylolpropane triacrylate, and pentaerythritol triacrylate.

[0121] For example, some of the above-mentioned reactive diluents can improve the wetting performance of the substrate when the nanoimprint adhesive is coated onto the substrate as a colloid, some can participate in the curing reaction and improve the wear resistance and service life of the nanoimprint adhesive after curing, and some are water-based systems that can reduce the volatilization of toxic compounds.

[0122] The type and source of the fourth component of the nanoimprint adhesive of this application are described below.

[0123] In some embodiments of this application, the nanoparticles are metal oxide nanoparticles. Metal oxide nanoparticles can improve the structural stability of the nanoimprint adhesive after imprinting, making it less prone to collapse during demolding and etching processes.

[0124] In some embodiments of this application, the particle size range of the nanoparticles is 10nm to 20nm, for example, values ​​of 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 18nm, and 20nm. Nanoparticles within the above range can not only disperse quickly in the solution, reducing entanglement between polymers, but also maintain the viscosity within a certain range, making the entire colloid easy to coat. Furthermore, the nanoparticles can be embedded in the cross-linking network of optical monomers, which can increase the hardness of the entire cured nanoimprint adhesive, which is beneficial to improving Young's modulus and preventing the collapse of the micro-nano structures on the nanoimprint adhesive during demolding.

[0125] In some embodiments of this application, the nanoparticles are metal oxide nanoparticles with a particle size range of 10 nm to 20 nm. The specific technical effects can be referred to the above description and will not be repeated here.

[0126] In a further embodiment, the nanoparticles are titanium dioxide nanoparticles or zirconium oxide nanoparticles. Titanium dioxide can absorb ultraviolet light, protecting the stability of the imprinting adhesive during ultraviolet curing. Titanium dioxide has a refractive index of 2.2–2.6, which can significantly increase the refractive index of the nanoimprinting adhesive even with a small amount added. Zirconia has high stability and a refractive index of 2.1–2.3, and can also rapidly increase the refractive index of the nanoimprinting adhesive even with a certain amount added.

[0127] In a specific embodiment, the nanoparticles are selected from PixClear Zirconia 10nm, PixClear Titania 20nm, and One or more of the core-shell 20nm process, without limitation.

[0128] The fifth component of the nanoimprint adhesive of this application is described below, along with its type and source.

[0129] In some embodiments of this application, the photoinitiator is selected from 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 chloride)diphenylphosphine oxide), TPO-L (i.e., ethyl 2,4,6-trimethylbenzoylphosphonate), photoinitiator 127 (i.e., 2-hydroxy-1-(4-(2-hydroxy-2-methylpropionylphenyl)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, and ANTHRACURE. TM UVS-1331, ANTHRACURE TM At least one of UVS-1101, Easepi 6992, Easepi 1176, and Easepi 250.

[0130] For example, the photoinitiators provided above can all adjust the curing rate and degree of curing of nanoimprint adhesives. By selecting different photoinitiators, nanoimprint adhesives can be cured under light of different wavelengths. For instance, (2,4,6-trimethylbenzoyl chloride)diphenylphosphine oxide (also known as TPO) has an absorption wavelength of 350 nm to 400 nm. After light irradiation, it can generate two free radicals, benzoyl and phosphoryl, both of which can initiate polymerization. It has a fast photocuring speed, low volatility, non-yellowing coating, low polymerization effect, and no residue, and can be used in transparent layer structures. Ethyl 2,4,6-trimethylbenzoylphosphonate (also known as photoinitiator TPO-L) has an absorption wavelength of 270 nm to 370 nm. 2-Hydroxy-2-methyl-1-phenyl-1-propanone (also known as photoinitiator 1173) has an absorption wavelength of 244 nm. It is a liquid product, easy to blend, and easy to combine with other photoinitiators. It is highly efficient, has low yellowing, and exhibits some volatility at high temperatures. Benzoin dimethyl ether (also known as photoinitiator BDK) has an absorption wavelength of 205 nm to 253 nm. It is a highly efficient and stable photoinitiator, with stronger absorption performance compared to 1173 and 184, thus more effectively promoting the cross-linking reaction of double bonds. 2-Hydroxy-1-(4-(2-hydroxy-2-methylpropionylphenyl)benzyl)-2-methyl-1-propanone (also known as photoinitiator 127) has an absorption wavelength of 259 nm. It has low oxygen sensitivity, good surface curing effect, low volatility, and low odor from both its own odor and photolysis products.

[0131] The type and source of the sixth component of the nanoimprint adhesive of this application are described below.

[0132] In some embodiments of this application, the coupling agent is at least one of γ-(methacryloyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, vinyltri(2-methoxyethoxy)silane, vinyltriethoxysilane, γ-(methacryloyloxy)propyltriethoxysilane, methacryloyloxymethyltriethoxysilane, 3-methacryloyloxypropyltri(methoxyethoxy)silane, methacryloyloxypropyltri(dimethylsiloxane)silane, γ-(acryloyloxy)propyltrimethoxysilane, γ-(acryloyloxy)propyltriethoxysilane, allyltri(trimethylsiloxy)silane, 1,3-bis(3-methacryloyloxypropyl)tetra(trimethylsiloxy)disiloxane, and N-(3-acryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane.

[0133] For example, the organosilanes provided above can all promote adhesion to the substrate, prevent the adhesive film from detaching from the substrate during the imprinting process, prevent the migration of free coupling agents, and effectively reduce the probability that the cured nanoimprint adhesive will be peeled off from the substrate during demolding.

[0134] The type and source of the seventh component of the nanoimprint adhesive of this application are described below.

[0135] In some embodiments of this application, the organic solvent is at least one selected from propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, ethyl acetate, N,N-dimethylformamide, methyl ethyl ketone, dimethyl sulfoxide, and butyl acetate.

[0136] For example, the organic solvent can make the components uniformly dispersed, and the organic solvent can also adjust the viscosity and evaporation rate of the nanoimprint adhesive, thereby facilitating the control of the film thickness and surface smoothness during spin coating.

[0137] The preparation method of the nanoimprint adhesive in the foregoing embodiments of this application will now be described.

[0138] According to the present invention, a method for preparing nanoimprint adhesive based on the foregoing embodiments is provided, such as... Figure 2 As shown, it includes the following steps:

[0139] Step S210: Add the organic solvent to the container, and add the optical monomer, acrylate prepolymer, and reactive diluent to the protective gas. Stir and mix to form a homogeneous first solution. The types and molar ratios of the optical monomer, acrylate prepolymer, reactive diluent, and organic solvent can be referred to the previous text and will not be repeated here.

[0140] In step S210 of some embodiments, a first stirring speed of 400 r / min to 600 r / min can be used during stirring, for example, values ​​such as 400 r / min, 450 r / min, 500 r / min, and 600 r / min. This allows the components to mix slowly, preventing agglomeration and enabling the components to disperse quickly and evenly.

[0141] In step S210 of some embodiments, the temperature in the container is 21°C to 25°C, for example, it can be 21°C, 22°C, 23°C, 24°C and 25°C, so that the various components are mixed more gently and are less likely to decompose.

[0142] In step S210 of some embodiments, the stirring time is 20 min to 40 min, for example, it can be 20 min, 30 min and 40 min, so that the components are fully mixed and uniform.

[0143] In step S210 of some embodiments, during the process of stirring and mixing evenly, gases such as nitrogen, helium, or argon can be introduced into the container to reduce the oxygen concentration inside the container. The specific gas to be introduced can be selected according to the actual situation.

[0144] Step S220: Stir the first solution and add the coupling agent and photoinitiator, then continue stirring to form a homogeneous second solution. The types, amounts, and functions of the coupling agent and photoinitiator are described above and will not be repeated here.

[0145] In step S220 of some embodiments, a first stirring speed of 700 r / min to 900 r / min can be used during stirring, for example, values ​​such as 700 r / min, 750 r / min, 800 r / min, 850 r / min, and 900 r / min. This allows the coupling agent and photoinitiator to be dispersed more quickly and uniformly.

[0146] In step S220 of some embodiments, the temperature in the container is 21°C to 25°C, for example, it can be 21°C, 22°C, 23°C, 24°C and 25°C, so that the mixing is more gentle and less prone to decomposition during the process of adding components.

[0147] In some embodiments, in step S220, the stirring time is 20 min to 40 min, for example, it can be 20 min, 30 min and 40 min, so that the components are fully mixed and uniform.

[0148] In step S220 of some embodiments, during the process of stirring and mixing evenly, gases such as nitrogen, helium or argon can be introduced into the container to reduce the oxygen concentration inside the container. The specific gas to be introduced can be selected according to the actual situation.

[0149] Step S230: Add nanoparticles to the second solution and continue stirring until homogeneous, then let it stand. The types, particle sizes, and functions of the nanoparticles are as described above and will not be repeated here.

[0150] In step S230 of some embodiments, the temperature in the container is 21°C to 25°C, for example, it can be 21°C, 22°C, 23°C, 24°C and 25°C, so that the mixing is relatively gentle during the process of adding nanoparticles and the temperature of the system before and after is consistent.

[0151] In step S230 of some embodiments, the stirring time is 10h to 14h, for example, it can be 10h, 11h, 12h, 13h and 14h, so that the nanoparticles are fully dispersed in the system.

[0152] In step S230 of some embodiments, the settling time is 20 min to 40 min, for example, it can be 20 min, 30 min and 40 min.

[0153] Step S240: Obtain nano-imprint adhesive by pressurized filtration and encapsulation.

[0154] In some embodiments of this application, the pressure filtration encapsulation uses a 0.22 μm organic filter membrane to filter out impurities and obtain the nanoimprint adhesive of this application.

[0155] As can be seen from the above, the nanoimprint adhesive prepared by the above method has sufficient mixing among its components, is not prone to agglomeration, and can form a relatively uniform coating adhesive, which is convenient for subsequent coating and imprinting. The prepared nanoimprint adhesive is easy to use and ensures that it has the aforementioned properties of nanoimprint adhesive.

[0156] The preparation method of the nanoimprint adhesive of this application and the performance test of the obtained nanoimprint adhesive are described below with reference to specific embodiments.

[0157] Example 1

[0158] 40g of the organic solvent propylene glycol methyl ether acetate (PGMEA) was added to a container, and the mixture was stirred at 500 rpm under nitrogen protection. Then, 30g of optical monomer, 8g of HR6200 acrylate prepolymer, and 5g of hydroxyethyl acrylate were slowly added, and the mixture was stirred for 30 minutes to ensure complete dispersion and dissolution, resulting in a homogeneous first solution. The liquid temperature in the container was maintained at 23°C throughout the process. The optical monomer used was the aforementioned first optical monomer—2,4,6-tris(1-(2-thiophene sulfide)-2-propylacrylate)-1,3,5-triazine sulfide, with the structural formula […].

[0159] Adjust the rotation speed to 800 r / min, then slowly add 1 g of γ-(methacryloyloxy)propyltrimethoxysilane coupling agent and 3 g of TPO photoinitiator, and continue stirring for 30 minutes to completely disperse and dissolve the system to obtain a uniform second solution. During the process, maintain the liquid temperature in the container at 23°C.

[0160] Slowly add 13g of PixClear Zirconia 10nm nanoparticle dispersion and continue stirring for 12 hours, maintaining the liquid temperature in the container at 23°C during the process. After stirring is complete, let stand for 30 minutes.

[0161] Semi-transparent to semi-transparent nanoimprint adhesives can be obtained by pressurizing and encapsulating a 0.22μm organic filter membrane.

[0162] Example 2

[0163] The preparation method is largely the same as in Example 1, except that the optical monomer is replaced with a structure having the following structural formula: The second optical monomer, 2,4,6-tris(1-phenyl sulfide-2-propyl acrylate)-1,3,5-triazine sulfide, was used to obtain a nanoimprinting adhesive.

[0164] Example 3

[0165] The preparation method is largely the same as in Example 1, except that the optical monomer is replaced with a structure having the following structural formula: The third optical monomer, 2,4,6-tris(1-(4-methylthiobenzenethiool)-2-propylacrylate)-1,3,5-triazine sulfide, was used to obtain a nanoimprinting adhesive.

[0166] Example 4

[0167] The preparation method is largely the same as in Example 1, except that the optical monomer is replaced with a structure having the following structural formula: The fourth optical monomer, 2,4,6-tris(1-(2-naphthyl thioether)-2-propyl acrylate)-1,3,5-triazine thioether, was used to obtain a nanoimprinting adhesive.

[0168] Comparative Example 1

[0169] The preparation steps are largely the same as in Example 1, except that the optical monomer in Example 1 is replaced with o-phenylphenoxyethyl acrylate (OPPEA) to prepare the ultraviolet nanoimprint adhesive. The OPPEA monomer does not have the phenyl sulfide group or the S atom of this application.

[0170] Test case

[0171] The nanoimprint enamel prepared in Examples 1-4 and the UV nanoimprint enamel prepared in Comparative Example 1 were subjected to the following performance tests, and the test methods are as follows:

[0172] 1. Appearance Test

[0173] A certain amount of the nanoimprint adhesive prepared in Examples 1 to 4 and the ultraviolet nanoimprint adhesive prepared in Comparative Example 1 were poured into colorless and transparent glass bottles respectively, and the appearance characteristics of the adhesive were observed under white light or natural light.

[0174] 2. Viscosity test

[0175] The refractive index of the nanoimprint adhesives prepared in Examples 1-4 and the ultraviolet nanoimprint adhesive prepared in Comparative Example 1 at 20°C was tested on a Brookfield rheometer.

[0176] 3. Solid content test

[0177] The nanoimprint adhesives prepared in Examples 1-4 and the ultraviolet nanoimprint adhesives prepared in Comparative Example 1 were weighed on an analytical balance, and then baked in a forced-air drying oven at 120°C for 2 hours. The weight of the baked adhesives was measured and their solid content was calculated.

[0178] 4. Hardness test

[0179] The nanoimprint adhesives prepared in Examples 1-4 and the ultraviolet nanoimprint adhesives prepared in Comparative Example 1 were spin-coated onto silicon wafers according to certain parameters. After baking, they were exposed and imprinted on an imprinting device to form a uniform film layer with a thickness of 1μm to 3μm. The hardness of the film was tested using a nanoindenter.

[0180] 5. Young's modulus test

[0181] The nanoimprint adhesives prepared in Examples 1-4 and the ultraviolet nanoimprint adhesives prepared in Comparative Example 1 were spin-coated onto silicon wafers according to certain parameters. After baking, they were 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 using a nanoindenter.

[0182] 6. Surface water droplet angle test

[0183] The nanoimprint adhesives prepared in Examples 1-4 and the ultraviolet nanoimprint adhesives prepared in Comparative Example 1 were spin-coated onto silicon wafers according to certain parameters. After baking, they were exposed and imprinted on an imprinting device to form a uniform film layer with a thickness of 1-3 μm. The surface water droplet angle was measured using a water droplet angle meter.

[0184] 7. Refractive index test

[0185] The nanoimprint adhesives prepared in Examples 1-4 and the ultraviolet nanoimprint adhesives prepared in Comparative Example 1 were spin-coated onto silicon wafers according to certain parameters. After baking, they were exposed and imprinted on an imprinting device to form a uniform film layer with a thickness of 1-3 μm. The refractive index was measured at 589 nm using an ellipsometer.

[0186] 8. Transmittance Test

[0187] The nanoimprint adhesives prepared in Examples 5-8 and the ultraviolet nanoimprint adhesives prepared in Comparative Example 2 were spin-coated onto the surface of a glass substrate. After baking, the substrate was exposed and imprinted on an imprinting device to form a uniform film layer with a thickness of 1-3 μm. The transmittance was measured using a haze meter.

[0188] 9. Yellowness Test

[0189] The adhesive is spin-coated onto the surface of a glass substrate, baked, and then exposed and imprinted on an imprinting device to form a uniform film layer with a thickness of 1 to 3 μm. The yellowness is measured using a haze meter.

[0190] 10. Haze Test

[0191] The adhesive was spin-coated onto the surface of a glass substrate, baked, and then exposed and imprinted on an imprinting device to form a uniform film layer with a thickness of 1–3 μm. The haze was measured using a haze meter. The final measured performance parameters are compared in Table 1 below.

[0192] Table 1 Performance test results of Examples 1-4 and Comparative Example 1

[0193]

[0194] The measured performance data shows that the nanoimprint adhesive prepared using optical monomers in this application has a higher refractive index than the ultraviolet nanoimprint adhesive prepared using OPPEA. The refractive index of the optical monomers in this application is higher than that of OPPEA. Compared with the ultraviolet nanoimprint adhesive prepared using OPPEA under the same preparation conditions, the nanoimprint adhesive prepared using the optical monomers in this application has a higher refractive index after curing. Therefore, this application can obtain a higher refractive index with the addition of the same amount of nanoparticles. In contrast, Comparative Example 1 requires the use of more nanoparticles to achieve the same refractive index as this application. The nanoimprint adhesive with optical monomers in this application can control the amount of nanoparticles added within a suitable range while ensuring that the nanoimprint adhesive has the required high refractive index after curing. This results in a nanoimprint adhesive with good flowability and easy coating.

[0195] Compared to the UV nanoimprinting adhesive of Comparative Example 1, the Young's modulus of the nanoimprinting adhesive of this application is significantly improved, indicating that the nanoimprinting adhesive with optical monomer components of this application can significantly improve its own structural strength. During the imprinting and demolding process, the formed micro-nano structure is not easily damaged, which can ensure a certain production yield and reduce the residual adhesive on the mold, making it convenient for the mold to be reused.

[0196] Meanwhile, the viscosity of the nanoimprint adhesive of this application is slightly higher than that of Comparative Example 1, but the overall viscosity is lower. The nanoimprint adhesive of this application has good fluidity and is easy to coat, which is conducive to filling micro-nano structures to form high-precision patterns. Moreover, the adhesive is easy to adhere to the substrate and is not easy to peel off from the substrate during demolding. It is easy to process and use, and is matched with efficient imprinting process to improve efficiency and facilitate large-scale mass production.

[0197] The droplet angle of the nanoimprint adhesive in this application is smaller than that of the UV nanoimprint adhesive in the comparative example, indicating that the nanoimprint adhesive in this application is easier to spread and coat, has good wetting and leveling properties on the substrate, excellent uniform coating performance, more uniform coating, high appearance yield after imprinting, and easier removal of hydrophilic contaminants on the surface of the adhesive.

[0198] The transmittance, yellowness, and haze of the nanoimprinting adhesive of this application are similar to the corresponding properties of the UV nanoimprinting adhesive of the comparative example, indicating that the nanoimprinting adhesive of this application has good transparency like the comparative example, and the optical device made therefrom can achieve good light propagation.

[0199] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed in the present invention, and these modifications or substitutions should all be covered within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A nanoimprinting adhesive, characterized in that, The nanoimprint adhesive is prepared from the following raw materials: optical monomers, acrylate prepolymers, reactive diluents, nanoparticles, photoinitiators, coupling agents, and organic solvents. The general structural formula of the optical monomers is as follows: Wherein, R1 is a substituted or unsubstituted aromatic group, R2 is methyl or hydrogen, R3 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 adhesive as described in claim 1, characterized in that, The weight parts of each component in the raw material are as follows: 20-30 parts of optical monomers; 5 to 10 parts of acrylate prepolymer; 3 to 5 parts of reactive diluent; 10 to 15 parts nanoparticles; 1 to 5 parts of photoinitiator; 1 to 5 parts coupling agent; 30 to 60 parts organic solvent.

3. The nanoimprint adhesive as described in claim 1 or 2, characterized in that, The optical monomer is prepared using the following steps: Compound P1, the first catalyst, and the first solvent are mixed evenly, and epichlorohydrin or methyl epichlorohydrin is added to react and generate the first product; the compound P1 is a compound containing thiol and aromatic groups; 2,4,6-trimercapto-1,3,5-triazine, a second catalyst, and a second solvent are mixed evenly, and the first product is added to catalyze a reaction to generate the second product, wherein the molar ratio of the first product to 2,4,6-trimercapto-1,3,5-triazine is (3~4):1; The second product, auxiliaries, and stabilizers are added to the third solvent and mixed evenly. The solution is cooled, and under gas protection, acryloyl chloride or methacryloyl chloride is added to react with the third catalyst to generate the optical monomer, wherein the molar ratio of acryloyl chloride or methacryloyl chloride to the second product is (3~4):

1.

4. The nanoimprint adhesive as described in claim 3, characterized in that, The compound P1 is selected from one of 2-mercaptothiophene, thiophene, 4-methylthiophene, and 2-mercaptonaphthalene; 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 adjuvant is selected from triethylamine or 1,8-diazabicycloundec-7-ene; The stabilizer is selected from at least one of butylated hydroxytoluene, butylated hydroxyanisole and tert-butylhydroquinone; The third solvent is selected from dichloromethane or tetrahydrofuran; The third catalyst is 4-dimethylaminopyridine.

5. The nanoimprint adhesive as described in claim 3, characterized in that, The molar ratio of compound P1, the first catalyst, the first solvent, and epichlorohydrin is 100:(70~90):(1317~1505):(100~120); or, the molar ratio of compound P1, the first catalyst, the first solvent, and methyl epichlorohydrin is 100:(70~90):(1317~1505):(100~120). The reaction temperature of compound P1 with epichlorohydrin or methyl epichlorohydrin is room temperature, and the reaction time is 14h~18h. The molar ratio of the 2,4,6-trimercapto-1,3,5-triazine, the second catalyst, the second solvent, and the first product is 50:(50~55):(847~1035):(150~200). The reaction temperature of 2,4,6-trimercapto-1,3,5-triazine with the first product is room temperature, and the reaction time is 18h~22h. The molar ratio of the second product, auxiliary agent, stabilizer, third solvent, methacryloyl chloride, and third catalyst is 35:(200~300):(2.5~2.8):(1714~2026):(105~140):(5.0~6.0); or the molar ratio of the second product, auxiliary agent, stabilizer, third solvent, methacryloyl chloride, and third catalyst is 35:(200~300):(2.5~2.8):(1714~2026):(105~140):(5.0~6.0). The second product reacts with acryloyl chloride or methacryloyl chloride at a temperature of 0°C or under ice bath conditions, and under a protective atmosphere of nitrogen or an inert gas.

6. The nanoimprinting adhesive as described in claim 1 or 2, characterized in that, The acrylate prepolymers are selected from Kunshan Castel's 9537; Changxing Materials 6151, Changxing Materials DR-U084, Changxing Materials DR-U299, Changxing Materials DR-U379, Changxing Materials DR-U384, Changxing Materials DR-U388, Changxing Materials 6371, and Changxing Materials 6372; The following are some of the following: Midea HR6100, Midea HR6200, Midea PS4500, Midea PS4040, Midea PS610; and at least one of the following: Sartoma CN2254NS, CN2303, CN293, CN750, CN790, CN8008NS, CN8201NS, CN983NS, CN996NS.

7. The nanoimprint adhesive as described in claim 1 or 2, characterized in that, The reactive diluent is selected from at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, propoxylated glycerol triacrylate, ethoxylated trimethylolpropane triacrylate, cyclotrimethylolpropane methyl acetal acrylate, 4-hydroxybutyl acrylate, dicyclopentadiene methacrylate, tetrahydrofuran methacrylate, tetrahydrofuran acrylate, 4-tert-butylcyclohexyl acrylate, 4-acryloylmorpholine, trimethylcyclohexyl acrylate, trimethylolpropane triacrylate, and pentaerythritol triacrylate.

8. The nanoimprinting adhesive as described in claim 1 or 2, characterized in that, The nanoparticles are metal oxide nanoparticles, and / or the particle size range of the nanoparticles is 10 nm to 20 nm.

9. The nanoimprinting adhesive as described in claim 8, characterized in that, The nanoparticles are titanium oxide nanoparticles or zirconium oxide nanoparticles.

10. The nanoimprinting adhesive as described in claim 1 or 2, characterized in that, The photoinitiator is selected from at least one of photoinitiator 1173, photoinitiator 1176, photoinitiator 184, TPO, TPO-L, photoinitiator 127, photoinitiator 369, ITX, BDK, photoinitiator 819, photoinitiator 754, BMF, ANTHRACURE™ UVS-1331, ANTHRACURE™ UVS-1101, Easepi 6992, and Easepi 250.

11. The nanoimprinting adhesive as described in claim 1 or 2, characterized in that, The coupling agent is at least one of γ-(methacryloyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, vinyltri(2-methoxyethoxy)silane, vinyltriethoxysilane, γ-(methacryloyloxy)propyltriethoxysilane, methacryloyloxymethyltriethoxysilane, 3-methacryloyloxypropyltri(methoxyethoxy)silane, methacryloyloxypropyltri(dimethylsiloxane)silane, γ-(acryloyloxy)propyltrimethoxysilane, γ-(acryloyloxy)propyltriethoxysilane, allyltri(trimethylsiloxy)silane, 1,3-bis(3-methacryloyloxypropyl)tetra(trimethylsiloxy)disiloxane, and N-(3-acryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane.

12. The nanoimprint adhesive as described in claim 1 or 2, characterized in that, The organic solvent 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.

13. The nanoimprinting adhesive as described in claim 1 or 2, characterized in that, The R1 includes thiophene, phenyl, methylthiophenyl, or naphthyl.

14. A method for preparing a nanoimprint adhesive as described in any one of claims 1 to 13, characterized in that, The steps include: adding an organic solvent to a container, adding an optical monomer, an acrylate prepolymer, and a reactive diluent to a protective gas atmosphere, stirring and mixing to form a homogeneous first solution; Stir the first solution and add the coupling agent and photoinitiator, then continue stirring to form a homogeneous second solution; Add nanoparticles to the second solution and continue stirring until homogeneous, then let stand. Nanoimprint adhesive was obtained by pressure filtration and encapsulation.

15. The method for preparing the nanoimprint adhesive as described in claim 14, characterized in that, During the reaction, the temperature in the container is 21℃~25℃; the pressurized filtration encapsulation uses a 0.22μm organic filter membrane.

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