Fluorine-containing organosilicon epoxy monomer and preparation method thereof, and application thereof in preparing embossing adhesive, embossing adhesive and preparation method thereof, and an embossing method

Abstract

The present invention relates to the field of photocurable embossing adhesives, particularly to a fluorinated organosilicon epoxy monomer, its preparation method, its use in preparing embossing adhesives, an embossing adhesive and its preparation method, and an embossing method. The fluorinated organosilicon epoxy monomer has a general structural formula of one of the following: #imgabs0#, where R is a fluorinated alkyl chain with 12 or fewer carbon atoms, and n is an integer from 0 to 3. Nanoimprint adhesives prepared using the fluorinated organosilicon epoxy monomers of the present invention exhibit excellent transfer performance, are easily demoldable, and can transfer complete patterns.

Description

Technical Field

[0001] The present invention relates to the technical field of photocurable embossing adhesives, and in particular to a fluorine-containing organosilicon epoxy monomer and a preparation method thereof, and an application thereof in preparing embossing adhesives, the embossing adhesive and a preparation method thereof, and an embossing method. Background Art

[0002] Nanoimprint lithography is a next-generation micro-nanofabrication technology that uses imprint adhesives for mechanical pattern transfer. This technology can achieve ultra-high resolution and is expected to replace traditional photolithography in the future, becoming a key processing method in the fields of microelectronics and materials. As a key material in imprint lithography, the performance of imprint adhesives directly affects the quality of nanoimprint lithography.

[0003] Nanoimprinting can be categorized into hot embossing and UV embossing based on the pattern formation mechanism. Consequently, nanoimprint adhesives are also divided into hot embossing adhesives and UV embossing adhesives. UV embossing adhesives utilize small-molecule monomers or oligomers as prepolymers, eliminating the need for the high temperatures and pressures typically associated with hot embossing. These adhesives offer improved alignment and are suitable for multi-layer processing, shortening processing times and increasing production efficiency. Recent statistics indicate that UV embossing adhesives account for over 90% of nanoimprint adhesive patent applications, demonstrating their continued importance as a research focus and mainstream technology.

[0004] To achieve ultra-high-precision pattern imprinting and transfer, UV imprint adhesives must simultaneously meet requirements such as low viscosity, fast light curing rate, excellent demolding properties, good adhesion to the substrate, and excellent resistance to dry etching. Currently commercialized organic imprint adhesives do not meet these seemingly contradictory requirements and cannot meet the requirements for ultra-high-precision pattern imprinting and transfer.

[0005] Therefore, those skilled in the art are committed to developing a fluorine-containing silicone epoxy monomer and a preparation method thereof, and its application in the preparation of a stamping adhesive, a stamping adhesive and a preparation method thereof, and a stamping method, which uses the stamping adhesive prepared by the raw materials and method of the present invention to achieve excellent demolding performance and stamping effect. Summary of the Invention

[0006] In view of the above-mentioned defects in the prior art, the technical problem to be solved by the present invention is to provide a fluorine-containing silicone epoxy monomer and a preparation method thereof, and its application in the preparation of embossing adhesives, embossing adhesives and their preparation method, and an embossing method, which uses the embossing adhesives prepared by the raw materials and methods of the present invention to achieve excellent demolding performance and embossing effect.

[0007] To achieve the above objectives, the present invention provides a fluorine-containing organosilicon epoxy monomer, the general structural formula of which is one of the following two:

[0008]

[0009] Here, R is a fluorine-containing alkyl chain having 12 or less carbon atoms, and n is an integer of 0 to 3.

[0010] The present invention also provides a method for preparing the fluorine-containing organosilicon epoxy monomer as described above, comprising the following steps:

[0011] S1: Dichlorosilane containing a fluorinated side chain is used as a raw material and is added dropwise to a mixed solution of 2.7 times the molar equivalent of triethylamine, 2.2 times the molar equivalent of 1-hydroxy-3-cyclohexene and tetrahydrofuran. After refluxing for 10 to 30 hours, the organic phase is collected and impurities are removed to generate cyclohexenesiloxane containing a fluorinated side chain, whose molecular structure is:

[0012]

[0013] Where R1 is C2H4CF3 or C2H4C6F 13 ;

[0014] S2: The prepared cyclohexene siloxane containing a fluorinated side chain is dissolved in dichloromethane and oxidized with 2.5 times the molar equivalent of m-chloroperbenzoic acid at 0°C. The reaction is quenched and washed with water and dried to generate a fluorinated organosilicon epoxy resin monomer, the molecular structure of which is as follows:

[0015]

[0016] Where R1 is C2H4CF3 or C2H4C6F 13 .

[0017] The present invention further provides a method for preparing the above-mentioned fluorine-containing organosilicon epoxy monomer, comprising the following steps:

[0018] F1: Dichlorosilane or trifluoropropylmethylcyclotrisiloxane or 1,3,5-trimethyl-1,3,5-tris(1H,1H,2H,2H-perfluorooctyl)cyclotrisiloxane containing fluorinated side chains is used as raw material and 2.2 times the molar equivalent of 1,1,3,3-tetramethylsiloxane is hydrolyzed under the catalysis of water or trifluoromethanesulfonic acid to generate methylsiloxane containing fluorinated side chains. Its molecular structure is as follows:

[0019]

[0020] Where R2 is C2H4CF3 or C2H4C6F 13 , n is an integer from 0 to 3;

[0021] F2: Using the prepared fluorinated side chain methylsiloxane as raw material, petroleum ether and Karstedt catalyst were stirred evenly, and 2.5 times the molar equivalent of 1,2-epoxy-4-vinylcyclohexane was added dropwise. After the addition was complete, the mixture was refluxed to generate a fluorinated organosilicon epoxy resin monomer. Its molecular structure is as follows:

[0022]

[0023] Where R2 is C2H4CF3 or C2H4C6F 13 , n is an integer from 0 to 3.

[0024] The present invention also provides an application of a fluorine-containing organosilicon epoxy monomer in preparing a embossing adhesive. The fluorine-containing organosilicon epoxy monomer as described above is used to prepare the embossing adhesive.

[0025] The present invention provides a embossing adhesive comprising the following components by weight:

[0026] 50-90 parts of the fluorine-containing organosilicon epoxy monomer according to claim 1, 5-20 parts of an organosilicon crosslinking agent, 0-30 parts of a reactive diluent, 0.5-5 parts of a cationic photoinitiator, and 0-5 parts of an auxiliary agent.

[0027] Preferably, the organosilicon crosslinking agent is selected from one or more of the following:

[0028]

[0029] Preferably, the active diluent is selected from one or more of the following:

[0030]

[0031]

[0032] Preferably, the cationic photoinitiator is one or more of diaryliodonium salts or triarylsulfonium salts; and the auxiliary agent includes a leveling agent or a defoaming agent.

[0033] The present invention also provides a method for preparing the above-mentioned embossing adhesive, which is characterized by comprising the following steps:

[0034] M1: Add silicone crosslinking agent, reactive diluent, photoinitiator and auxiliary agent to the fluorine-containing silicone epoxy resin monomer and stir in a dark environment for 15 to 30 hours;

[0035] M2: Degas under vacuum for 0.5 to 3 hours to obtain.

[0036] The present invention also provides an embossing method, using the above-mentioned embossing adhesive, comprising the following steps:

[0037] (a) using a thermoplastic polymer or a thermosetting polymer as a base layer;

[0038] (b) spin-coating a layer of adhesion promoter on the base layer, and then spin-coating a layer of the embossing adhesive as the embossing layer, wherein the viscosity of the embossing adhesive is 5 mPa·s to 5000 mPa·s;

[0039] (c) The embossing layer is pressed onto the surface of the stamp with a pattern after being treated with an anti-adhesive agent, and the embossing is performed under conditions of 0.5 to 3 atm. After the embossing adhesive completely fills the gaps in the stamp, ultraviolet light is irradiated through the back of the base layer stamp to polymerize it. The curing time is less than or equal to 5 minutes. After the embossing adhesive is cured and formed, it is demolded to obtain the embossed pattern.

[0040] The beneficial effects of the present invention are as follows: when the embossing adhesive of the present invention is used, the epoxy group of cationic polymerization initiated by ultraviolet light in ultraviolet nanoimprinting is used as a polymerization unit, which can effectively avoid high-temperature operation, reduce volume shrinkage during curing, and is not affected by oxygen inhibition; the addition of the silicone monomer can improve the heat resistance and hydrophobicity of the epoxy resin, and can effectively improve the etching resistance of the embossing adhesive after curing; the bond energy of the C-F bond is higher than that of the C-H bond, and the shared electron pair of the fluorine-carbon atom is greatly biased towards the fluorine atom, forming a layer of negative charge protection, which can effectively reduce the surface energy of the embossing adhesive after curing, making demolding easier, thereby efficiently obtaining nano-patterns with high resolution and aspect ratio; the embossing adhesive prepared using the fluorine-containing silicone epoxy monomer of the present invention has an excellent transfer effect, is easy to demold, and can transfer a complete pattern. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 The embossing pattern is obtained by curing and then demoulding the embossing adhesive prepared in Example 1 of the present invention.

[0042] Figure 2 The embossing pattern is obtained by curing and then demoulding the embossing adhesive prepared in Example 2 of the present invention.

[0043] Figure 3 The embossing pattern is obtained by curing and then demoulding the embossing adhesive prepared in Example 3 of the present invention.

[0044] Figure 4 The embossing pattern is obtained by curing and then demoulding the embossing adhesive prepared in Example 4 of the present invention.

[0045] Figure 5 The embossed pattern is obtained by curing and then demoulding the embossed adhesive prepared in the comparative example of the present invention. DETAILED DESCRIPTION

[0046] The present invention will be further described below with reference to the accompanying drawings and examples. In this embodiment, unless otherwise stated, all raw materials used are commercially available. Chemical reagents are analytically pure reagents. 1 H NMR and 19 The solvent for F NMR measurements was deuterated chloroform, and the internal standard was tetramethylsilane.

[0047] The present invention provides a fluorine-containing organosilicon epoxy monomer, the general structural formula of which is one of the following two:

[0048]

[0049] Here, R is a fluorine-containing alkyl chain having 12 or less carbon atoms, and n is an integer of 0 to 3.

[0050] There are two preparation methods:

[0051] The first preparation method comprises the following steps:

[0052] S1: Dichlorosilane containing a fluorinated side chain is used as a raw material and is added dropwise to a mixed solution of 2.7 times the molar equivalent of triethylamine, 2.2 times the molar equivalent of 1-hydroxy-3-cyclohexene and tetrahydrofuran. After refluxing for 10 to 30 hours, the organic phase is collected and impurities are removed to generate cyclohexenesiloxane containing a fluorinated side chain, whose molecular structure is:

[0053] Where R1 is C2H4CF3 or C2H4C6F 13 ;

[0054] S2: The prepared cyclohexene siloxane containing fluorinated side chains was dissolved in dichloromethane and oxidized with 2.5 times the molar equivalent of m-chloroperoxybenzoic acid at 0°C, quenched, washed with water, and dried to produce

[0055] The fluorinated silicone epoxy resin monomer has the following molecular structure:

[0056]

[0057] Where R1 is C2H4CF3 or C2H4C6F 13 .

[0058] The second method includes the following steps:

[0059] F1: Dichlorosilane or trifluoropropylmethylcyclotrisiloxane or 1,3,5-trimethyl-1,3,5-tris(1H,1H,2H,2H-perfluorooctyl)cyclotrisiloxane containing fluorinated side chains is used as raw material and 2.2 times the molar equivalent of 1,1,3,3-tetramethylsiloxane is hydrolyzed under the catalysis of water or trifluoromethanesulfonic acid to generate methylsiloxane containing fluorinated side chains. Its molecular structure is as follows:

[0060]

[0061] Where R2 is C2H4CF3 or C2H4C6F 13 , n is an integer from 0 to 3;

[0062] F2: Using the prepared fluorinated side chain methylsiloxane as raw material, petroleum ether and Karstedt catalyst were stirred evenly, and 2.5 times the molar equivalent of 1,2-epoxy-4-vinylcyclohexane was added dropwise. After the addition was complete, the mixture was refluxed to generate a fluorinated organosilicon epoxy resin monomer. Its molecular structure is as follows:

[0063]

[0064] Where R2 is C2H4CF3 or C2H4C6F 13 , n is an integer from 0 to 3.

[0065] The present invention also provides a use of the fluorine-containing organosilicon epoxy monomer described above in preparing an embossing adhesive.

[0066] When using the fluorinated organosilicon epoxy monomer of the present invention to prepare a embossing adhesive, 50-90 parts of the above-mentioned fluorinated organosilicon epoxy monomer, 5-20 parts of an organosilicon crosslinking agent, 0-30 parts of a reactive diluent, 0.5-5 parts of a cationic photoinitiator, and 0-5 parts of an auxiliary agent are used. The organosilicon crosslinking agent may be one or more of the following:

[0067]

[0068] The active diluent is selected from one or more of the following:

[0069]

[0070] The cationic photoinitiator is one or more of a diaryliodonium salt or a triarylsulfonium salt.

[0071] The additives include leveling agents and defoaming agents, and specifically one or more of BYK-333, BYK-3455, BYK-3510, BYK-024, BYK-054, Tego Glide400, Tego Glide100, and TegoGlide405 can be selected.

[0072] The preparation method of the embossing adhesive comprises the following steps:

[0073] M1: Add silicone crosslinking agent, reactive diluent, photoinitiator and auxiliary agent to the fluorine-containing silicone epoxy resin monomer and stir in a dark environment for 15 to 30 hours;

[0074] M2: Degas under vacuum for 0.5 to 3 hours to obtain.

[0075] In order to prepare the embossing adhesive of the present invention, the present invention provides four specific examples and comparative examples to prepare corresponding fluorine-containing silicone epoxy monomers and the embossing adhesive of the present invention, and illustrate their effects.

[0076] Example 1

[0077] 1) Preparation of fluorinated organosilicon epoxy monomer

[0078] To a 500mL three-necked flask, add 16.8g of 1-hydroxy-3-cyclohexene, 13.6g of triethylamine, and 150mL of tetrahydrofuran. Then, dropwise add a mixture of trifluoropropylmethyldichlorosilane and 50mL of tetrahydrofuran. The tetrahydrofuran solvent is used; its concentration and amount are not critical. The molar ratio of trifluoropropylmethyldichlorosilane to triethylamine is 1:2.7, and the molar ratio of trifluoropropylmethyldichlorosilane to 1-hydroxy-3-cyclohexene is 1:2.2. After the addition is complete, reflux for 20 hours. Add 300mL of 20% by volume dilute hydrochloric acid. Collect the organic phase, wash once with sodium bicarbonate solution and once with water, then dry over anhydrous sodium sulfate. Remove the solvent under reduced pressure and purify by column chromatography using dichloromethane as the eluent to obtain a colorless, transparent liquid (14.34g, 79.7% yield), cyclohexenesiloxane containing fluorinated side chains.

[0079] 8g of the above product and 120mL of dichloromethane were added to a 250mL flask and stirred in an ice-water bath for half an hour until the temperature reached 0°C. 11.1g of m-chloroperbenzoic acid was added for oxidation. The molar ratio of cyclohexenesiloxane containing a fluorinated side chain and m-chloroperbenzoic acid was 1:2.5. After all the fluorinated side chains were dissolved, the mixture was heated to room temperature and stirred for 5h. After the raw materials reacted completely, sodium hydroxide solution was added to quench the reaction. The organic phase was washed with sodium bicarbonate solution and water once each and dried over anhydrous sodium sulfate. After the solvent was removed under reduced pressure, column chromatography was performed for purification using dichloromethane as the eluent. A colorless, transparent liquid was obtained as a fluorinated organosilicon epoxy monomer (7.55g, 87% yield), hereinafter referred to as the first fluorinated organosilicon epoxy monomer. The structural confirmation results are as follows: 1 H NMR (CDCl3, 400MHz): 3.35-3.49(m,4H),3.10-3.16(m,4H),1.91-2.16(m,6H),1.78-1.86(m,1H),1.61-1 .74(m,2H),1.35-1.51(m,5H),1.04-1.14(m,1H),0.90-1.00(m,1H),0.72-0.77(m,2H),0.08(s,3H)ppm. 19 F NMR (CDCl3, 400MHz): -68.78, -68.80, -68.83ppm.

[0080] The reaction steps are:

[0081]

[0082] 2) preparing an embossing adhesive, specifically comprising the following steps:

[0083] M1: Add silicone crosslinking agent, reactive diluent, photoinitiator and leveling agent to the first fluorine-containing silicone epoxy resin monomer and stir for 15 hours in a dark environment;

[0084] M2: Degas under vacuum for 0.5 h to obtain the embossing adhesive.

[0085] The formulas of various ingredients in Example 1 are shown in Table 1.

[0086] Table 1

[0087]

[0088] Example 2

[0089] 1) Preparation of fluorinated organosilicon epoxy monomer

[0090] To a 250 mL single-necked flask, 45.6 g of trifluoropropylmethyldichlorosilane, 57.8 g of 1,1,3,3-tetramethyldisiloxane, and 25 μL of water were added and stirred at room temperature for 3 days. The molar ratio of trifluoropropylmethyldichlorosilane to 1,1,3,3-tetramethyldisiloxane was 1:2.2. Trifluoropropylmethyldichlorosilane and 2.2 molar equivalents of 1,1,3,3-tetramethyldisiloxane were hydrolyzed in water to produce a methylsiloxane containing a fluorinated side chain. The reaction was quenched by adding ice water. After stirring to room temperature, the organic phase was washed with sodium bicarbonate solution and then water, and dried over anhydrous sodium sulfate. The solvent was removed by swirl and the mixture was subjected to rectification. The 53°C fraction was collected to obtain a colorless, transparent liquid (50.91 g, 81.4% yield).

[0091] 42.2 g of the above product, 70 mL of petroleum ether, and 10 drops of Karstedt catalyst were added to a 250 mL three-necked flask and heated to reflux. 28 g of 1,2-epoxy-4-vinylcyclohexane was slowly added dropwise and refluxed overnight. The molar ratio of the above product to 1,2-epoxy-4-vinylcyclohexane was 1:2.5. After the reaction was complete, the solvent was removed under reduced pressure and purified by column chromatography using dichloromethane as the eluent. A transparent liquid was obtained, which was the fluorinated organosilicon epoxy monomer (21.5 g, 86% yield), hereinafter referred to as the second fluorinated organosilicon epoxy monomer. The structural confirmation results are as follows: 1H NMR (CDCl3, 400MHz): 3.10-3.16(m,4H),2.10-2.19(m,2H),1.93-2.06(m,4H),1.77-1.85(m,1H),1.65-1.73(m,1H),1.46-1.51(m, 1H),1.24-1.41(m,4H),1.00-1.19(m,6H),0.84-0.91(m,1H),0.62-0.66(m,2H),0.45-0.51(m,4H),0.05(d,12H),0.03(s,3H)ppm. 19 F NMR (CDCl3, 400MHz): -68.71ppm.

[0092] The reaction steps are:

[0093]

[0094] 2) preparing an embossing adhesive, specifically comprising the following steps:

[0095] M1: Add silicone crosslinker, reactive diluent and photoinitiator to the fluorine-containing silicone epoxy resin monomer and stir for 30 hours in a dark environment;

[0096] M2: Degassing under vacuum for 0.5 h to obtain a fluorine-containing organosilicon epoxy resin light-curing embossing adhesive, namely the embossing adhesive of the present invention.

[0097] Among them, the formula of various ingredients is shown in Table 2

[0098] Table 2

[0099]

[0100] Example 3:

[0101] 1) Preparation of fluorinated organosilicon epoxy monomer

[0102] To a 250 mL single-necked flask, 25 g of trifluoropropylmethylcyclotrisiloxane and 17.7 g of 1,1,3,3-tetramethyldisiloxane were added. The molar ratio of trifluoropropylmethylcyclotrisiloxane to 1,1,3,3-tetramethyldisiloxane was 1:2.2. After stirring in an ice-water bath for 20 min, 0.8 mL of trifluoromethanesulfonic acid was added, and the reaction was continued for 17 min. 37 mL of hexamethyldisilazane was added to quench the reaction, and the mixture was directly warmed to room temperature. After the reaction solution became turbid, it was filtered, and low-boiling substances were removed under reduced pressure and then distilled. The fraction at 140°C was collected to obtain a colorless transparent liquid (29.1 g, yield 90.5%), which was the product - methylsiloxane containing fluorinated side chains.

[0103] 27.8g of the above product, 50mL of petroleum ether, and 10 drops of Karstedt catalyst were added to a 250mL three-necked flask and heated to reflux. 14.9g of 1,2-epoxy-4-vinylcyclohexane was slowly added dropwise, with the molar ratio of the above product to 1,2-epoxy-4-vinylcyclohexane being 1:2.5. After the addition was complete, the mixture was refluxed overnight. After the reaction was complete, the solvent was removed under reduced pressure and purified by column chromatography using dichloromethane as the eluent to obtain a transparent liquid, which was the fluorinated organosilicon epoxy monomer (34.2g, 87.7% yield), hereinafter referred to as the third fluorinated organosilicon epoxy monomer. The structural confirmation results are as follows: 1 H NMR (CDCl3, 400MHz): 3.12-3.18(m,4H),1.96-2.20(m,10H),1.78-1.87(m,2H),1.24-1.52(m,5H),1 .04-1.20(m,6H),0.68-0.92(m,7H),0.48-0.53(m,4H),0.13(s,3H),0.10(s,6H),0.08(s,12H)ppm. 19 F NMR (CDCl3, 400MHz): -69.25, -69.35ppm.

[0104] The reaction steps are:

[0105]

[0106] S2: preparing an embossing adhesive, specifically comprising the following steps:

[0107] 1) Adding a silicone crosslinker, a reactive diluent, a photoinitiator, and an auxiliary agent to a fluorine-containing silicone epoxy resin monomer and stirring the mixture in a dark environment for 24 hours;

[0108] 2) Degassing under vacuum for 1 hour to obtain a fluorine-containing organosilicon epoxy resin light-curing embossing adhesive, namely, the embossing adhesive of the present invention.

[0109] Among them, the formula of various ingredients is shown in Table 3

[0110] Table 3

[0111]

[0112] Example 4:

[0113] 1) Preparation of fluorinated organosilicon epoxy monomer

[0114] To a 250 mL single-necked flask, 32 g of 1,3,5-trimethyl-1,3,5-tris(1H,1H,2H,2H-perfluorooctyl)cyclotrisiloxane and 8.8 g (2.2 times the molar equivalent) of 1,1,3,3-tetramethyldisiloxane were added. After stirring in an ice-water bath for 20 min, 0.4 mL of trifluoromethanesulfonic acid was added, and the reaction was allowed to proceed for 17 min. 19 mL of hexamethyldisilazane was added to quench the reaction. The reaction solution was warmed to room temperature, and after it became turbid, it was filtered, and low-boiling substances were removed by vacuum distillation. The fraction at 153°C was collected to obtain a colorless transparent liquid (32.8 g, yield 92%).

[0115] 25.1g of the above product, 50mL of petroleum ether, and 10 drops of Karstedt catalyst were added to a 250mL three-necked flask and heated to reflux. 7g, or 2.5 times the molar equivalent of 1,2-epoxy-4-vinylcyclohexane, was slowly added dropwise. After the addition was complete, the mixture was refluxed overnight. After the reaction was complete, the solvent was removed under reduced pressure and purified by column chromatography using dichloromethane as the eluent. A transparent liquid was obtained, which was fluorinated organosilicon epoxy monomer 4 (25.5g, 86% yield), hereinafter referred to as the fourth fluorinated organosilicon epoxy monomer. The structural confirmation results are as follows: 1 H NMR (CDCl3, 400MHz): 3.10 (m, 4H), 0.45-2.16 (m, 38H), 0.13 (s, 3H), 0.09 (s, 6H), 0.05 (s, 12H) ppm. 19 F NMR (CDCl3, 400MHz): -81.51, -116.81, -122.52, -123.50, -123.99, -126.80ppm.

[0116] The reaction steps are:

[0117]

[0118] 2) preparing an embossing adhesive, specifically comprising the following steps:

[0119] M1: Add silicone crosslinker, reactive diluent, photoinitiator and auxiliary agent to the fluorine-containing silicone epoxy resin monomer and stir for 24 hours in a dark environment;

[0120] M2: Degassing under vacuum for 1 hour to obtain a fluorine-containing organosilicon epoxy resin light-curing embossing adhesive, namely the embossing adhesive of the present invention.

[0121] Among them, the formula of various ingredients is shown in Table 4

[0122] Table 4

[0123]

[0124] Comparative Example

[0125] The present invention sets a comparative example to prepare a embossing adhesive, wherein a commercially available silicone epoxy resin monomer is used instead of the silicone epoxy monomer in the present invention. The specific ingredients are shown in Table 5

[0126] Table 5

[0127]

[0128] The preparation method of the comparative example embossed adhesive is as follows:

[0129] 1) Adding a silicone crosslinker, a photoinitiator, a reactive diluent, a leveling agent, and a defoamer to a commercial silicone epoxy resin monomer and stirring for 24 hours in a dark environment;

[0130] 2) Degassing was performed under vacuum for 1 hour to obtain a fluorine-containing organosilicon epoxy resin light-curing embossing adhesive, i.e., a comparative example embossing adhesive.

[0131] The imprint adhesives prepared in Examples 1-4 and the comparative example were subjected to nanoimprint testing in the following manner:

[0132] (a) First, a thermoplastic polymer or a thermosetting polymer is used as a base layer. The base layer can be selected from one of polymethacrylate, polyethylene terephthalate, polystyrene, epoxy polymer, polyamide, polyimide, polyurethane or polycarbonate. In this embodiment, polyethylene terephthalate is used.

[0133] (b) Spin-coating a layer of adhesion promoter on the substrate. The adhesion promoter is a silane coupling agent with epoxy or amino functional groups, and can be one or more of KH-186, KH-560, KH-561, KH550, or KH792. In this embodiment, KH-560 is selected to increase the adhesion between the embossing adhesive and the substrate. The thickness is 2 nm. Then, spin-coating another layer of the embossing adhesive as an embossing layer. The viscosity of the embossing adhesive is 5 mPa·s to 5000 mPa·s.

[0134] (c) The embossing layer is pressed onto the surface of a stamp with a pattern that has been treated with an anti-sticking agent. The embossing is performed at 2 atm. After the embossing adhesive completely fills the gaps in the stamp, ultraviolet light is irradiated through the back of the base layer stamp to polymerize it. The curing time is 5 minutes. After the embossing adhesive is cured and formed, it is demolded to obtain the embossed pattern.

[0135] The embossed patterns obtained in Examples 1 to 4 are as follows: Figures 1 to 4 As shown in the figure, the embossing test of the embossing glue prepared in the comparative example is as follows: Figure 5 The demolding force of each embodiment and comparative example during the test was tested by a tensile testing machine, and the results are shown in Table 6:

[0136] Table 6:

[0137] Release force Pattern completeness Example 1 Smaller A small amount of incomplete Example 2 Smaller basically complete Example 3 Smaller basically complete Example 4 Small whole Comparative Example big Incomplete

[0138] It can be seen from the above embodiments that the embossing adhesive of the present invention has the characteristics of low viscosity (low demolding force) and high embossing quality.

[0139] The above describes in detail the preferred embodiments of the present invention. It should be understood that those skilled in the art can make numerous modifications and variations based on the concepts of the present invention without inventive effort. Therefore, any technical solutions that can be derived by those skilled in the art through logical analysis, reasoning, or limited experimentation based on the concepts of the present invention and the prior art should be within the scope of protection defined by the claims.

Claims

1. A stamping adhesive, characterized in that: By weight, it includes the following components: 50-90 parts of fluorinated organosilicon epoxy monomer, 5-20 parts of organosilicon crosslinking agent, 0-30 parts of reactive diluent, 0.5-5 parts of cationic photoinitiator, 0-5 parts of auxiliary agent; The general structural formula of the fluorine-containing organosilicon epoxy monomer is one of the following two: Here, R is a fluorine-containing alkyl chain having 12 or less carbon atoms, and n is an integer of 0 to 3.

2. A stamping adhesive as claimed in claim 1, characterized in that: The preparation method of the fluorine-containing organosilicon epoxy monomer comprises the following steps: S1: Dichlorosilane containing a fluorinated side chain is used as a raw material and is added dropwise to a mixed solution of 2.7 times the molar equivalent of triethylamine, 2.2 times the molar equivalent of 1-hydroxy-3-cyclohexene and tetrahydrofuran. After refluxing for 10 to 30 hours, the organic phase is collected and impurities are removed to generate cyclohexenesiloxane containing a fluorinated side chain, whose molecular structure is: Where R1 is C2H4CF3 or C2H4C6F 13 ; S2: The prepared cyclohexene siloxane containing a fluorinated side chain is dissolved in dichloromethane and oxidized with 2.5 times the molar equivalent of m-chloroperbenzoic acid at 0°C. The reaction is quenched and washed with water and dried to generate a fluorinated organosilicon epoxy resin monomer, the molecular structure of which is as follows: Where R1 is C2H4CF3 or C2H4C6F 13 .

3. The embossing adhesive according to claim 1, wherein: The preparation method of the fluorine-containing organosilicon epoxy monomer comprises the following steps: F1: Trifluoropropylmethyldichlorosilane or trifluoropropylmethylcyclotrisiloxane or 1,3,5-trimethyl-1,3,5-tris(1H,1H,2H,2H-perfluorooctyl)cyclotrisiloxane as raw materials and 2.2 times the molar equivalent of 1,1,3,3-tetramethylsiloxane are hydrolyzed under the catalysis of water or trifluoromethanesulfonic acid to generate methylsiloxane containing fluorinated side chains. Its molecular structure is as follows: Where R2 is C2H4CF3 or C2H4C6F 13 , n is an integer from 0 to 3; F2: Using the prepared fluorinated side chain methylsiloxane as raw material, petroleum ether and Karstedt catalyst were stirred evenly, and 2.5 times the molar equivalent of 1,2-epoxy-4-vinylcyclohexane was added dropwise. After the addition was complete, the mixture was refluxed to generate a fluorinated organosilicon epoxy resin monomer. Its molecular structure is as follows: Where R2 is C2H4CF3 or C2H4C6F 13 , n is an integer from 0 to 3.

4. The embossing adhesive according to claim 1, wherein: The organosilicon crosslinking agent is selected from one or more of the following:

5. The embossing adhesive according to claim 1, wherein: The active diluent is selected from one or more of the following:

6. The embossing adhesive according to claim 1, wherein: The cationic photoinitiator is one or more of diaryliodonium salts or triarylsulfonium salts; and the auxiliary agent includes a leveling agent or a defoaming agent.

7. A method for preparing the embossing adhesive according to any one of claims 1 to 6, characterized in that: The following steps are involved: M1: Add silicone crosslinking agent, reactive diluent, photoinitiator and auxiliary agent to the fluorine-containing silicone epoxy resin monomer and stir in a dark environment for 15 to 30 hours; M2: Degas under vacuum for 0.5 to 3 hours to obtain.

8. A stamping method, characterized in that: The method of using the embossing adhesive according to any one of claims 1 to 6 comprises the following steps: (a) using a thermoplastic polymer or a thermosetting polymer as a base layer; (b) spin-coating a layer of adhesion promoter on the base layer, and then spin-coating a layer of the embossing adhesive as the embossing layer, wherein the viscosity of the embossing adhesive is 5 mPa·s to 5000 mPa·s; (c) The embossing layer is pressed onto the surface of the stamp with a pattern after being treated with an anti-adhesive agent, and the embossing is performed under conditions of 0.5 to 3 atm. After the embossing adhesive completely fills the gaps in the stamp, ultraviolet light is irradiated through the back of the base layer stamp to polymerize it. The curing time is less than or equal to 5 minutes. After the embossing adhesive is cured and formed, it is demolded to obtain the embossed pattern.

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