Polythionocarbamate-propylene derivative block polymer, preparation method thereof, nanoimprint optical adhesive containing polythionocarbamate-propylene derivative block polymer and application of nanoimprint optical adhesive

Abstract

The invention provides a polythionocarbamate-propylene derivative block polymer, a preparation method of the polythionocarbamate-propylene derivative block polymer, a nanoimprint optical adhesive containing the polythionocarbamate-propylene derivative block polymer and application of the nanoimprint optical adhesive. The polythionocarbamate-propylene derivative block polymer is prepared from the following raw materials: a polythionocarbamate oligomer and a polyfunctional propylene derivative monomer; the molecular structure of the polythionocarbamate oligomer contains a carbon-carbon double bond; the functionality of the multifunctional propylene derivative monomer is greater than or equal to 2; the polyfunctional propylene derivative monomer comprises polyfunctional acrylic ester and / or polyfunctional allyl ether. The polythionocarbamate-propylene derivative block polymer has high refractive index, crosslinking degree and photocuring reaction activity, and the nanoimprint optical adhesive prepared from the polythionocarbamate-propylene derivative block polymer also has high refractive index, good light transmittance performance and processability, high hardness and adhesive force, and can be used for preparing the nanoimprint optical adhesive. The damp-heat aging resistance and the cold and hot impact resistance are good, the transfer printing efficiency is high, and the precision is high.

Description

Technical Field

[0001] The present invention belongs to the technical field of optical materials, and in particular relates to a polythiourethane-propylene derivative block polymer and a preparation method thereof, a nanoimprint optical adhesive containing the same, and applications thereof. Background Art

[0002] With the continuous updating and iteration of technology, the demand for miniaturization, performance improvement and manufacturing process innovation of optical devices is increasing. High refractive index optical nanoimprint glue can meet the urgent demand for high-performance optical devices in AR / VR, consumer electronics, optical communications and other fields through low-cost and high-precision preparation processes. Specifically, high refractive index optical adhesive (OCR) has significant advantages in miniaturization and performance improvement of optical devices, such as in the optical waveguide design of AR / VR devices, microlens array (MLA) and 3D display technology, as well as optical sensors and optical communications. At the same time, nanoimprint glue can replace traditional photolithography technology (such as ArF / KrF photoresist), which not only reduces the high cost and complex process requirements, but also has excellent fluidity and filling properties, and can completely replicate nanoscale structures, thereby further improving the performance and precision of optical devices.

[0003] Nanoimprint technology is a revolutionary micro-nano manufacturing process that combines the advantages of high throughput, high resolution and low cost, and provides an innovative solution for the batch preparation of large-scale, high-precision micro-nano structures. This technology can efficiently prepare lightweight (density <1.5g / cm2) optical resins by directly transferring pre-designed micro-nano topological patterns into high-refractive index optical resin polymers. 3 ), high performance (optical loss <0.1dB / cm) and high integration characteristics of optical components, showing significant advantages in reducing manufacturing costs (about 40% lower than traditional photolithography processes). However, the refractive index of organic optical resins is generally low (usually <1.60). This is mainly due to the fact that the introduction of high refractive index groups often leads to enhanced intermolecular forces, which in turn affects the light transmittance and processing characteristics of the material; such as the introduction of condensed ring aromatic hydrocarbons, although it can increase the refractive index of the resin, it will lead to significant limitations on the inherent solubility and transmittance of the material (transmittance decreases by 15-30%), which seriously restricts its molding processing performance and optical properties; while maintaining the excellent light transmittance of the material (transmittance in the visible light region>90%) and good processing performance (heat deformation temperature>150℃), it still faces major technical challenges to improve the refractive index of the resin. In addition, the existing technology of high refractive index organic optical resins generally relies on multi-step synthesis processes. The cumbersome synthesis route leads to low product yield (usually <65%), resulting in high industrialization costs; and its photocuring activity is low, and thermal curing is mostly used, which has low reaction efficiency.

[0004] In addition, although other optical resins such as polythiourethane resin also have a high refractive index, their common defects are slow photocuring rate and low cross-linking degree, which in turn lead to problems such as low precision of nano-transfer adhesive and pattern loss.

[0005] For example, CN118853064A discloses a nanoimprint adhesive and a preparation method thereof, which includes modified metal oxide particles, a photocurable composition, a thermal curable composition, a photoinitiator, and an auxiliary agent. The nanoimprint adhesive has the advantages of low viscosity, high filling capacity, and high refractive index, but its preparation process is relatively complicated, requiring photocuring before thermal curing for complete reaction, which is inefficient. Another example is CN114149589A discloses a high-refractive index UV-curable nanoimprint adhesive, which is obtained by dissolving a high-refractive index UV-curable resin in an organic solvent together with a photoinitiator. The nanoimprint adhesive of this invention has a resin main chain of a Ti-O-Ti structure oligomer, and the oligomer has o-phenylphenoxy and a double bond on the side chain, which effectively increases the refractive index, but the system introduces a solvent, which does not meet environmental protection requirements. In addition, the hardness and adhesion of the aforementioned imprint adhesive need to be further improved, and the shrinkage rate and curing time need to be further reduced.

[0006] Therefore, developing an optical resin that can ensure that the nanoimprint optical adhesive has high refractive index, excellent light transmittance and good processing performance, as well as good aging resistance, resistance to cold and hot shock, high hardness and adhesion, is an urgent problem to be solved in this field. Summary of the Invention

[0007] In response to the shortcomings of the prior art, the present invention aims to provide a polythiourethane-propylene derivative block polymer, a preparation method thereof, a nanoimprint optical adhesive containing the same, and applications thereof. The polythiourethane-propylene derivative block polymer solves the problems of low refractive index, low crosslinking degree, low photocuring reactivity, and low reaction efficiency of organic optical resins in the prior art. The nanoimprint optical adhesive prepared from the polythiourethane-propylene derivative block polymer combines high refractive index, good light transmittance, and processability, with high hardness and adhesion, good resistance to wet and hot aging, and good resistance to thermal shock. It also offers the advantages of high precision, high transfer efficiency, and guaranteed pattern integrity.

[0008] To achieve this object, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides a polythiourethane-propylene derivative block polymer, wherein the raw materials for preparing the polythiourethane-propylene derivative block polymer include a polythiourethane oligomer and a multifunctional propylene derivative monomer; the molecular structure of the polythiourethane oligomer contains a carbon-carbon double bond; the functionality of the multifunctional propylene derivative is ≥2; the multifunctional propylene derivative monomer includes a multifunctional acrylate and / or a multifunctional allyl ether; and the raw materials for preparing the polythiourethane oligomer include a polyisocyanate, and the polyisocyanate includes an aliphatic polyisocyanate and / or an alicyclic polyisocyanate.

[0010] In the present invention, the polythiourethane oligomer is prepared from a specific type of polyisocyanate as a raw material, and a multifunctional propylene derivative monomer is introduced. The resulting polythiourethane-propylene derivative block polymer has a high refractive index, a high degree of crosslinking, and a high photocuring reaction activity. The nanoimprint optical adhesive prepared from the polythiourethane-propylene derivative block polymer also has a high refractive index and good light transmittance and processing properties. At the same time, it has high hardness and adhesion, good resistance to moisture and heat aging and resistance to cold and hot shock, high transfer efficiency, high precision, and low cost.

[0011] Preferably, the carbon-carbon double bonds are distributed at the ends of the molecular structure of the polythiourethane oligomer.

[0012] Preferably, the refractive index of the polythiourethane oligomer is greater than 1.6, for example, it may be 1.62, 1.64, 1.66, 1.68, 1.7, 1.72, 1.74, 1.76, 1.78, 1.8, 1.82, 1.84, 1.86, 1.88, 1.9, etc.

[0013] Preferably, the raw materials for preparing the polythiourethane oligomer further include polythiol and monofunctional acrylate; the molecular structure of the monofunctional acrylate contains isocyanate groups or hydroxyl groups.

[0014] In the present invention, the polythiourethane oligomer uses polythiol, polyisocyanate and monofunctional acrylate as raw materials, and constructs a cross-linked network through the reaction of the thiol group of the polythiol with the isocyanate group, which is beneficial to improving the cross-linking degree, refractive index and photocuring reaction activity of the polymer, so that the transmittance of the prepared optical adhesive is improved while maintaining processing fluidity, effectively overcoming the shortcomings of traditional condensed ring aromatic hydrocarbon systems that cannot have both good optical and performance processing properties.

[0015] Preferably, the molar ratio of the polythiol, polyisocyanate and monofunctional acrylate is (0.9-1.3):(0.3-2):1, wherein the specific value of (0.9-1.3) can be, for example, 0.9, 0.92, 0.95, 0.98, 1, 1.02, 1.05, 1.08, 1.1, 1.12, 1.15, 1.18, 1.2, 1.22, 1.25, 1.28, 1.3, etc. ; The specific values in (0.3~2) can be, for example, 0.3, 0.32, 0.34, 0.36, 0.38, 0.4, 0.42, 0.44, 0.46, 0.48, 0.5, 0.52, 0.54, 0.56, 0.58, 0.6, 0.62, 0.64, 0.66, 0.68, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.4, 1.6, 1.8, 2, etc.

[0016] In the present invention, the monofunctional acrylate contains an isocyanate group, and the molar ratio of the polythiol, polyisocyanate and monofunctional acrylate is (0.9-1.3):(0.3-0.7):1; the monofunctional acrylate contains a hydroxyl group, and the molar ratio of the polythiol, polyisocyanate and monofunctional acrylate is (0.9-1.3):(1-2):1.

[0017] Preferably, the polythiol is selected from the compound having the structure shown in Formula I and / or the compound having the structure shown in Formula II, more preferably the compound having the structure shown in Formula II.

[0018] HS-R-SH Formula I.

[0019] HS-R1-S-R2-SH Formula II.

[0020] Wherein, R, R1, and R2 are each independently selected from any one of substituted or unsubstituted C1-C10 straight or branched alkylene, substituted or unsubstituted C3-C8 cycloalkylene, and substituted or unsubstituted C6-C20 arylene; and the substituted substituent includes a hydroxyl group.

[0021] In the present invention, the C1-C10 straight or branched chain alkylene group may be, for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10 straight or branched chain alkylene groups; examples thereof include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups; the C3-C8 cycloalkylene group may be, for example, C3, C4, C5, C6, C7, or C8 cycloalkylene groups; the C6-C20 arylene group may be, for example, C6, C7, C8, C9, C10, C12, C14, C16, C18, or C20 arylene groups; examples thereof include, but are not limited to, phenylene groups. The same expressions hereinafter have the same meanings.

[0022] Preferably, the polythiol includes at least one of 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,2-benzenedithiol, 1,4-benzenedithiol, 1,2-cyclohexanedithiol, dimercaprol, 4,4-thiodiphenylthiol or 2-mercaptoethyl sulfide.

[0023] In the present invention, it is more preferred to compound a polythiol containing a flexible thioether bond with an alicyclic isocyanate, and the resulting block polymer to prepare the nanoimprint optical adhesive has better hardness, adhesion, optical properties, resistance to moisture and heat aging, and resistance to cold and hot shock, and has a shorter curing time and higher reaction efficiency.

[0024] Preferably, the polyisocyanate includes at least one of hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane-4,4'-diisocyanate.

[0025] Preferably, the monofunctional acrylate includes at least one of isocyanateethyl acrylate, isocyanateethyl methacrylate, isocyanate acrylate prepolymer, hydroxyethyl acrylate, hydroxypropyl acrylate or hydroxyethyl methacrylate.

[0026] Preferably, the molar ratio of the monofunctional acrylate to the multifunctional propylene derivative monomer is 1:(0.6-3), wherein the specific value of (0.6-3) can be, for example, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, etc.

[0027] Preferably, the multifunctional propylene derivative monomer includes at least one of 1,6-hexanediol diacrylate, triethylene glycol dimethacrylate, tripropylene glycol diacrylate, dioxanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol triallyl ether or pentaerythritol tetraacrylate.

[0028] In the present invention, the content of the multifunctional propylene derivative monomer is within a specific range, that is, the molar ratio of the monofunctional acrylate to the multifunctional propylene derivative monomer is within a specific range, which can enable the optical adhesive to have both a short curing time and a low shrinkage rate, thereby being more conducive to subsequent transfer.

[0029] In the present invention, the polythiourethane-propylene derivative block polymer has a structure shown in Formula III or Formula IV:

[0030]

[0031] In formula III or formula IV, R1 is selected from substituted or unsubstituted C1-C10 straight or branched alkylene, substituted or unsubstituted C3-C8 cycloalkylene, substituted or unsubstituted C6-C20 arylene, -R N1 -SR N2 -Any one of; R N1 、R N2 Each is independently selected from any one of a substituted or unsubstituted C1-C10 straight or branched alkylene group, a substituted or unsubstituted C3-C8 cycloalkylene group, and a substituted or unsubstituted C6-C20 arylene group; the substituted substituent includes a hydroxyl group.

[0032] In formula III or formula IV, R2 is selected from any one of substituted or unsubstituted C1~C10 straight or branched alkylene, substituted or unsubstituted C3~C8 cycloalkylene, -Ar1-(CH2)m1-Ar2- or -(CH2)m2-Ar3-(CH2)m3-; Ar1, Ar2, Ar3 are each independently selected from any one of substituted or unsubstituted C3~C8 cycloalkylene; the number of the substituted substituents is ≥1, and the substituted substituents include C1~C6 alkyl; m1, m2, m3 are each independently selected from an integer ≥0.

[0033] In formula III or formula IV, R3 is selected from a linear or branched alkylene group having ≥1 carbon atom.

[0034] In formula III or formula IV, R4 is selected from any one of substituted or unsubstituted C1-C20 straight or branched alkylene, substituted or unsubstituted C3-C10 cycloalkylene; at least one C in the C1-C20 straight or branched alkylene and C3-C10 cycloalkylene can be independently replaced by O; the number of the substituted substituents is ≥1, and the substituted substituents include C1-C6 alkyl, hydroxyl, -O-CO-CR 11 =CR 11 R 12 、-O-(CH2)m4-CR 11 =CR 11 R 12 Any one of ; m4 is selected from an integer ≥0.

[0035] In the present invention, the above structure involves R 11 are the same or different and are independently selected from C1-C5 alkyl, C1-C5 alkoxy or hydrogen atom; R 12 Selected from C1-C5 alkyl, C1-C5 alkoxy or hydrogen atom.

[0036] In Formula III or Formula IV, n1, n2, and n3 are each independently selected from integers ≥ 0. In the present invention, the polythiourethane-propylene derivative block polymer has a structure shown in Formula V or Formula VI:

[0037]

[0038] In Formula V or Formula VI, R1, R2, R3, R4, R 11 、R 12 , n1, n2, and n3 are each independently selected from the same ranges as those of Formula III and Formula IV.

[0039] In Formula III, Formula IV, Formula V, and Formula VI, Each independently represents a branched structure, which may be a polythiourethane segment, an acrylate segment or an allyl ether segment.

[0040] In a second aspect, the present invention provides a method for preparing the polythiourethane-propylene derivative block polymer according to the first aspect, the preparation method specifically comprising the following steps:

[0041] The polythiourethane oligomer is reacted with a multifunctional propylene derivative monomer to obtain the polythiourethane-propylene derivative block polymer.

[0042] Preferably, the preparation method of the polythiourethane oligomer comprises:

[0043] In the presence of a catalyst, polythiol, polyisocyanate and monofunctional acrylate are mixed and reacted to obtain the polythiourethane oligomer.

[0044] Preferably, the catalyst comprises at least one of triethylamine, triethanolamine, 1,6-hexamethylenediamine, isophoronediamine, 1,4-cyclohexanediamine or 4,4-diaminodicyclohexylmethane.

[0045] In the present invention, the mass of the catalyst is 0.01-0.1% of the total mass of the polythiol, polyisocyanate and monofunctional acrylate, for example, it can be 0.01%, 0.02%, 0.04%, 0.06%, 0.08%, 0.1%, etc.

[0046] In the present invention, the reaction of the polythiol, polyisocyanate and monofunctional acrylate is carried out in the presence of a protective atmosphere, which includes but is not limited to nitrogen; the reaction temperature is room temperature, the reaction time is 1 to 10 hours, and the reaction is carried out until transparent.

[0047] Preferably, the reaction temperature of the polythiourethane oligomer and the multifunctional propylene derivative is room temperature, and the reaction time is 0.5 to 24 hours, for example, 0.5 hours, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, etc.

[0048] In the present invention, after the reaction of the polythiourethane oligomer and the multifunctional propylene derivative is completed, a post-treatment step is further included; the post-treatment includes rotary evaporation, the rotary evaporation temperature is 50 to 100° C., the rotary evaporation time is 2 to 24 hours, and the vacuum degree is -0.09 to -0.098 MPa.

[0049] The preparation method described herein utilizes a one-step bulk polymerization technique catalyzed by an amine catalyst, where a thiol-click reaction is performed between a polythiol, a polyisocyanate, and an acrylate to construct a crosslinked network. The introduction of a multifunctional propylene derivative monomer enhances the crosslinking degree and photocuring activity, resulting in an optical adhesive with high transfer efficiency and precision. Compared to traditional multi-step processes, this method shortens reaction time, improves yield, and reduces costs, resulting in a product yield of over 89%.

[0050] In a third aspect, the present invention provides a composite resin comprising the polythiourethane-propylene derivative block polymer according to the first aspect and inorganic nanoparticles.

[0051] Preferably, the inorganic nanoparticles are formed in the polythiourethane-propylene derivative block polymer by in-situ polymerization.

[0052] In the present invention, uniformly dispersed inorganic nanoparticles are constructed in a polymer matrix through an in-situ generation method, and the inorganic nanoparticles are compounded with polymers to obtain a composite resin with a higher refractive index, which is beneficial to further improve the optical properties, processing properties, resistance to moisture and heat aging, resistance to cold and hot shocks, as well as hardness, adhesion, refractive index, etc. of the optical adhesive.

[0053] Preferably, the inorganic nanoparticles include titanium dioxide and / or zirconium dioxide.

[0054] Preferably, the mass ratio of the precursor of the inorganic nanoparticles to the polythiourethane-propylene derivative block polymer is 1:(5-14), wherein the specific value of (5-14) can be, for example, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, etc.

[0055] In a fourth aspect, the present invention provides a method for preparing the composite resin according to the second aspect, the preparation method comprising the following steps:

[0056] The polythiourethane-propylene derivative block polymer is mixed with the precursor of the inorganic nanoparticles and reacted under acid catalysis conditions to obtain the composite resin.

[0057] Preferably, the precursor of the inorganic nanoparticles includes at least one of zirconium n-propoxide, tetrabutyl titanate or zirconium butoxide.

[0058] In the present invention, taking tetrabutyl titanate as the precursor as an example, the in-situ polymerization reaction route is as follows.

[0059] Ti(OR)4+H2O→Ti(OH)4+ROH

[0060] Ti(OH)4→TiO2+H2O, wherein R is selected from n-butyl.

[0061] Preferably, the mixed raw materials further include a silane coupling agent.

[0062] Preferably, the mass ratio of the silane coupling agent to the precursor of the inorganic nanoparticles is (1-3):1, wherein the specific values in (1-3) can be, for example, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, etc.

[0063] Preferably, the silane coupling agent includes at least one of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(β-methoxyethoxy)silane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane or 3-mercaptopropyltriethoxysilane.

[0064] In the present invention, by adding a silane coupling agent and adopting a unique interface coupling design, the compatibility of the inorganic nanoparticles and the system is improved, which is beneficial to improving the light transmittance of the optical adhesive.

[0065] Preferably, the reaction temperature is room temperature, and the reaction time is 0.5 to 3 h, for example, 0.5 h, 0.6 h, 0.8 h, 1 h, 1.2 h, 1.4 h, 1.6 h, 1.8 h, 2 h, 2.2 h, 2.4 h, 2.6 h, 2.8 h, 3 h, etc.

[0066] In the present invention, the raw materials for mixing the polythiourethane-propylene derivative block polymer with the precursor of the inorganic nanoparticles further include a solvent.

[0067] Preferably, the preparation method of the composite resin includes: stirring and mixing the polythiourethane-propylene derivative block polymer with a first solvent and an acid catalyst at room temperature until transparent; then, adding a precursor of inorganic nanoparticles, an optional silane coupling agent and a second solvent thereto to obtain a mixed liquid; then reacting the mixed liquid at room temperature for 0.5 to 3 hours, and rotary evaporating the obtained reactant at a temperature of 50 to 100° C. and a vacuum degree of -0.09 to -0.098 MPa for 2 to 24 hours to obtain the composite resin.

[0068] In the present invention, the first solvent and the second solvent are the same or different, and each independently includes any one or more of anhydrous ethanol, deionized water, N-methylpyrrolidone, methanol, tetrahydrofuran, ethyl acetate, toluene, benzyl alcohol, N,N-dimethylformamide, isopropyl alcohol, acetylacetone, chloroform, dimethyl sulfoxide, isobutanol, propylene glycol methyl ether, n-butanol, cyclohexane, n-hexane or methyl isobutyl ketone.

[0069] In the present invention, the acid catalyst includes any one or more of glacial acetic acid, hydrochloric acid, and sulfuric acid.

[0070] In the present invention, the mass of the acid catalyst is 1 to 6% of the mass of the polythiourethane-propylene derivative block polymer, for example, it can be 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, etc.

[0071] In the present invention, the mass of the solvent is such that the solid content of the mixed solution (ie the total mass percentage of other components excluding the solvent) is 20 to 50%.

[0072] In a fifth aspect, the present invention provides a nanoimprint optical adhesive, which comprises, by weight, 45 to 100 parts of the composite resin described in the third aspect, 5 to 30 parts of an acrylate reactive diluent, and 0.1 to 5 parts of a photoinitiator.

[0073] The nanoimprint optical adhesive described in this invention exhibits low viscosity, high adhesion, and rapid curing properties through the coordinated interaction of its components. The resulting material system is RoHS-certified and suitable for roll-to-roll nanoimprinting processes, demonstrating significant advantages in the manufacture of optoelectronic components such as AR diffraction waveguides.

[0074] In the present invention, 45 to 100 parts of the composite resin described in the third aspect can be, for example, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, etc.

[0075] In the present invention, the content of the composite resin is relatively low, the refractive index and hardness are significantly reduced, the adhesion is poor and the shrinkage rate is high.

[0076] In the present invention, 5 to 30 parts of acrylic acid ester reactive diluent can be, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, etc.

[0077] Preferably, the acrylic ester reactive diluent includes at least one of isobornyl acrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, o-phenylphenoxyethyl acrylate, lauryl methacrylate, octadecyl methacrylate, isooctyl acrylate, 1,6-hexanediol diacrylate, triethylene glycol dimethacrylate or dipropylene glycol diacrylate.

[0078] Preferably, the photoinitiator includes at least one of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, dibenzophenone, isopropylthioxanthone or methyl o-benzoylbenzoate.

[0079] Preferably, the nanoimprint optical adhesive further includes 0.1 to 5 parts of an auxiliary agent in parts by weight, for example, 0.1, 0.2, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, etc.

[0080] In the present invention, the auxiliary agent includes but is not limited to any one or more of a coupling agent, a plasticizer, a defoaming agent, and a leveling agent.

[0081] In the present invention, the preparation method of the nanoimprint optical adhesive comprises: stirring and mixing a composite resin, an acrylate reactive diluent, a photoinitiator and optional auxiliary agents at a temperature not exceeding 50° C. for 0.5 to 3 hours, and then performing vacuum degassing to obtain the nanoimprint optical adhesive.

[0082] In a sixth aspect, the present invention provides an optical device, wherein the material of the optical device includes the polythiourethane-propylene derivative block polymer described in the first aspect, the composite resin described in the third aspect, or the nanoimprint optical adhesive described in the fifth aspect.

[0083] Preferably, the optical device includes a device prepared using nanoimprint technology.

[0084] The numerical range described in the present invention includes not only the point values listed above, but also any point values between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range.

[0085] Compared with the prior art, the present invention has the following beneficial effects:

[0086] The polythiourethane-propylene derivative block polymer provided by the present invention adopts a specific type of polyisocyanate as the raw material for preparing the polythiourethane oligomer, and simultaneously introduces a multifunctional propylene derivative structural unit. The formed polythiourethane-propylene derivative block polymer has a high refractive index, a degree of crosslinking, and a photocuring reaction activity. The nanoimprint optical adhesive prepared from the polythiourethane-propylene derivative block polymer also has a high refractive index and both good light transmittance and processing properties. At the same time, it has high hardness and adhesion, good resistance to wet and hot aging and resistance to cold and hot shock, high transfer efficiency, high precision, and low cost. DETAILED DESCRIPTION

[0087] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0088] Example 1

[0089] This embodiment provides a polythiourethane-acrylate block polymer, wherein raw materials for preparing the polythiourethane-acrylate block polymer include a polythiourethane oligomer and 1,6-hexanediol diacrylate; the raw materials for preparing the polythiourethane oligomer include 4,4-thiodiphenylmercaptan, dicyclohexylmethane-4,4'-diisocyanate, and ethyl isocyanate acrylate in a molar ratio of 1:0.5:1; the molar ratio of ethyl isocyanate acrylate to 1,6-hexanediol diacrylate is 1:1.5, and the raw materials for preparing the polythiourethane oligomer also include triethylamine, and the amount of triethylamine used is 0.02% of the total mass of 4,4-thiodiphenylmercaptan, dicyclohexylmethane-4,4'-diisocyanate, and ethyl isocyanate acrylate.

[0090] This embodiment provides a method for preparing a polythiourethane-acrylate block polymer, which specifically comprises the following steps:

[0091] According to the formula, 4,4-thiodiphenylmercaptan and dicyclohexylmethane-4,4'-diisocyanate are placed in a reaction kettle, ethyl isocyanate acrylate and triethylamine are slowly added thereto, and the mixture is stirred at room temperature for 3 hours. The mixture is mixed evenly until transparent to obtain a polythiourethane oligomer; then 1,6-hexanediol diacrylate is slowly added thereto, and the mixture is stirred at room temperature for 8 hours. The obtained reactant is rotary evaporated at a temperature of 50°C and a vacuum degree of -0.05 MPa for 8 hours, and then cooled to room temperature to obtain the polythiourethane-acrylate block polymer.

[0092] In the present invention, the reaction scheme of the polythiourethane-acrylate block polymer provided in Example 1 is shown below.

[0093]

[0094] Example 2

[0095] This embodiment provides a polythiourethane-acrylate block polymer, wherein raw materials for preparing the polythiourethane-acrylate block polymer include a polythiourethane oligomer and 1,6-hexanediol diacrylate; the raw materials for preparing the polythiourethane oligomer include 2-mercaptoethyl sulfide, dicyclohexylmethane-4,4'-diisocyanate, and ethyl isocyanate acrylate in a molar ratio of 1.1:0.55:1; the molar ratio of ethyl isocyanate acrylate to 1,6-hexanediol diacrylate is 1:1; the raw materials for preparing the polythiourethane oligomer also include triethylamine, and the amount of triethylamine used is 0.05% of the total mass of 2-mercaptoethyl sulfide, dicyclohexylmethane-4,4'-diisocyanate, and ethyl isocyanate acrylate.

[0096] This embodiment provides a method for preparing a polythiourethane-acrylate block polymer, and the specific steps are the same as those in Example 1.

[0097] Example 3

[0098] This embodiment provides a polythiourethane-acrylate block polymer. The raw materials for preparing the polythiourethane-acrylate block polymer include a polythiourethane oligomer and 1,6-hexanediol diacrylate. The raw materials for preparing the polythiourethane oligomer include 4,4-thiodiphenylmercaptan, isophorone diisocyanate, and ethyl isocyanate methacrylate in a molar ratio of 0.95:0.43:1. The molar ratio of ethyl isocyanate methacrylate to 1,6-hexanediol diacrylate is 1:1.9. The raw materials for preparing the polythiourethane oligomer also include triethylamine, and the amount of triethylamine used is 0.02% of the total mass of 4,4-thiodiphenylmercaptan, isophorone diisocyanate, and ethyl isocyanate methacrylate.

[0099] This embodiment provides a method for preparing a polythiourethane-acrylate block polymer. The only difference from Example 1 is that 1,6-hexanediol diacrylate is added and the reaction is continued with stirring at room temperature for 10 hours. Other process parameters are the same as those in Example 1.

[0100] Example 4

[0101] This embodiment provides a polythiourethane-acrylate block polymer, wherein raw materials for preparing the polythiourethane-acrylate block polymer include a polythiourethane oligomer and 1,6-hexanediol diacrylate; the raw materials for preparing the polythiourethane oligomer include 4,4-thiodiphenylmercaptan, hexamethylene diisocyanate, and ethyl isocyanate acrylate in a molar ratio of 1.14:0.52:1; the molar ratio of ethyl isocyanate acrylate to 1,6-hexanediol diacrylate is 1:1.19; and the raw materials for preparing the polythiourethane oligomer also include triethylamine, and the amount of triethylamine used is 0.02% of the total mass of 4,4-thiodiphenylmercaptan, hexamethylene diisocyanate, and ethyl isocyanate acrylate.

[0102] This embodiment provides a method for preparing a polythiourethane-acrylate block polymer, and the specific steps are the same as those in Example 1.

[0103] Example 5

[0104] This embodiment provides a polythiourethane-acrylate block polymer, wherein raw materials for preparing the polythiourethane-acrylate block polymer include a polythiourethane oligomer and 1,6-hexanediol diacrylate; the raw materials for preparing the polythiourethane oligomer include 4,4-thiodiphenylmercaptan, dicyclohexylmethane-4,4'-diisocyanate, and ethyl isocyanate acrylate in a molar ratio of 1.25:0.55:1; the molar ratio of ethyl isocyanate acrylate to 1,6-hexanediol diacrylate is 1:1.5; the raw materials for preparing the polythiourethane oligomer also include triethylamine, and the amount of triethylamine used is 0.02% of the total mass of 4,4-thiodiphenylmercaptan, dicyclohexylmethane-4,4'-diisocyanate, and ethyl isocyanate acrylate.

[0105] This embodiment provides a method for preparing a polythiourethane-acrylate block polymer. The only difference from Example 1 is that 1,6-hexanediol diacrylate is added, and the reaction is continued with stirring at room temperature for 12 hours, and rotary evaporation is performed for 12 hours. Other process parameters are the same as those in Example 1.

[0106] Example 6

[0107] This embodiment provides a polythiourethane-acrylate block polymer, which differs from Example 1 only in that the content of 1,6-hexanediol diacrylate is adjusted so that the molar ratio of ethyl isocyanate acrylate to 1,6-hexanediol diacrylate is 1:0.4. Other raw materials, amounts used, and preparation methods are the same as those in Example 1.

[0108] Example 7

[0109] This embodiment provides a polythiourethane-acrylate block polymer, which differs from Example 1 only in that the content of 1,6-hexanediol diacrylate is adjusted so that the molar ratio of ethyl isocyanate acrylate to 1,6-hexanediol diacrylate is 1:4. Other raw materials, amounts used, and preparation methods are the same as those in Example 1.

[0110] Example 8

[0111] This embodiment provides a polythiourethane-acrylate block polymer, which differs from Example 1 only in that 4,4-thiodibenzenethiol is replaced with an equal molar amount of 1,4-benzenedithiol. Other raw materials, amounts used, and preparation methods are the same as those in Example 1.

[0112] Example 9

[0113] This embodiment provides a polythiourethane-allyl ether block polymer, which differs from Example 1 only in that ethyl isocyanate acrylate is replaced with an equal molar amount of hydroxyethyl acrylate, and the content of dicyclohexylmethane-4,4'-diisocyanate is adjusted so that the molar ratio of 4,4-thiodiphenylmercaptan, dicyclohexylmethane-4,4'-diisocyanate, and hydroxyethyl acrylate is 1:1.5:1; other raw materials, amounts, and preparation methods are the same as in Example 1.

[0114] Comparative Example 1

[0115] This comparative example provides a polythiourethane, namely the polythiourethane oligomer obtained in Example 1.

[0116] Comparative Example 2

[0117] This comparative example provides a high-refractive index aromatic acrylate resin, which is R1601-L4 from Double Bond Chemical.

[0118] Comparative Example 3

[0119] This comparative example provides a polythiourethane-acrylate block polymer, which differs from Example 1 only in that dicyclohexylmethane-4,4'-diisocyanate is replaced by an equimolar amount of toluene diisocyanate, and the other raw materials, amounts and preparation methods are the same as those in Example 1.

[0120] Application Example 1-1

[0121] This application example provides a composite resin, which includes the polythiourethane-acrylate block polymer provided in Example 1 and titanium dioxide; the titanium dioxide is prepared by an in-situ polymerization method using tetrabutyl titanate as a raw material and is formed in the polythiourethane-acrylate block polymer; the mass ratio of the tetrabutyl titanate to the polythiourethane-acrylate block polymer is 1:14.

[0122] This application example provides a method for preparing a composite resin, which specifically includes the following steps:

[0123] 50 parts of anhydrous ethanol, 1 part of glacial acetic acid and 1 part of deionized water were placed in a reactor, and then 70 parts of polythiourethane-acrylate block polymer were added thereto. After stirring and mixing evenly, 5 parts of tetrabutyl titanate, 10 parts of silane coupling agent (3-(methacryloyloxy)propyltrimethoxysilane, the mass ratio of silane coupling agent to tetrabutyl titanate is 2:1) and 50 parts of N-methylpyrrolidone were added dropwise. The reaction was stirred at room temperature for 1 hour. The obtained reactant was rotary evaporated at a temperature of 50°C and a vacuum degree of -0.05 MPa for 12 hours and cooled to room temperature to obtain the composite resin with a yield of 90%.

[0124] Application Example 1-2

[0125] This application example provides a composite resin, which includes the polythiourethane-acrylate block polymer provided in Example 2 and titanium dioxide; the titanium dioxide is prepared by an in-situ polymerization method using tetrabutyl titanate as a raw material and is formed in the polythiourethane-acrylate block polymer; the mass ratio of the tetrabutyl titanate to the polythiourethane-acrylate block polymer is 1:14.

[0126] This application example provides a method for preparing a composite resin, which specifically includes the following steps:

[0127] 60 parts of anhydrous ethanol, 2 parts of glacial acetic acid and 1 part of deionized water were placed in a reactor, and then 70 parts of polythiourethane-acrylate block polymer were added thereto. After stirring and mixing evenly, 5 parts of tetrabutyl titanate, 15 parts of silane coupling agent (3-(2,3-epoxypropoxy)propyltrimethoxysilane, the mass ratio of silane coupling agent to tetrabutyl titanate is 3:1) and 60 parts of N-methylpyrrolidone were added dropwise. The reaction was stirred at room temperature for 1 hour. The obtained reactant was rotary evaporated at a temperature of 50°C and a vacuum degree of -0.05 MPa for 12 hours, and cooled to room temperature to obtain the composite resin with a yield of 90%.

[0128] Application Examples 1-3

[0129] This application example provides a composite resin, which includes the polythiourethane-acrylate block polymer provided in Example 3 and titanium dioxide; the titanium dioxide is prepared by an in-situ polymerization method using tetrabutyl titanate as a raw material and is formed in the polythiourethane-acrylate block polymer; the mass ratio of tetrabutyl titanate to polythiourethane-acrylate block polymer is 1:12.5.

[0130] This application example provides a method for preparing a composite resin, which specifically includes the following steps:

[0131] 100 parts of anhydrous ethanol, 3 parts of glacial acetic acid and 2 parts of deionized water were placed in a reactor, and then 100 parts of polythiourethane-acrylate block polymer were added thereto. After stirring and mixing evenly, 8 parts of tetrabutyl titanate, 15 parts of silane coupling agent (3-mercaptopropyltriethoxysilane, the mass ratio of silane coupling agent to tetrabutyl titanate is 1.875:1) and 100 parts of N-methylpyrrolidone were added dropwise. The reaction was stirred at room temperature for 1 hour. The obtained reactant was rotary evaporated at a temperature of 50°C and a vacuum degree of -0.05 MPa for 12 hours and cooled to room temperature to obtain the composite resin with a yield of 90%.

[0132] Application Examples 1-4

[0133] This application example provides a composite resin, which includes the polythiourethane-acrylate block polymer provided in Example 4 and titanium dioxide; the titanium dioxide is prepared by an in-situ polymerization method using tetrabutyl titanate as a raw material and is formed in the polythiourethane-acrylate block polymer; the mass ratio of the tetrabutyl titanate to the polythiourethane-acrylate block polymer is 1:5.

[0134] This application example provides a method for preparing a composite resin, which specifically includes the following steps:

[0135] 100 parts of anhydrous ethanol, 1 part of glacial acetic acid and 1 part of deionized water were placed in a reactor, and then 50 parts of polythiourethane-acrylate block polymer were added thereto. After stirring and mixing evenly, 10 parts of tetrabutyl titanate, 20 parts of silane coupling agent (3-(methacryloyloxy)propyltrimethoxysilane, the mass ratio of silane coupling agent to tetrabutyl titanate is 2:1) and 100 parts of N-methylpyrrolidone were added dropwise. The reaction was stirred at room temperature for 1 hour. The obtained reactant was rotary evaporated at a temperature of 50°C and a vacuum degree of -0.05 MPa for 12 hours, and cooled to room temperature to obtain the composite resin with a yield of 90%.

[0136] Application Examples 1-5

[0137] This application example provides a composite resin, which includes the polythiourethane-acrylate block polymer provided in Example 5 and titanium dioxide; the titanium dioxide is prepared by an in-situ polymerization method using tetrabutyl titanate as a raw material and is formed in the polythiourethane-acrylate block polymer; the mass ratio of the tetrabutyl titanate to the polythiourethane-acrylate block polymer is 1:12.

[0138] This application example provides a method for preparing a composite resin, which specifically includes the following steps:

[0139] 80 parts of anhydrous ethanol, 3 parts of glacial acetic acid and 1 part of deionized water were placed in a reactor, and then 60 parts of polythiourethane-acrylate block polymer were added thereto. After stirring and mixing evenly, 5 parts of tetrabutyl titanate, 10 parts of silane coupling agent (3-(2,3-epoxypropoxy)propyltrimethoxysilane, the mass ratio of silane coupling agent to tetrabutyl titanate is 2:1) and 80 parts of N-methylpyrrolidone were added dropwise. The reaction was stirred at room temperature for 1 hour. The obtained reactant was rotary evaporated at a temperature of 50°C and a vacuum degree of -0.05 MPa for 12 hours, and cooled to room temperature to obtain the composite resin with a yield of 90%.

[0140] Application Examples 1-6 to 1-9

[0141] Application Examples 1-6 to 1-9 respectively provide a composite resin, which differs from Application Example 1-1 only in that the polythiourethane-acrylate block polymers are provided by Examples 6 to 9 respectively, and other raw materials, amounts and preparation methods are the same as those of Application Example 1-1.

[0142] Application Examples 1-10

[0143] This application example provides a composite resin, which differs from application example 1-1 only in that the total mass of the tetrabutyl titanate and the polythiourethane-acrylate block polymer remains unchanged, with a mass ratio of 1:2, and other raw materials, amounts, and preparation methods are the same as those in application example 1-1.

[0144] Application Examples 1-11

[0145] This application example provides a composite resin, which differs from application example 1-1 only in that the total mass of the tetrabutyl titanate and the polythiourethane-acrylate block polymer remains unchanged, with a mass ratio of 1:16. Other raw materials, amounts, and preparation methods are the same as those in application example 1-1.

[0146] Comparative Application Example 1-1

[0147] This comparative application example provides a composite resin, which differs from Application Example 1-1 only in that the polythiourethane-acrylate block polymer provided in Example 1 is replaced with an equal mass of polythiourethane provided in Comparative Example 1, and the other raw materials, amounts used, and preparation methods are the same as those in Application Example 1-1.

[0148] Comparative Application Examples 1-2

[0149] This comparative application example provides a composite resin, which differs from Application Example 1-1 only in that the polythiourethane-acrylate block polymer provided in Example 1 is replaced with an aromatic acrylate resin of equal mass provided in Comparative Example 2, and the other raw materials, amounts used, and preparation methods are the same as those in Application Example 1-1.

[0150] Comparative Application Examples 1-3

[0151] This comparative application example provides a composite resin, which differs from Application Example 1-1 only in that the polythiourethane-acrylate block polymer provided in Example 1 replaces the polythiourethane-acrylate block polymer provided in Comparative Example 3, and the other raw materials, amounts used, and preparation methods are the same as those in Application Example 1-1.

[0152] Application Example 2-1

[0153] This application example provides a nanoimprint optical adhesive, which includes, by weight, 70 parts of the composite resin provided in Application Example 1-1, 30 parts of o-phenylphenoxyethyl acrylate, 2 parts of a photoinitiator (2-hydroxy-2-methylphenyl acetone) and 1 part of KH-570.

[0154] This application example provides a method for preparing the nanoimprint optical adhesive, which specifically includes the following steps:

[0155] According to the formula, the composite resin, o-phenylphenoxyethyl acrylate, photoinitiator and KH-570 are placed in a reaction kettle and stirred at room temperature for 60 minutes, with the temperature not exceeding 50°C, so that the components are evenly mixed. The obtained glue solution is then placed in a vacuum degassing box and vacuumed for 30 minutes at a vacuum degree of -0.1 MPa to obtain the nanoimprint optical glue.

[0156] Application Example 2-2

[0157] This application example provides a nanoimprint optical adhesive, which includes, in parts by weight, 60 parts of the composite resin provided in Application Example 1-2, 40 parts of o-phenylphenoxyethyl acrylate, 2 parts of a photoinitiator (diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide) and 1 part of KH-570.

[0158] This application example provides a method for preparing the nanoimprint optical adhesive, and the specific steps are the same as those of application example 2-1.

[0159] Application Example 2-3

[0160] This application example provides a nanoimprint optical adhesive, which includes, in parts by weight, 80 parts of the composite resin provided in Application Examples 1-3, 20 parts of o-phenylphenoxyethyl acrylate, 2 parts of a photoinitiator (diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide) and 1 part of KH-570.

[0161] This application example provides a method for preparing the nanoimprint optical adhesive, and the specific steps are the same as those of application example 2-1.

[0162] Application Examples 2-4

[0163] This application example provides a nanoimprint optical adhesive, which includes, by weight, 70 parts of the composite resin provided in Application Examples 1-4, 30 parts of isobornyl acrylate, 2 parts of a photoinitiator (2-hydroxy-2-methylphenyl acetone) and 1 part of KH-570.

[0164] This application example provides a method for preparing the nanoimprint optical adhesive, and the specific steps are the same as those of application example 2-1.

[0165] Application Examples 2-5

[0166] This application example provides a nanoimprint optical adhesive, which includes, by weight, 60 parts of the composite resin provided in Application Examples 1-5, 40 parts of lauryl methacrylate, 2 parts of a photoinitiator (2-hydroxy-2-methylphenyl acetone), and 1 part of KH-570.

[0167] This application example provides a method for preparing the nanoimprint optical adhesive, and the specific steps are the same as those of application example 2-1.

[0168] Application Examples 2-6 to 2-11

[0169] Application Examples 2-6 to 2-11 respectively provide a nanoimprint optical adhesive, which differs from Application Example 2-1 only in that the composite resin is provided by Application Examples 1-6 to 1-11, and the other components, amounts and preparation methods are the same as those of Application Example 2-1.

[0170] Comparative Application Example 2-1

[0171] This comparative application example provides a nanoimprint optical adhesive, which differs from Application Example 2-1 only in that the composite resin is replaced with an equal mass of composite resin provided in Comparative Application Example 1-1, and the other components, amounts and preparation methods are the same as those in Application Example 2-1.

[0172] Comparative Application Example 2-2

[0173] This comparative application example provides a nanoimprint optical adhesive, which differs from Application Example 2-1 only in that the composite resin is replaced with an equal mass of composite resin provided in Comparative Application Example 1-2, and the other components, amounts and preparation methods are the same as those in Application Example 2-1.

[0174] Comparative Application Example 2-3

[0175] This comparative application example provides a nanoimprint optical adhesive, which differs from Application Example 2-1 only in that the composite resin is replaced with an equal mass of the polythiourethane-acrylate block polymer provided in Example 1, and the other components, amounts and preparation methods are the same as those in Application Example 2-1.

[0176] Comparative Application Examples 2-4

[0177] This comparative application example provides a nanoimprint optical adhesive, which differs from Application Example 2-1 only in that the amount of the composite resin is 40 parts by weight, and the other components, amounts and preparation methods are the same as those of Application Example 2-1.

[0178] Comparative Application Examples 2-5

[0179] This comparative application example provides a nanoimprint optical adhesive, which differs from application example 2-1 only in that the composite resin provided in application example 1-1 is replaced with the composite resin provided in comparative application example 1-3 of equal mass. The other components, dosages, and preparation methods are the same as those in application example 2-1.

[0180] Performance Testing

[0181] The obtained nanoimprint optical adhesive was subjected to the following performance tests:

[0182] (1) Refractive index: Refer to GB / T 6488-2008 Liquid chemical products - Determination of refractive index (20°C) for refractive index testing.

[0183] (2) Hardness: Hardness test shall be conducted with reference to GB / T 531.1-2008 Test method for indentation hardness of vulcanized rubber or thermoplastic rubber - Part 1: Shore hardness tester method (Shore hardness)

[0184] (3) Light transmittance and haze: Refer to the standard "GB / T 2410-2008 Transparent plastics - Determination of light transmittance and haze" for light transmittance and haze testing.

[0185] (4) Adhesion: Refer to GB / T 1727-92 General Preparation Method for Paint Films for a 100-grid adhesion test.

[0186] (5) Shrinkage: Shrinkage test was performed with reference to the standard GB / T 24148.9-2014 Plastics Unsaturated Polyester Resins (UP-R) Part 9: Determination of Total Volume Shrinkage.

[0187] (6) Curing time: Use a four-sided scraper to apply a 5 μm film and cure it on a 365 nm LED lamp curing machine with a curing energy of 3000 mj / cm 2 , record the time required for complete curing.

[0188] (7) Resistance to moisture and heat aging: The nanoimprint optical adhesive was coated on a 10-inch glass cover plate, and then another glass cover plate was attached. The adhesive layer was cured to obtain a bonding test sample with a thickness of 250 μm. After being placed at a temperature of 85°C and a humidity of 85 RH% for 240 h, the nanoimprint optical adhesive was observed to see if there were any external cracks, cracks, debonding, or delamination.

[0189] (8) Resistance to cold and hot shock: The nanoimprint optical adhesive was coated on a 10-inch glass cover plate, and then attached to another glass cover plate. The adhesive layer was cured to obtain a bonding test sample with a thickness of 250 μm. The adhesive was subjected to cold and hot shock at -40 to 105 °C for 240 h to observe whether the nanoimprint optical adhesive showed any external cracking, splitting, delamination, etc.

[0190] The specific test results are shown in Table 1.

[0191] Table 1

[0192]

[0193]

[0194] As shown in Table 1, the polythiourethane-propylene derivative block polymer provided by the present invention, which incorporates multifunctional propylene derivative structural units, exhibits a high refractive index, a high degree of crosslinking, and a high photocuring reactivity. Nanoimprint optical adhesives prepared from these polythiourethane-propylene derivative block polymers also possess a high refractive index, excellent light transmittance, and good processing properties. Furthermore, they exhibit high hardness and adhesion, excellent resistance to wet heat aging and thermal shock, high transfer efficiency, high precision, and low cost. The optical adhesives containing these polythiourethane-propylene derivative block polymers exhibit a refractive index ≥1.67, a curing time ≤10s, and no surface abnormalities after wet heat aging or thermal shock.

[0195] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A polythiourethane-propylene derivative block polymer, characterized in that: The raw materials for preparing the polythiourethane-propylene derivative block polymer include polythiourethane oligomer and multifunctional propylene derivative monomer; The molecular structure of the polythiourethane oligomer contains a carbon-carbon double bond; the functionality of the multifunctional propylene derivative monomer is ≥2; the multifunctional propylene derivative monomer includes a multifunctional acrylate and / or a multifunctional allyl ether; The raw materials for preparing the polythiourethane oligomer include polyisocyanate, and the polyisocyanate includes aliphatic polyisocyanate and / or alicyclic polyisocyanate.

2. The polythiourethane-propylene derivative block polymer according to claim 1, characterized in that The carbon-carbon double bonds are distributed at the ends of the molecular structure of the polythiourethane oligomer; Preferably, the raw materials for preparing the polythiourethane oligomer further include polythiol and monofunctional acrylate; the molecular structure of the monofunctional acrylate contains isocyanate group or hydroxyl group; Preferably, the molar ratio of the polythiol, polyisocyanate and monofunctional acrylate is (0.9-1.3):(0.3-2):

1.

3. The polythiourethane-propylene derivative block polymer according to claim 2, characterized in that: The polythiol is selected from a compound having a structure shown in Formula I and / or a compound having a structure shown in Formula II, more preferably a compound having a structure shown in Formula II; HS-R-SH formula I; HS-R1-S-R2-SH formula II; wherein R, R1, and R2 are each independently selected from any one of substituted or unsubstituted C1-C10 straight or branched alkylene, substituted or unsubstituted C3-C8 cycloalkylene, and substituted or unsubstituted C6-C20 arylene; and the substituted substituent includes a hydroxyl group; Preferably, the polythiol includes at least one of 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,2-benzenedithiol, 1,4-benzenedithiol, 1,2-cyclohexanedithiol, dimercaprol, 4,4-thiodiphenylthiol or 2-mercaptoethyl sulfide; Preferably, the polyisocyanate comprises at least one of hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane-4,4'-diisocyanate; Preferably, the monofunctional acrylate includes at least one of isocyanateethyl acrylate, isocyanateethyl methacrylate, isocyanate acrylate prepolymer, hydroxyethyl acrylate, hydroxypropyl acrylate or hydroxyethyl methacrylate.

4. The polythiourethane-propylene derivative block polymer according to claim 2 or 3, characterized in that: The molar ratio of the monofunctional acrylate to the multifunctional propylene derivative monomer is 1:(0.6-3); Preferably, the multifunctional propylene derivative monomer includes at least one of 1,6-hexanediol diacrylate, triethylene glycol dimethacrylate, tripropylene glycol diacrylate, dioxanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol triallyl ether or pentaerythritol tetraacrylate.

5. A method for preparing the polythiourethane-propylene derivative block polymer according to any one of claims 1 to 4, characterized in that: The preparation method specifically comprises the following steps: reacting a polythiourethane oligomer with a multifunctional propylene derivative monomer to obtain the polythiourethane-propylene derivative block polymer; Preferably, the preparation method of the polythiourethane oligomer comprises: In the presence of a catalyst, polythiol, polyisocyanate and monofunctional acrylate are mixed and reacted to obtain the polythiourethane oligomer; Preferably, the catalyst comprises at least one of triethylamine, triethanolamine, 1,6-hexamethylenediamine, isophoronediamine, 1,4-cyclohexanediamine or 4,4-diaminodicyclohexylmethane; Preferably, the temperature for reacting the polythiourethane oligomer with the multifunctional propylene derivative monomer is room temperature, and the reaction time is 0.5 to 24 hours.

6. A composite resin, characterized in that The composite resin comprises the polythiourethane-propylene derivative block polymer according to any one of claims 1 to 4 and inorganic nanoparticles.

7. The composite resin according to claim 6, characterized in that The inorganic nanoparticles are formed in the polythiourethane-propylene derivative block polymer by in-situ polymerization; Preferably, the inorganic nanoparticles include titanium dioxide and / or zirconium dioxide; Preferably, the mass ratio of the precursor of the inorganic nanoparticles to the polythiourethane-propylene derivative block polymer is 1:(5-14).

8. A method for preparing a composite resin according to claim 6 or 7, characterized in that: The preparation method comprises the following steps: Mixing the polythiourethane-propylene derivative block polymer with the precursor of the inorganic nanoparticles and reacting them under acid catalysis to obtain the composite resin; Preferably, the precursor of the inorganic nanoparticles comprises at least one of zirconium n-propoxide, tetrabutyl titanate or zirconium butoxide; Preferably, the mixed raw materials further include a silane coupling agent; Preferably, the mass ratio of the silane coupling agent to the precursor of the inorganic nanoparticles is (1-3):1; Preferably, the silane coupling agent includes at least one of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(β-methoxyethoxy)silane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane or 3-mercaptopropyltriethoxysilane; Preferably, the reaction temperature is room temperature and the reaction time is 0.5 to 3 hours.

9. A nanoimprint optical adhesive, characterized in that: In parts by weight, the nanoimprint optical adhesive comprises 45 to 100 parts of the composite resin according to claim 6 or 7, 5 to 30 parts of an acrylate reactive diluent, and 0.1 to 5 parts of a photoinitiator; Preferably, the acrylic acid ester reactive diluent includes at least one of isobornyl acrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, o-phenylphenoxyethyl acrylate, lauryl methacrylate, octadecyl methacrylate, isooctyl acrylate, 1,6-hexanediol diacrylate, triethylene glycol dimethacrylate or dipropylene glycol diacrylate; Preferably, the photoinitiator comprises at least one of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, benzophenone, isopropylthioxanthenone or methyl o-benzoylbenzoate; Preferably, the nanoimprint optical adhesive further comprises 0.1 to 5 parts of an auxiliary agent in parts by weight.

10. An optical device, characterized in that: The material of the optical device comprises the polythiourethane-propylene derivative block polymer according to any one of claims 1 to 4, the composite resin according to claim 6 or 7, or the nanoimprint optical adhesive according to claim 9; Preferably, the optical device includes a device prepared using nanoimprint technology.

Images