Resin composition for imprinting

Abstract

The present invention provides a resin composition for imprinting that has excellent optical properties such as high refractive index and low haze, along with imprintability. The present invention comprises (A) the following general formula (1) (In general formula (1), R1, R2, and R3 are each independently a hydrogen atom, a hydroxyl group, an alkoxy group, a hydrocarbon group having 1 to 12 carbon atoms, or a substituent having 1 to 12 carbon atoms having one or more crosslinking functional groups; when each of R1, R2, and R3 is present in multiples, they may be different, and at least one of R1, R2, and R3 is a substituent having 1 to 12 carbon atoms having one or more crosslinking functional groups, and a, b, c, and d are numbers satisfying 0.001 ≤ a ≤ 1.00, 0 ≤ b ≤ 0.999, 0 ≤ c ≤ 0.30, 0 ≤ d ≤ 0.30, and a + b + c + d = 1.0.) a polysiloxane resin represented by (B) and an inorganic oxide The present invention relates to a resin composition for imprinting that includes fine particles, wherein the weight ratio of the total weight of the polysiloxane resin (A), optional alkoxysilane compound and curable resin, and the weight of the inorganic oxide fine particles (B) is 0.2 to 2.5.

Description

Technology Field

[0001] The present invention relates to a resin composition for imprinting. Background Technology

[0002] Due to the miniaturization of optical devices such as microlenses and diffractive optical elements and the simplification of manufacturing processes, the imprint method, which performs sub-micron or smaller microfabrication by applying a mold to a substrate and transferring the shape of the mold, has been utilized instead of electron beam lithography, which requires multiple processes such as exposure and development. For such imprint methods, resin materials that are processable by the imprint process and exhibit high transparency and high refractive index are required. To increase the refractive index, it is necessary to increase the content of compounds containing aromatic rings or high-refractive-index inorganic materials, but the development of compositions that provide cured products with good optical properties and viscosity applicable to the UV imprint process has not yet been achieved.

[0003] Patent Document 1 discloses an imprint composition comprising polysiloxane and silica microparticles. However, in the examples, only compositions with a low silica content were considered, and additionally, it is based on the premise of using a bottom coat.

[0004] Patent Document 2 discloses a composition comprising polysiloxane and fine particles, and an imprint application. However, cyclic polysiloxane is used, and no specific evaluation regarding imprintability has been conducted.

[0005] Patent Document 3 discloses an imprint composition containing fine particles. However, only compositions using acrylic resin and silica, and with a small amount of silica in the examples, have been considered. Prior art literature

[0006] Japanese Published Patent Application No. 2005-527110, Japanese Published Patent Application No. 2016-160285, International Publication No. 2008 / 105309 The problem to be solved

[0007] The present invention aims to provide a resin composition for imprinting that has excellent optical properties, such as high refractive index and low haze, along with imprintability. means of solving the problem

[0008] The inventors, after examining the imprintability, discovered that in a resin composition comprising a polysiloxane resin and inorganic oxide microparticles, if the content of the inorganic oxide microparticles is increased and the weight ratio of the total weight of the polysiloxane resin (A), optional alkoxysilane compound and curable resin, and the weight of the inorganic oxide microparticles (B) is 0.2 to 2.5, the imprintability and optical properties can be compatible, and thus completed the present invention.

[0009] That is, the present invention is,

[0010] (A) The following general formula (1)

[0011]

[0012] (of general formula (1), R 1 , R 2 , R 3 Each is independently a hydrogen atom, a hydroxyl group, an alkoxy group, a hydrocarbon group having 1 to 12 carbon atoms, or a substituent having 1 to 12 carbon atoms having one or more crosslinkable functional groups, wherein R 1 , R 2 , R 3 If each of exists in multiple forms, they may be different, and R 1 , R 2 , R 3 At least one of them is a carbon-1 to carbon-12 substituent having one or more crosslinkable functional groups, and

[0013] a, b, c, and d are numbers satisfying 0.001 ≤ a ≤ 1.00, 0 ≤ b ≤ 0.999, 0 ≤ c ≤ 0.30, 0 ≤ d ≤ 0.30, and a + b + c + d = 1.0.

[0014] It comprises a polysiloxane resin represented by and (B) inorganic oxide microparticles,

[0015] The present invention relates to a resin composition for imprinting in which the weight ratio of the total weight of a polysiloxane resin (A), an optional alkoxysilane compound and a curable resin, and the weight of an inorganic oxide fine particle (B) is 0.2 to 2.5.

[0016] The crosslinking functional group having a substituent with 1 to 12 carbon atoms is preferably a (meth)acrylic group, a (meth)acryloxy group, a vinyl group, or an epoxy group.

[0017] It is preferable that the weight average molecular weight of the polysiloxane resin (A) is 1,000 to 5,000.

[0018] It is preferable that the average particle size of the inorganic oxide fine particles (B) after dispersion is 10 to 70 nm.

[0019] It is preferable that the weight ratio of the total weight of the polysiloxane resin (A), optional alkoxysilane compound and curable resin, and the weight of the inorganic oxide fine particles (B) is 0.25 to 1.

[0020] It is preferable that the inorganic oxide microparticles (B) be zirconium oxide or titanium oxide.

[0021] In addition, the present invention relates to an imprint substrate having a convex or concave portion formed by a substrate and a cured product of the imprint resin composition.

[0022] In addition, the present invention relates to a method for manufacturing an imprint substrate comprising a process of applying the imprint resin composition to a substrate and a process of patterning by a nanoimprint method. Effects of the invention

[0023] The imprint resin composition of the present invention has excellent imprintability and optical properties because the weight ratio of the total weight of the polysiloxane resin (A), optional alkoxysilane compound and curable resin, and the weight of the inorganic oxide fine particles (B) is 0.2 to 2.5. Specific details for implementing the invention

[0024] <<Resin Composition for Imprint Substrates>>

[0025] The resin composition for imprinting of the present invention is,

[0026] (A) The following general formula (1)

[0027]

[0028] (of general formula (1), R 1 , R 2 , R 3 Each is independently a hydrogen atom, a hydroxyl group, an alkoxy group, a hydrocarbon group having 1 to 12 carbon atoms, or a substituent having 1 to 12 carbon atoms having one or more crosslinkable functional groups, wherein R 1 , R 2 , R 3 If each of exists in multiple forms, they may be different, and R 1 , R 2 , R 3 At least one of them is a carbon-1 to carbon-12 substituent having one or more crosslinkable functional groups, and

[0029] a, b, c, and d are numbers satisfying 0.001 ≤ a ≤ 1.00, 0 ≤ b ≤ 0.999, 0 ≤ c ≤ 0.30, 0 ≤ d ≤ 0.30, and a + b + c + d = 1.0.

[0030] It comprises a polysiloxane resin represented by and (B) inorganic oxide microparticles,

[0031] It is characterized by the weight ratio of the total weight of the polysiloxane resin (A), optional alkoxysilane compound and curable resin, and the weight of the inorganic oxide fine particles (B) being 0.2 to 2.5.

[0032] <(A) Polysiloxane Resin>

[0033] Polysiloxane resin (A) is the following general formula (1)

[0034]

[0035] (of general formula (1), R 1 , R 2 , R 3 Each is independently a hydrogen atom, a hydroxyl group, an alkoxy group, a hydrocarbon group having 1 to 12 carbon atoms, or a substituent having 1 to 12 carbon atoms having one or more crosslinkable functional groups, wherein R 1 , R 2 , R 3 If each of exists in multiple forms, they may be different, and R 1 , R 2 , R 3 At least one of them is a carbon-1 to carbon-12 substituent having one or more crosslinkable functional groups, and

[0036] a, b, c, and d are numbers satisfying 0.001 ≤ a ≤ 1.00, 0 ≤ b ≤ 0.999, 0 ≤ c ≤ 0.30, 0 ≤ d ≤ 0.30, and a + b + c + d = 1.0.

[0037] It is represented as.

[0038] R 1 , R 2 , R 3Each is independently a hydrogen atom, a hydroxyl group, an alkoxy group, a hydrocarbon group having 1 to 12 carbon atoms, or a substituent having 1 to 12 carbon atoms having one or more crosslinkable functional groups. A hydrocarbon group is a group composed of carbon and hydrogen, examples of which include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. A substituent having 1 to 12 carbon atoms having one or more crosslinkable functional groups refers to a hydrocarbon having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with a crosslinkable functional group. Here, the number of carbon atoms in the hydrocarbon group is preferably 1 to 6. R 1 , R 2 , R 3 If each of exists in multiple forms, they may be different. Also, R 1 , R 2 , R 3 At least one of them needs to be a carbon-1 to carbon-12 substituent having one or more crosslinkable functional groups. Examples of crosslinkable functional groups include (meth)acrylic groups, (meth)acryloxy groups, vinyl groups, epoxy groups, etc.

[0039] a is preferably 0.1 to 1, b is preferably 0 to 0.7, c is preferably 0 to 0.2, and d is preferably 0 to 0.1. If within the above ranges, a composition with good compatibility with an inorganic fine particle dispersion and good curability is obtained.

[0040] The method for manufacturing polysiloxane resin is not particularly limited, but is obtained, for example, by the hydrolysis and condensation reaction of an alkoxysilane.

[0041] (Alkoxysilane)

[0042] As for the alkoxysilane, it may be a compound represented by the following formula (a).

[0043] SiR4(a)

[0044] In formula (a), each of the four Rs is a hydrogen, a hydroxyl group, an alkoxy group, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group, and at least one of the four Rs is an alkoxy group. Also, the alkoxy group, the aliphatic hydrocarbon group, and the aromatic hydrocarbon group may each have a substituent.

[0045] Among the four Rs, if one R is an alkoxy group, it is called monoalkoxysilane; if two Rs are alkoxy groups, it is called dialkoxysilane; if three Rs are alkoxy groups, it is called trialkoxysilane; and if four Rs are alkoxy groups, it is called tetraalkoxysilane. The alkoxysilane used in the manufacture of polysiloxane resin may be any of monoalkoxysilane, dialkoxysilane, trialkoxysilane, and tetraalkoxysilane.

[0046] Examples of alkoxy groups include C1-4 alkoxy groups such as methoxy groups and ethoxy groups. Examples of aliphatic hydrocarbon groups include C1-20 alkyl groups such as methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, s-butyl groups, and t-butyl groups. Examples of aromatic hydrocarbon groups include aryl groups such as phenyl groups, tolyl groups, and xylyl groups; and aralkyl groups such as benzyl groups.

[0047] Substituents on aliphatic hydrocarbon groups and aromatic hydrocarbon groups include crosslinking functional groups such as (meth)acrylic groups, (meth)acryloxy groups, vinyl groups, and epoxy groups, primary amino groups, thiol groups, and styryl groups.

[0048] As for alkoxysilanes, for example, alkoxysilanes having an aliphatic hydrocarbon group such as methyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methoxytrimethylsilane; alkoxysilanes having an aromatic hydrocarbon group such as phenyltrimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane; Alkoxysilanes having an amino group such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 2-aminophenyltrimethoxysilane, 3-aminophenyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane; alkoxysilanes having a (meth)acryl group such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane; Examples include alkoxysilanes having vinyl groups such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane; and alkoxysilanes having epoxy groups such as β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane.

[0049] In hydrolysis and condensation reactions, an alkoxysilane having a crosslinkable functional group and, if necessary, an alkoxysilane not having a crosslinkable functional group may be used in combination. In addition, hydrolyzable silanes such as dimethylsilanediol, diisopropylsilanediol, diisobutylsilanediol, di-n-propylsilanediol, di-n-butylsilanediol, di-t-butylsilanediol, phenylmethylsilanediol, dicyclohexylsilanediol, ethylsilantriol, and diphenylsilanediol may be used in combination.

[0050] (Hydrolysis and condensation reactions)

[0051] The hydrolysis and condensation reactions can be carried out under temperature and time conditions, preferably 30 to 120 ℃ for 1 to 24 hours, more preferably 40 to 90 ℃ for 2 to 12 hours, and even more preferably 45 to 80 ℃ for 3 to 8 hours.

[0052] Polysiloxane resin is obtained by forming siloxane bonds between the alkoxy groups in the alkoxysilane through hydrolysis and condensation reactions, and some unreacted alkoxy groups or hydroxyl groups formed by the hydrolysis of alkoxy groups may remain in the polysiloxane resin.

[0053] Hydrolysis and condensation reactions may be carried out using a catalyst, and examples of such catalysts include basic catalysts and acidic catalysts. Examples of basic catalysts include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, potassium-t-butoxide, sodium bicarbonate, sodium carbonate, barium hydroxide, sodium hydroxide, and potassium hydroxide. Among these, tetramethylammonium hydroxide, potassium-t-butoxide, sodium bicarbonate, sodium carbonate, barium hydroxide, sodium hydroxide, and potassium hydroxide are preferably used due to their high catalytic activity. Examples of acidic catalysts include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid, boric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid.

[0054] Solvents may be used as needed in hydrolysis and condensation reactions. Such solvents include, for example, water; alcohols such as methanol and ethanol; ethers such as tetrahydrofuran (THF); glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol monobutyl ether; alkylene glycol monoalkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate (PGMEA), and 3-methoxybutyl-1-acetate; and aromatic hydrocarbons such as toluene and xylene. Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone (MIBK), methyl amyl ketone, and cyclohexanone, and ketones, alkylene glycol monoalkyl ether acetates, or aromatic hydrocarbons are preferred. These solvents may be used alone or in combination of two or more types.

[0055] As for the amount of solvent, 50 to 500 parts by mass is preferred per 100 parts by mass of alkoxysilane, and 100 to 400 parts by mass is more preferred.

[0056] The weight average molecular weight of the polysiloxane resin (A) is not particularly limited, but is preferably 1000 to 5000, and more preferably 1300 to 3700. Within the above range, the curability is excellent, and there is a tendency for excellent optical properties or imprintability.

[0057] <(B) Inorganic oxide microparticles>

[0058] The inorganic oxide particles (B) are not particularly limited, but examples include metal oxides composed of one metal element or complex metal oxides composed of two or more metal elements. Examples of metal oxides composed of 1 type of metal element include zirconium oxide (ZrO2), titanium oxide (TiO2), silicon oxide (SiO2), aluminum oxide (Al2O3), iron oxide (Fe2O3, FeO, Fe3O4), copper oxide (CuO, Cu2O), zinc oxide (ZnO), yttrium oxide (Y2O3), niobium oxide (Nb2O5), molybdenum oxide (MoO3), indium oxide (In2O3, In2O), tin oxide (SnO2), tantalum oxide (Ta2O5), tungsten oxide (WO3, W2O5), lead oxide (PbO, PbO2), bismuth oxide (Bi2O3), cerium oxide (CeO2, Ce2O3), antimony oxide (Sb2O5), germanium oxide (GeO2, GeO), etc. These inorganic oxide fine particles may be used alone or in combination of two or more types. Zirconium oxide and titanium oxide are preferred as inorganic fine particles because they are easy to obtain and easy to adjust optical properties such as refractive index.

[0059] Examples of composite oxides composed of two or more metal elements include titanates such as barium titanate, titanium / silicon composite oxides, and yttrium-stabilized zirconia. Such composite oxides include not only compounds or solid solutions composed of multiple elements, but also structures having a core-shell structure in which a core metal oxide particle is coated with a metal oxide composed of another metal element, or structures having a multi-component dispersed type in which multiple metal oxide particles are dispersed within a single metal oxide particle.

[0060] The primary particle size of the inorganic oxide microparticles is not particularly limited, but is preferably 1 to 50 nm, and more preferably 5 to 30 nm. If it is less than 1 nm, the specific surface area of ​​the inorganic oxide microparticles is large and the cohesive energy is high, so it may be difficult to maintain dispersion stability. On the other hand, if it exceeds 50 nm, light scattering by the inorganic oxide microparticles in the thin film or molded body becomes violent, so it may not be possible to maintain high transparency. In addition, the primary particle size can be measured using an electron microscope such as SEM or TEM, or by conversion from the specific surface area.

[0061] As for the inorganic oxide fine particles, those that have been dispersed in various solvents in advance may be used. Examples of solvents include alcohols such as methanol, ethanol, 2-propanol, and butanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, and γ-butyrolactone; ethers such as diethyl ether, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; and amides such as dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more. The mixing ratio of the solvent and the metal oxide fine particles is not particularly limited, but 30:70 to 90:10 is preferred.

[0062] To disperse inorganic oxide fine particles, a dispersant may be added. The dispersant is not particularly limited as long as it can be dispersed in a solvent, but examples include polyacrylic acid-based dispersants, polycarboxylic acid-based dispersants, phosphate-based dispersants, and silicone-based dispersants.

[0063] Examples of polyacrylic acid-based dispersants include sodium polyacrylate, and commercially available products include the Aaron series (manufactured by Toa Synthetic Co., Ltd.) and the Charol series (manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.).

[0064] Examples of polycarboxylic acid-based dispersants include acidic types that are not neutralized by cations or ammonium polycarboxylate salts, and commercially available products include AH-103P (manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.), SN Dispersant 5020, SN Dispersant 5468 (manufactured by Sannopco Co., Ltd.), Poise 532A, Poise 2100 (manufactured by Kao Corporation), Malialim AKM-0531, Malialim AKM-1511-60, Malialim HKM-50A, and Malialim HKM-150A (manufactured by Nichiyu Corporation).

[0065] Examples of phosphate-based dispersants include polyoxyethylene alkyl ether phosphate esters. Examples of commercially available products include Phosphanol RA-600, ML-220 (manufactured by Toho Chemical Industry Co., Ltd.), and Dispalon PW-36 (manufactured by Kusumoto Chemical Co., Ltd.).

[0066] Examples of silicone-based dispersants include modified silicone oil. An example of a commercially available product is ES-5612 (manufactured by DuPont Toray Specialty Materials Co., Ltd.).

[0067] The amount of dispersant added is preferably 0.25 to 30 parts by weight per 100 parts by weight of inorganic oxide fine particles, more preferably 0.25 to 8 parts by weight, even more preferably 0.5 to 7 parts by weight, and most preferably 1 to 5 parts by weight. If the amount added is less than 0.25 parts by weight, the inorganic oxide fine particles may not be sufficiently dispersed, and if it exceeds 30 parts by weight, the light resistance or heat resistance may be reduced when processed into a thin film, a molded body, etc., or the characteristics of the inorganic oxide fine particles may not be sufficiently obtained.

[0068] In order to increase the affinity between the inorganic oxide microparticles and the polysiloxane resin when the dispersion is mixed with the polysiloxane resin, an alkoxysilane compound may be added. When the dispersion is subjected to acidic or alkaline conditions, the hydroxyl groups present on the surface of the inorganic oxide microparticles react with the alkoxysilane compound, thereby allowing for surface treatment of the inorganic oxide microparticles.

[0069] As for alkoxysilane compounds,

[0070] The following formula (I)

[0071] SiR4(I)

[0072] (In the formula, R is hydrogen, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkyl group that may have substituents, or a phenyl group that may have substituents. Provided, at least one of the four Rs is an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group.)

[0073] A compound represented by is preferred.

[0074] Specific examples of alkoxysilane compounds include 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxysilane, and other trialkoxysilanes, as well as 3-methacryloxypropylmethyldimethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, and other trialkoxysilanes. These may be used alone or in combination of two or more types. Among these, trialkoxysilane is preferred, and 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and phenyltrimethoxysilane are more preferred.

[0075] The amount of alkoxysilane compound is preferably 4 to 50 parts by weight per 100 parts by weight of inorganic oxide fine particles, more preferably 6 to 38 parts by weight, and even more preferably 8 to 20 parts by weight. If the amount is less than 4 parts by weight, it may be difficult to uniformly disperse the inorganic oxide fine particles, and if it exceeds 50 parts by weight, the inorganic oxide may not be filled to a high degree, and the desired characteristics may not be obtained.

[0076] When a dispersion contains a dispersant and an alkoxysilane compound, the weight ratio of the dispersant to the alkoxysilane compound is preferably 20:80 to 5:95, more preferably 18:82 to 7:93, and even more preferably 18:82 to 9:91. If the weight ratio of the alkoxysilane compound to 20 of the dispersant is less than 80, the dispersant becomes excessive, which may cause a decrease in properties when processed into a thin film, a molded body, etc., and if the weight ratio of the alkoxysilane compound to 5 of the dispersant exceeds 95, it may be difficult to produce a uniform dispersion.

[0077] The average particle size of inorganic oxide microparticles in the resin composition for imprinting is preferably 10 to 70 nm, and more preferably 10 to 50 nm. To make it less than 10 nm, it is necessary to use particles with a small primary particle size, which may make dispersion difficult. On the other hand, if it exceeds 70 nm, it may become cloudy when formed into cured products such as thin films or molded bodies. The average particle size can be measured using devices such as dynamic light scattering or laser diffraction.

[0078] The weight ratio of the total weight of the polysiloxane resin (A), optional alkoxysilane compound, and curable resin to the weight of the inorganic oxide microparticles (B) is 0.2 to 2.5, but is preferably 0.25 to 1.0. In addition, the weight ratio of the total weight of the polysiloxane resin (A) and optional alkoxysilane compound to the weight of the inorganic oxide microparticles (B) is preferably 0.2 to 2.5, and more preferably 0.25 to 1.0. Within the above range, the imprintability is excellent and sufficiently satisfies the optical characteristics required for optical devices.

[0079] In addition, the inorganic oxide microparticles (B) are preferably 25 to 80 weight% of the solid content of the resin composition for imprinting, more preferably 30 to 80 weight%, and even more preferably 35 to 75 weight%. Within the above range, the imprintability is excellent and sufficiently satisfies the optical properties required for optical properties.

[0080] <Optional Components>

[0081] The resin composition for imprinting according to the present invention may optionally contain other components in addition to the aforementioned components. Examples of other components include curable resins other than polysiloxane resins, such as epoxy resin, acrylate, or melamine; thermoplastic resins such as acrylic resin, polyester resin, urethane resin, or polyolefin resin; polymerization initiators; leveling agents; surfactants; photosensitizers; defoaming agents; neutralizing agents; antioxidants; release agents; ultraviolet absorbers; solvents; etc.

[0082] Curable resins include, for example, bisphenol A type, bisphenol F type, phenol novolak type, polyfunctional tetrakis(hydroxyphenyl)ethane type or tris(hydroxyphenyl)methane type having multiple benzene rings, biphenyl type, triphenolmethane type, naphthalene type, ortho novolak type, dicyclopentadiene type, aminophenol type, fluorene type, alicyclic epoxy resins, etc., epoxy resins such as silicone epoxy resin; 2-Hydroxyethyl (meth)acrylate, 2-Hydroxypropyl (meth)acrylate, 3-Hydroxypropyl (meth)acrylate, Trimethylolpropane triacrylate, Ditrimethylolpropane tetraacrylate, Pentaerythritol triacrylate, Pentaerythritol tetraacrylate, Dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate, Alkyl modified dipentaerythritol pentaacrylate, Ethylene glycol (meth)acrylate, Diethylene glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, Tetraethylene glycol di(meth)acrylate, Tetramethylene glycol di(meth)acrylate, Polyethylene glycol di(meth)acrylate, Glycerin tri(meth)acrylate, Examples include acrylates such as 9,9-bis(4-(meth)acryloyloxyphenyl)fluorene, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, or 1,6-hexanediol diglycidyl ether, or epoxy compounds having fluorene such as 9,9-bis(4-glycidyloxyphenyl)fluorene, and melamine.

[0083] Regarding the amount of curable resin, 0 to 100 parts by weight is preferred and 0.1 to 50 parts by weight is more preferred per 100 parts by weight of inorganic fine particles. In addition, regarding the amount of curable resin, 0 to 50,000 parts by weight is preferred and 0 to 10,000 parts by weight is more preferred and 0 to 1,000 parts by weight is even more preferred and 1 to 100 parts by weight is particularly preferred and 5 to 50 parts by weight is most preferred per 100 parts by weight of polysiloxane resin (A).

[0084] The amount of polysiloxane resin (A) is preferably 0.01 to 500 parts by weight, more preferably 0.1 to 300 parts by weight, and even more preferably 0.2 to 200 parts by weight, based on 100 parts by weight of inorganic fine particles.

[0085] As polymerization initiators, photoradical polymerization initiators, thermal radical polymerization initiators, etc., may be used. These polymerization initiators may be used alone, or two or more polymerization initiators may be used in combination, for example, two or more photoradical polymerization initiators or two or more thermal radical polymerization initiators, or a photoradical polymerization initiator and a thermal radical polymerization initiator may be used in combination.

[0086] Examples of photoradical polymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc.

[0087] Examples of thermal radical polymerization initiators include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexine-3,1,3-bis(t-butylperoxyisopropyl)benzene, 1,1-bis(t-butylperoxy)valerate, benzoyl peroxide, t-butylperoxybenzoate, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluyl peroxide, etc.

[0088] As for the amount of polymerization initiator, 0.1 to 25 parts by weight is preferred and 1 to 20 parts by weight is more preferred per 100 parts by weight of a component having a crosslinkable functional group.

[0089] <Leveling Agent>

[0090] Leveling agents are not particularly limited and include, for example, siloxane-based compounds such as polyether-modified polydimethylsiloxane, polyether-modified siloxane, polyether-ester-modified hydroxyl-containing polydimethylsiloxane, polyether-modified acrylic-containing polydimethylsiloxane, polyester-modified acrylic-containing polydimethylsiloxane, perfluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, and perfluoropolyester-modified polydimethylsiloxane; fluorine-based compounds such as perfluoroalkylcarboxylic acids and perfluoroalkylpolyoxyethyleneethanol; polyether-based compounds such as polyoxyethylenealkylphenyl ether, propylene oxide polymer, and ethylene oxide polymer; carboxylic acids such as palm oil fatty acid amine salts and gum rosin; and ester-based compounds such as castor oil sulfate esters, phosphate esters, alkyl ether sulfates, sorbitan fatty acid esters, sulfonic acid esters, and succinic acid esters. Examples include sulfonate compounds such as alkylarylsulfonate amine salts and sodium dioctyl sulfosuccinate; phosphate compounds such as sodium lauryl phosphate; amide compounds such as palm oil fatty acid ethanolamide; and acrylic compounds.

[0091] When using a leveling agent, the amount of the leveling agent is preferably 0.001 to 5 weight% in the solid content of the resin composition for imprinting, more preferably 0.01 to 1 weight%, and even more preferably 0.05 to 0.5 weight%.

[0092] <Solvent>

[0093] As solvents, although not particularly limited, examples include alcohols such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol; ethers such as tetrahydrofuran; ethylene glycol ethers such as ethylene glycol monomethyl ether (methylcellosolve), ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether (ethylcellosolve); ethylene glycol alkyl ether acetates such as methylcellosolve acetate and ethylcellosolve acetate; diethylene glycol dialkyl ethers such as diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, and diethylene glycol ethyl methyl ether; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; and propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether. Alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and 3-methoxybutyl-1-acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; Examples include esters such as 2-ethyl hydroxypropionate, 2-methyl-2-hydroxypropionate, 2-ethyl hydroxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-methyl-2-methylbutanoate, 3-methyl methoxypropionate, 3-ethyl methoxypropionate, 3-methyl ethoxypropionate, 3-ethyl ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, dimethyl succinate, diethyl succinate, diethyl adipyrate, diethyl malonicate, and dibutyl oxalate.Among these, ethylene glycol ethers, alkylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, ketones, and esters are preferred, and ethyl 3-ethoxypropionate, ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), diethylene glycol monoethyl ether acetate, and methyl amyl ketone are more preferred. These solvents may be used alone or in combination of two or more.

[0094] The solid content of the composition is not particularly limited, but is preferably 10 to 85 weight%, more preferably 20 to 80 weight%, and even more preferably 30 to 75 weight%. Within the above range, dispersion stability and imprintability are excellent, and a sufficient film thickness is obtained.

[0095] The viscosity of the resin composition for imprinting according to the present invention is not particularly limited, but is preferably 0.1 to 100 mPa·s, and more preferably 3.0 to 50 mPa·s. Within the above range, the applicability is excellent.

[0096] The refractive index of the cured product of the resin composition for imprinting is not particularly limited, but is preferably 1.62 to 2.0, and more preferably 1.65 to 1.9. Within the above range, sufficient optical properties can be maintained as an optical element.

[0097] The Abbe number of the cured product of the resin composition for imprinting is not particularly limited, but is preferably 15 to 40, and more preferably 20 to 40. Within the above range, sufficient optical properties can be maintained as an optical element.

[0098] The total light transmittance of the cured product of the resin composition for imprinting is not particularly limited, but 85% or more is preferred, 90% or more is more preferred, and 95% or more is even more preferred. Within the above range, sufficient optical properties can be maintained as an optical element.

[0099] The lower the haze value of the cured product of the resin composition for imprinting, the better the optical properties become, which is desirable. For example, 1% or less is desirable, and 0.5% or less is more desirable.

[0100] <Mixing Process>

[0101] The mixing order of optional components, such as polysiloxane resin (A), inorganic oxide fine particles (B), a dispersant, an alkoxysilane compound, and a solvent, is not particularly limited, and optional components such as polysiloxane resin, inorganic oxide fine particles, a dispersant, and an alkoxysilane compound may be added to the solvent in any order, and optional components such as polysiloxane resin (A) and optional components such as a curable resin, a polymerization initiator, and a leveling agent may be added to the dispersion in which the inorganic fine particles are dispersed in the solvent.

[0102] <Wet Grinding Process>

[0103] When using inorganic fine particles dispersed in a solvent, they may be used dispersed by a wet grinding process. In the wet grinding process, a mixture of inorganic oxide fine particles (B), a dispersant blended as needed, an alkoxysilane compound, and a solvent may be ground by wet grinding. By wet grinding in a solvent, the grinding of the inorganic oxide fine particles and the dispersion of the ground material are carried out simultaneously. Examples of wet grinders used in the wet grinding process include ball mills and bead mills, but devices having mechanisms different from these mills may also be used. When a bead mill is used as a wet grinder, the bead diameter is preferably 30 to 100 μm, and the rotation speed is preferably 6 to 12 m / sec.

[0104] <<Method for Manufacturing an Imprint Substrate>>

[0105] The method for manufacturing an imprint substrate according to the present invention is characterized by comprising the steps of applying the imprint resin composition to a substrate and patterning using a nanoimprint method. Additionally, a step of curing the coating film obtained by patterning may be performed.

[0106] The method for manufacturing an imprint substrate according to the present invention selects a light-transmitting material for at least one of the substrate and / or the original substrate. The material of the substrate is not particularly limited and can be selected according to the application, and is not particularly restricted, for example, quartz, glass, ceramic material, deposited film, magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (spin-on glass), TFT array substrate, electrode plate of PDP, conductive substrate such as ITO, insulating substrate, semiconductor fabrication substrate such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, polymer substrate such as polyethylene, polypropylene, polyester, polyethylene naphthalate, polycarbonate, polyimide, cycloolefin, polystyrene, polytetrafluoroethylene, PMMA, ABS resin, etc. Furthermore, the shape of the substrate is not particularly limited and may be plate-shaped or roll-shaped. In addition, as described above, depending on the combination with the original plate, a light-transmitting or non-light-transmitting material can be selected.

[0107] The method of applying the above-mentioned resin composition for imprinting to a substrate is not particularly limited, and examples include bar coating, spin coating, spray coating, dip coating, nozzle coating, gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, curtain coating, knife coating, transfer roll coating, squeeze coating, impregnation coating, kiss coating, calender coating, extrusion coating, etc.

[0108] The thickness of the film is not particularly limited, but 0.005 to 100 μm is preferred, 0.05 to 40 μm is more preferred, and 0.1 to 20 μm is even more preferred. Within the above range, the film has excellent imprintability and maintains sufficient optical properties.

[0109] Patterning in the nanoimprint method involves pressing a patterned plate (transfer imprint stamp) onto a substrate coated with a curable resin, and then curing the imprint resin composition by light or heat to transfer a microstructure pattern. After curing, the imprint substrate is fabricated by removing the plate.

[0110] The material of the base plate is not particularly limited. For example, light-transmitting base plates may include light-transmitting resins such as silicon, glass, quartz, PMMA, and polycarbonate resin, transparent metal deposition films, flexible films such as polydimethylsiloxane, photocurable films, and metal films. Additionally, non-light-transmitting base plates are not particularly limited, but they may have a predetermined strength. Specifically, examples include ceramic materials, deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, and are not particularly restricted. Furthermore, the shape of the mold is not particularly restricted and may be either a plate-shaped mold or a roll-shaped mold. Additionally, if a flexible resin mold is used, film imprinting can be easily performed using a roll-to-roll method.

[0111] The pressure applied is not particularly limited, but 0.001 to 10 MPa is preferred, and 0.01 to 5 MPa is more preferred. The time for applying pressure is not particularly limited, but 0.1 to 30 minutes is preferred, and 0.5 to 10 minutes is more preferred.

[0112] Patterns of the disc are not particularly limited, but examples include wiring patterns, line and space patterns, moth-eye patterns, cylindrical shapes, conical shapes, conical shapes, polygonal prism shapes (e.g., square prism shapes), polygonal conical shapes (e.g., square conical shapes), and patterns consisting of protrusions or indentations of polygonal conical shapes (e.g., square conical shapes).

[0113] The base plate used in the method for manufacturing the cured product of the present invention may be one that has undergone a release treatment to improve the peelability of the resin composition for imprinting and the surface of the base plate. The release treatment method is not particularly limited, but examples include treatment with surfactants such as silicone-based, fluorine-based, or non-ionic types, silane coupling agents, fluorine-containing diamond-like carbon, etc.

[0114] After the coating process, a solvent drying process may be performed according to the resin composition for imprinting. In particular, when a high-boiling-point solvent is used, a drying process may be performed to obtain a smooth coating film or to reduce shrinkage after pattern fabrication by the nanoimprinting method.

[0115] The curing method of the resin composition is not particularly limited and may be light curing or thermal curing. In the thermal curing method, the heating temperature is not particularly limited, but 60 to 300°C is preferred, and 100 to 250°C is more preferred. If the heating temperature is below 60°C, curing failure may occur, and if it exceeds 300°C, the shape of the substrate may be damaged depending on the material of the substrate. In addition, the heating time is not particularly limited, but 5 to 120 seconds is preferred, and 10 to 60 seconds is more preferred. If the heating time is less than 5 seconds, curing failure may occur, and if it exceeds 120 seconds, the shape of the substrate may be damaged depending on the material of the substrate, and it is also undesirable from the perspective of productivity because the time required for the process becomes long.

[0116] In the photocuring method, although not particularly limited, the amount of light irradiation in the process of irradiating light onto the pattern forming layer in the method for manufacturing the imprint resin composition of the present invention may be sufficiently greater than the amount of light required for curing. The amount of light required for curing is appropriately determined by irradiating the consumption of unsaturated bonds of the imprint resin composition or the tackiness of the cured film, but, for example, it is preferably in the range of 5 mJ / ㎠ to 2000 mJ / ㎠. The substrate temperature during light irradiation is typically carried out at room temperature, but to increase reactivity, light irradiation may be performed while heating.

[0117] The light used to cure the resin composition for imprinting according to the present invention is not particularly limited and may include, for example, light or radiation with wavelengths in the regions of high-energy ionizing radiation, near-ultraviolet, far-ultraviolet, visible, and infrared. As a source of high-energy ionizing radiation, electron beams accelerated by accelerators such as Cockcroft-type accelerators, Van de Graaff-type accelerators, linear accelerators, betatrons, and cyclotrons are most conveniently and economically used industrially; however, radiation such as gamma rays, X-rays, alpha rays, neutron rays, and proton rays emitted from radioactive isotopes or nuclear reactors may also be used. As a source of ultraviolet radiation, examples include ultraviolet fluorescent lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, carbon arc lamps, and solar lamps. Radiation includes, for example, microwaves and EUV. In addition, laser light used in the microprocessing of semiconductors, such as LEDs, semiconductor laser light, or 248 nm KrF excimer laser light or 193 nm ArF excimer laser light, can also be preferably used in the present invention. These lights may be monochromatic light or may be light with multiple different wavelengths (mixed light).

[0118] After performing patterning by the nanoimprint method and removing the original plate, a curing process may be performed if necessary.

[0119] The imprint substrate of the present invention is characterized by having a convex portion or a concave portion formed of a substrate and a cured product of the photocurable composition for imprinting.

[0120] The imprint substrate of the present invention can preferably be used in the form of an optical coating film, an optical member, or a molded body for optical devices, semiconductor devices, display devices, etc. Specific examples include, for instance, organic EL, touch panels, touch sensors, liquid crystal displays, CMOS, solar cells, transistors, light-emitting diodes, memory, IC, LSI, CPU, RFID, CCD, printed circuit boards, semiconductor mounting substrates, optical waveguides, optical filters, anti-reflective films, lenses, prisms, mirrors, lasers, resonators, PDPs, electronic paper, MEMS, etc.

[0121] Examples

[0122] The present invention will be described below with reference to examples, but the present invention is not limited to the following examples. Unless otherwise noted, “parts” or “%” hereafter mean “parts by weight” or “weight%”, respectively.

[0123] Below, the various drugs used in the examples and comparative examples are summarized and described.

[0124] (1) Inorganic oxide fine particles

[0125] Zirconium oxide (manufactured by Daiichi Kigenso Chemical Industry Co., Ltd., UEP-50, average primary particle size 20 nm)

[0126] Titanium oxide (manufactured by Nippon Aerosil Co., Ltd., P-90, average primary particle size 13 nm)

[0127] (2) Dispersant

[0128] Polymeric dispersant (Manufactured by Big Chem Japan Co., Ltd., BYK118)

[0129] (3) Alkoxysilane

[0130] 3-Methacryloxypropyltrimethoxysilane (Manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503)

[0131] Phenyltrimethoxysilane (Manufactured by Shin-Etsu Chemical Co., Ltd., KBM-103)

[0132] (4) solvent

[0133] Propylene Glycol Monomethyl Ether Acetate (Manufactured by Daicel Co., Ltd., PGMEA)

[0134] Methyl isobutyl ketone (manufactured by Tokyo Kasei Kogyo Co., Ltd., MIBK)

[0135] (5) Curable resin

[0136] Dipentaerythritol hexaacrylate (DPHA) (Manufactured by Shinnakamura Chemical Industry Co., Ltd.)

[0137] Fluorene-backed epoxy resin (Ogsol EA-0200) (Manufactured by Osaka Gas Chemical Co., Ltd.)

[0138] (6) Polymerization initiator

[0139] Photoradical polymerization initiator (Manufactured by IGM Resins, Inc., Omnirad 127)

[0140] Photoradical polymerization initiator (manufactured by IGM Resins, Inc., Omnirad TPO H)

[0141] (7) Leveling agent

[0142] Silicone-based leveling agent (Manufactured by Big Chem Japan Co., Ltd., BYK-331)

[0143] Synthesis Example 1

[0144] 3-methacryloxypropyltrimethoxysilane and phenyltrimethoxysilane were mixed in a molar ratio of 90:10, diluted with MIBK to 50 wt%, and water was added in an amount of 3 equivalents of the total amount of alkoxysilane. 0.05 equivalents of a 20 wt% aqueous sodium hydroxide solution was added dropwise to the total amount of alkoxysilane, and heated at 60°C for 3 hours. A separation process was performed three times by adding water to the solution after the reaction to remove it, and sodium sulfate was added to dehydrate it. Subsequently, the solution was concentrated using an evaporator to obtain polysiloxane A. The molecular weight of the obtained polysiloxane A was measured by GPC, and the weight-average molecular weight was 3300.

[0145] Synthesis Example 2

[0146] 3-methacryloxypropylmethyldimethoxysilane and phenyltrimethoxysilane were mixed in a molar ratio of 70:30, diluted to 50 wt% with MIBK, and 3 equivalents of water were added to the total amount of alkoxysilane. 0.05 equivalents of a 20 wt% aqueous sodium hydroxide solution were added dropwise to the total amount of alkoxysilane, and the mixture was heated at 60°C for 3 hours. A separation process was performed three times by adding water to the solution after the reaction to remove it, and sodium sulfate was added to dehydrate the solution. Subsequently, the solution was concentrated using an evaporator to obtain polysiloxane B. The molecular weight of the obtained polysiloxane B was measured by GPC, and the weight-average molecular weight was 2700.

[0147] Synthesis Example 3

[0148] 3-methacryloxypropyltrimethoxysilane and diphenylsilanediol were mixed in a molar ratio of 40:60, and 0.05 equivalents of Ba(OH)2 were added to the total molar amount of alkoxysilane and silanediol, and heated at 80°C for 3 hours. Toluene was added to the reaction solution, and the solution was concentrated under reduced pressure at 50 hPa while heating at 80°C. After diluting the reaction solution with toluene until the solid content was 50 wt%, the separation process of adding and removing water was repeated 3 times, and the solution was dehydrated with sodium sulfate. Subsequently, the solution was concentrated using an evaporator to obtain polysiloxane C. The molecular weight of the obtained polysiloxane C was measured by GPC, and the weight-average molecular weight was 2300.

[0149] Examples 1 to 14 and Comparative Examples 1 to 3

[0150] Inorganic oxide microparticles, a dispersant, an alkoxysilane compound, and a solvent were mixed in the same proportions as shown in Table 1. Subsequently, the obtained mixture was dispersed using a media-type disperser (bead mill) to obtain an inorganic oxide microparticle dispersion. The processing conditions of the bead mill were set as follows: total injection weight of the mixture 350 g, bead diameter 50 μm, rotation speed 10 m / sec, and dispersion time 180 min.

[0151] A resin composition for imprinting was prepared by mixing a polysiloxane resin, a curable resin, a polymerization initiator, and a leveling agent in the amounts shown in Table 1 into the obtained inorganic oxide fine particle dispersion and stirring at room temperature.

[0152] <Dispersed particle size of fine particles>

[0153] The inorganic oxide microparticle dispersion was diluted with PGMEA to a particle concentration of 1 wt% and measured using a Malvern Zetasizer Nano ZS.

[0154] <Viscosity>

[0155] For the obtained resin composition for imprinting, the viscosity at 25°C was measured using a viscometer (Type B viscometer manufactured by Toki Industry Co., Ltd.).

[0156] <Refractive Index and Abbe Number>

[0157] The obtained imprint resin composition was applied onto a silicon substrate using a spin coat method, the solvent was dried at 80°C for 2 minutes, and the film was cured by exposure at 1000 mJ / cm² to produce a 500 μm film. The refractive index and Abbe number of the obtained film were measured using a spectroscopic ellipsometer (M-2000C manufactured by J.A. Ulam Japan Co., Ltd.).

[0158] <Total Light Transmittance and Haze Value>

[0159] The obtained imprint resin composition was applied onto a 0.7 mm white glass substrate using a spin coat method, the solvent was dried at 80°C for 2 minutes, and the film was cured by exposure at 1000 mJ / cm² to produce a 3 μm film. The total light transmittance and haze value of the obtained film were measured according to JIS K 7150 using a haze computer (manufactured by Suga Testing & Research Co., HGM-2B).

[0160] <Imprint-like>

[0161] The obtained resin composition for imprinting was applied onto a 0.7 mm white glass substrate using a spin coat method, and the solvent was dried at 80°C for 2 minutes to obtain a 3 μm film. Next, a polydimethylsiloxane plate having an L / S pattern of 500 nm width and 500 nm depth was pressed at room temperature under a pressure of 10 bar, and then cured at 1000 mJ / cm² using Eitre3 manufactured by Obducat, after which the pattern was removed to obtain a cured product.

[0162] The transferred patterns were observed using SEM, and imprintability was evaluated in four stages according to the following criteria. The results are shown in Table 1.

[0163] ○ : The pattern is cleanly transferred, and the imprintability is good.

[0164] △ : The pattern is transcribed, but omissions and / or deformations are observed.

[0165] × : All or most of the pattern peeled off from the substrate during the molding process.

[0166] ×× : The pattern was not transferred because the mold did not go in the depth direction.

[0167]

[0168] As shown in Table 1, the imprint resin compositions of Examples 1 to 14 exhibited excellent imprintability along with optical properties. The imprint resin composition of Comparative Example 1, which contained only a small amount of polysiloxane resin and a large amount of inorganic oxide microparticles, and the imprint resin composition of Comparative Example 2, which contained a large amount of polysiloxane resin and a small amount of inorganic oxide microparticles, showed inferior imprintability. Additionally, the imprint resin composition of Comparative Example 3, which did not contain polysiloxane resin, also showed inferior imprintability.

Claims

Claim 1 (A) The following general formula (1) (of general formula (1), R 1 , R 2 , R 3 Each is independently a hydrogen atom, a hydroxyl group, an alkoxy group, a hydrocarbon group having 1 to 12 carbon atoms, or a substituent having 1 to 12 carbon atoms having one or more crosslinkable functional groups, wherein R 1 , R 2 , R 3 If each of exists in multiple forms, they may be different, and R 1 , R 2 , R 3 A resin composition for imprinting comprising a polysiloxane resin represented by (B) an inorganic oxide microparticle and an alkoxysilane compound, wherein at least one of the components is a carbon-1 to 12 substituent having one or more crosslinkable functional groups, and a, b, c, and d are numbers satisfying 0.001 ≤ a ≤ 1.00, 0 ≤ b ≤ 0.999, 0 ≤ c ≤ 0.30, 0 ≤ d ≤ 0.30, and a + b + c + d = 1.0), and (B) an inorganic oxide microparticle and an alkoxysilane compound, wherein the weight ratio of the total weight of the polysiloxane resin (A), the alkoxysilane compound, and the optional curable resin to the weight of the inorganic oxide microparticle (B) is 0.2 to 2.5, and the solid fraction of the composition is 10 to 85 weight%. Claim 2 A resin composition for imprinting according to claim 1, wherein the crosslinking functional group having a substituent having 1 to 12 carbon atoms is a (meth)acrylic group, (meth)acryloxy group, vinyl group, or epoxy group. Claim 3 A resin composition for imprinting according to claim 1 or 2, wherein the weight average molecular weight of the polysiloxane resin (A) is 1,000 to 5,000. Claim 4 A resin composition for imprinting according to claim 1 or 2, wherein the average particle size after dispersion of inorganic oxide microparticles (B) is 10 to 70 nm. Claim 5 A resin composition for imprinting according to claim 1 or 2, wherein the weight ratio of the total weight of the polysiloxane resin (A), the alkoxysilane compound, and the curable resin which is an optional component, to the weight of the inorganic oxide microparticles (B) is 0.25 to 1. Claim 6 A resin composition for imprinting according to claim 1 or 2, wherein the inorganic oxide microparticles (B) are zirconium oxide or titanium oxide. Claim 7 An imprint substrate having a convex or concave portion formed by a substrate and a cured product of the imprint resin composition described in claim 1 or 2. Claim 8 A method for manufacturing an imprint substrate comprising the steps of: applying an imprint resin composition described in claim 1 or 2 to a substrate; and patterning by a nanoimprint method.

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