JP5269449B2 - Curable resin composition for nanoimprint - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for nano-imprints stably forming fine patterns efficiently in high precision, and a cured product thereof. <P>SOLUTION: This photo-curable resin composition for nano-imprints comprises a combination of a cationically polymerizable compound and a radically polymerizable compound, or a heterolytically polymerizable compound having both cationic polymerizability and radical polymerizability. As the cationically polymerizable compound, for example, a cyclic ether compound, a vinyl ether compound, a polycarbonate-based compound and the like can be utilized. The method for producing the fine structural matter comprises preferably: (1) a process of forming a film comprising this resin composition on a support, (2) a process of transcribing patterns on the film by using a nano-stamper, and (3) a process of curing the film with transcribed patterns to obtain the fine structural matter. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a photocurable resin composition suitable for manufacturing a fine structure using a nanoimprint technique in the field of microlithography, and a fine cured product using the same.

  Miniaturization of electronic components that require resolution down to the range of less than 1 μm has been achieved substantially by photolithography techniques. Further resolution is being achieved with the development of immersion technology using ArF with a short exposure wavelength as the light source, but the technology for forming line widths of 32 nm or less has problems such as line edge roughness depending on the physical properties of the resin. It has become apparent. On the other hand, the cost of photolithographic equipment such as masks, mask aligners and steppers is rapidly increasing to meet the increasing demands for resolution, wall slope and aspect ratio (height to resolution ratio). In particular, the latest steppers are extremely expensive, which increases the overall cost of microchip manufacturing. In addition, studies have been made to make finer radiation using short-wavelength radiation such as electron beams and X-rays, but there is a problem of considerable investment in mass production.

  In general, in order to obtain an excellent viewing angle and brightness, a plurality of functional films including a light guide plate, a prism sheet, a polarizing plate, an antireflection film, and the like are used for a liquid crystal display. Since these functional films require the reproduction of fine patterns calculated with high precision in order to perform the desired functions, in recent years, vigorous development of films with fine irregularities on the surface has been made. Yes.

  As a method for forming a fine uneven pattern on a film, US Pat. No. 5,772,905 uses a rigid stamp having a relief on a resist made of a thermoplastic resin attached to the entire surface of a substrate (wafer). A nanoimprint method for performing thermoplastic deformation is disclosed. In this method, a thermoplastic resin (polymethyl methacrylate, PMMA) is used as a resist for thermal stamping. However, since there is a normal fluctuation width of about 100 nm across the entire wafer surface, a rigid stamp is used. It is very difficult to structure 6, 8 and 12 inch wafers in a single step. For this reason, a more complicated “step and repeat” method may be adopted as a pattern forming method. However, this method is not suitable for the manufacturing process because it reheats adjacent regions that are already structured. Further, when a thermoplastic resin is used as a material, there is a problem that expansion and contraction due to heat occur and it is difficult to obtain a film as designed.

International Publication No. WO99 / 22849 discloses a microstructuring method that takes an approach different from the above. Specifically, a flexible polydimethylsiloxane stamp having a desired microstructure is placed on a flat inorganic substrate, a TEOS solution is infiltrated into the microstructure using capillary action, and then the solvent ( This is a method of forming a target porous SiO ₂ structure by removing the TEOS solution. The porous bodies thus obtained are mainly used in the field of biomimetics (composite materials for teeth and bones). However, according to this method, it is difficult to accurately produce a very fine pattern as required in the semiconductor and liquid crystal fields.

  In US Pat. No. 5,900,160, US Pat. No. 5,925,259 and US Pat. No. 5,817,242, stamps are made of UV curable resists (self-assembled monolayers such as alkylsiloxanes). A method of wetting and then pressing onto a smooth substrate is disclosed. Similar to the conventional stamp process, this method is a method in which a structured resist material remains when the stamp is lifted from the substrate surface. Although the used resist material shows good wetting with respect to the substrate, there is a problem that it is difficult to peel off from the substrate after the circuit pattern is formed and the etching resistance is not sufficient. Moreover, the size (resolution) of the structure is in the region of 1 μm, and it has been difficult to accurately produce a fine pattern of nanometer order that is required in the fields of semiconductors and liquid crystals.

US Pat. No. 5,772,905 International Publication WO99 / 22849 Pamphlet US Pat. No. 5,900,160 US Pat. No. 5,925,259 US Pat. No. 5,817,242

The objective of this invention is providing the resin composition for nanoimprint which can form a fine pattern economically stably, and its hardened | cured material.
In addition to the above, another object of the present invention is to provide a resin composition for nanoimprinting capable of thick film processing and a structure thereof.

  As a result of intensive studies to achieve the above object, the present inventors have formed a fine pattern efficiently by applying nanoimprint processing according to the resin composition having both cationic polymerization reactivity and radical polymerization reactivity. It has been found that it is possible to produce a large amount of fine structures by nanoimprint processing using such a resin composition, and it is extremely advantageous economically, and the present invention has been completed.

（式中、Ｒ¹〜Ｒ¹⁸は、同一又は異なって、水素原子、ハロゲン原子、アルキル基又はアルコキシ基を示す）
で表される化合物、及び下記式（２）

（式中、Ｒ^19aは、同一又は異なって、水素原子、炭素数１〜１０の一価又は多価の炭化水素基、一価若しくは多価のアルキルエステル、又は一価若しくは多価のアルキルエーテルを示し、Ｒ^19bは、水素原子、アルキル基を示し、Ｒ²⁰〜Ｒ²³は、同一又は異なって、水素原子、ハロゲン原子、アルキル基又はアルコキシ基を示す。ｐは１〜６の整数を示し、ｍ及びｎは０〜３の整数を示し、Ｘ，Ｙ，Ｚは酸素原子又は硫黄原子を示す。但し、ｐが１のとき、Ｒ^19aは、水素原子又は炭素数１〜１０の一価のアルキル基、一価のアルキルエステル、又は一価のアルキルエーテルを示し、ｐが２以上のとき、Ｒ^19aは単結合、ｐ価の炭化水素基、ｐ価のアルキル基又はｐ価のアルコキシ基を示す）
で表される化合物からなる群から選択される少なくとも一つであり、
ラジカル重合性化合物が、下記式（ａ）又は（ｂ）

（式中、Ｒ¹は水素原子又はメチル基を示し、Ｒ^a及びＲ^bはそれぞれ水素原子、メチル基、又はエチル基を示し、Ｒ^cは炭素数１〜１０の２価の脂肪族炭化水素、炭素数１〜６の２価の脂環式炭化水素基、ｐ−キシレン、又はフェニレンを示し、ｍは４〜８の整数、ｎは１〜１０の整数を示す）
で表されるラクトン変性（メタ）アクリル系化合物であるナノインプリント用光硬化性樹脂組成物を提供する。 That is, the present invention is a photocurable resin composition for nanoimprint comprising a combination of a cationic polymerizable compound and a radical polymerizable compound,
The cationically polymerizable compound is represented by the following formula (1)

(Wherein R ^{1 to} R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group)
And a compound represented by the following formula (2)

Wherein R ^19a is the same or different and is a hydrogen atom, a monovalent or polyvalent hydrocarbon group having 1 to 10 carbon atoms, a monovalent or polyvalent alkyl ester, or a monovalent or polyvalent alkyl ether. R ^19b represents a hydrogen atom or an alkyl group, and R ^{20 to} R ²³ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and p represents an integer of 1 to 6. , M and n represent an integer of 0 to 3, and X, Y and Z represent an oxygen atom or a sulfur atom, provided that when p is 1, R ^19a is a hydrogen atom or a monovalent carbon atom having 1 to 10 carbon atoms. An alkyl group, a monovalent alkyl ester, or a monovalent alkyl ether, and when p is 2 or more, R ^19a is a single bond, a p-valent hydrocarbon group, a p-valent alkyl group or a p-valent alkoxy group. Indicate)
At least one selected from the group consisting of compounds represented by :
The radical polymerizable compound is represented by the following formula (a) or (b):

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ^a and R ^b represent a hydrogen atom, a methyl group, or an ethyl group, respectively, and R ^c represents a divalent aliphatic hydrocarbon having 1 to 10 carbon atoms. And a divalent alicyclic hydrocarbon group having 1 to 6 carbon atoms, p-xylene, or phenylene, m is an integer of 4 to 8, and n is an integer of 1 to 10)
A photocurable resin composition for nanoimprinting, which is a lactone-modified (meth) acrylic compound represented by the formula:

（式中、ｘ１〜ｘ４は０〜５の整数を示す。但し、ｘ１〜ｘ４の合計値が１以上である）
で表されるホウ酸塩類である感放射性カチオン重合開始剤を含んでいてもよい。本発明の樹脂組成物は、さらに、アントラセン系増感剤を含んでいてもよく、また、造膜助剤として、側鎖にラジカル重合性不飽和結合基及び／又はカチオン硬化性官能基を有する化合物を含んでいてもよい。 In the resin composition of the present invention, the anion moiety is further SbF ₆ ^- or the following formula (3).

(Wherein, x1 to x4 represent integers of 0 to 5. However, the total value of x1 to x4 is 1 or more)
The radiation sensitive cationic polymerization initiator which is borate represented by these may be included. The resin composition of the present invention may further contain an anthracene sensitizer, and has a radically polymerizable unsaturated bond group and / or a cationically curable functional group in the side chain as a film forming aid. It may contain a compound.

  The resin composition of the present invention further comprises oxides, nitrides, phosphides, carbonates, carboxylates, phosphates, sulfates, silicates, titanates, zirconates, aluminates Nanoscale particles made of at least one selected from the group consisting of salts, stannates, lead salts, and mixed oxides thereof may be included.

  Moreover, this invention provides the manufacturing method of the fine structure which gives a fine structure by giving the nanoimprint process to the resin composition of the said invention. The method of the present invention includes, for example, (1) a step of applying the resin composition of the present invention to form a coating, (2) a step of transferring a pattern to the coating using a nano stamper, and (3) a pattern comprising: A step of curing the transferred film to obtain a fine structure.

  In the step (1), a film made of a resin composition may be formed on a transparent support. In the step (2), at least one selected from silicone, glass, and silica glass is used as a material. A nano stamper can be used. In the steps (2) and (3), the nanostamper is pressed on the coating at a pressure of 0.1 to 10 MPa for 5 to 300 seconds to transfer the pattern, and at the same time, the coating is cured by heating or UV irradiation. And a step of obtaining a fine structure. The production method of the present invention may further include (4) a step of etching the cured film.

  The present invention provides a fine structure obtained by the production method of the present invention. The fine structure in the present invention includes, for example, a semiconductor material, a diffraction type condensing film, a polarizing film, an optical waveguide, or a hologram.

  In this specification, “nanoimprint” means not only a normal nanoimprint (nanoimprint in a narrow sense) that transfers a pattern by pressing a nanostamper on a coating provided on a support, but also a gold in which a fine pattern is formed instead of a nanostamper. Using a mold, a resin composition is poured onto the mold, a support is placed on the mold, and a fine pattern transfer technique (in a broad sense, nanoimprint) using a mold using a method of pressing from the top surface is used. .

  According to the present invention, since a resin composition that hardly cures and shrinks is used, a fine structure having a fine pattern of nanometer order can be efficiently manufactured with excellent accuracy by nanoimprint processing. The method of performing nanoimprint processing on such a resin composition is suitable for mass production of fine structures, and can produce fine structures such as semiconductor materials, optical waveguides, and holograms economically and efficiently.

[Cationically polymerizable compound]
The cationically polymerizable compound in the present invention is not particularly limited as long as it is a compound having a cationically polymerizable functional group, and may be any of a monomer, an oligomer, and a prepolymer. Many types of cationically polymerizable functional groups are known. Among them, as functional groups having high practicality, cyclic ether groups such as epoxy groups and oxetanyl groups; vinyl ether groups; carbonate groups (O—CO—O) Group) and the like.

  Representative cationic polymerizable compounds include cyclic ether compounds such as epoxy compounds and oxetane compounds; vinyl ether compounds; carbonate compounds such as cyclic carbonate compounds and dithiocarbonate compounds.

  The epoxy compound is not particularly limited as long as it is a cationically polymerizable compound having an epoxy group, and a liquid or a solid can be used. Epoxy compounds include, for example, alicyclic epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins having a biphenyl skeleton, naphthalene ring-containing epoxy resins, dicyclopentadiene. Dicyclopentadiene type epoxy resin having a skeleton, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, triphenylmethane type epoxy resin, aliphatic epoxy resin, triglycidyl isocyanurate, etc. are included . These epoxy compounds can be used alone or in combination of two or more. Especially, an alicyclic epoxy resin is suitable at the point which is excellent in a cure rate.

  Especially, the epoxy compound which has hardening expansibility is suitable at the point which can control hardening shrinkage and can provide the outstanding pattern formation property. As a typical curing-expandable epoxy compound, a compound represented by the above formula (1) and the like can be mentioned.

In formula (1), examples of the alkyl group for R ^{1 to} R ¹⁸ include aliphatic alkyl groups such as methyl, ethyl, and propyl; and cycloalkyl groups such as cyclohexyl. Examples of the alkoxyl group in R ^{1 to} R ¹⁸ include alkyloxy groups such as methoxy, ethoxy, pentyloxy, and pentenyloxy. The alkyl group or alkoxy group in R ^{1 to} R ¹⁸ may have an oxygen atom, a halogen atom, or a substituent. The said substituent is not specifically limited unless the hardening of this invention is impaired, A well-known thing can be utilized. Specific examples of the cyclic ether compound having a curing expansion property include, for example, 3,4,3 ′, 4′-diepoxybicyclohexyl (volume expansion coefficient 2.4%; trade name “CEL8000” manufactured by Daicel Chemical Industries, Ltd.). Etc.).

  As an example of an alicyclic epoxy resin as a commercial product of an epoxy compound, Daicel Chemical Co., Ltd. Celoxide 2000, 2021, 3000, EHPE3150CE; Mitsui Petrochemical Co., Ltd., Epomic VG-3101: Yuka Shell Epoxy Co., Ltd. ), F-1031S; Mitsubishi Gas Chemical Co., Ltd., TETRAD-X, TETRAD-C; Nippon Soda Co., Ltd., EPB-13, EPB-27, etc. are available. These can be used alone or in combination.

  As a vinyl ether compound, if it is a cationically polymerizable compound which has a vinyl ether group, it will not specifically limit, A well-known thing can be utilized. Examples of such vinyl ether compounds include alkyl vinyl ethers, aromatic vinyl ethers, α-substituted vinyl ethers, β-substituted vinyl ethers, and polyfunctional compounds having two or more functional groups in the molecule (divinyl ethers, trivinyl ethers, Vinyl ethers, etc.).

  Examples of the alkyl vinyl ethers include monofunctional or polyfunctional vinyl ether compounds and allyl ether compounds containing a hydrocarbon group. Specific examples of the monofunctional vinyl ether compound include alkyl vinyl ethers such as t-butyl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxybutyl vinyl ether and diethylene glycol monovinyl ether; and aromatic hydrocarbon groups such as phenyl and benzyl. Examples thereof include aromatic vinyl ethers contained in the molecule.

  Examples of the polyfunctional compound include divinyl ethers such as triethylene glycol divinyl ether, 1,4-cyclohexane diallyl ether, and trimethylolpropane divinyl ether; bifunctional compounds such as aromatic divinyl ethers such as bisphenol-A divinyl ether; Trifunctional compounds such as trimethylolpropane trivinyl ether; and tetrafunctional compounds such as pentaerythritol tetravinyl ether.

  The α-substituted vinyl ethers are vinyl ether compounds having a substituent such as an alkyl group or an allyl group at the α-position, such as α-methyl vinyl ethyl ether, α-ethyl vinyl ethyl ether, α-phenyl vinyl ethyl, Examples include ether. The β-substituted vinyl ethers are vinyl ether compounds having a substituent such as an alkyl group or an allyl group at the β-position, for example, β-methyl vinyl ethyl ether, β-methyl vinyl isopropyl ether, β-methyl vinyl n -Butyl ether, (beta) -methyl vinyl isobutyl ether, (beta) -methyl vinyl t-butyl ether, etc. are mentioned.

  Commercial products of such vinyl ether compounds include 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), 2-hydroxybutyl vinyl ether (HBVE), triethylene glycol divinyl ether, ISP, manufactured by Maruzen Petrochemical Co., Ltd. Examples include RAPI-CURE series, V-PYROLR (N-Viny-2-Pyrrolidone), and V-CAPTM (N-Vinyl-2-Caprolactam).

  The oxetane compound is not particularly limited as long as it is a cationically polymerizable compound having an oxetanyl group, and known compounds can be used.

  Specific examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 3-allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl- 3-Oxetanylmethyl) ether, ethyldiethylene Cole (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylethyl ( 3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3- Ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl) -3-Oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) Ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, 3,7- Bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, butanediol Bis (3-ethyl-3-oxetani Rumethyl) ether, hexanediol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether Tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO Modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO modified hydrogenated bisphenol A bis (3-ethyl-3-io) Cetanylmethyl) ether, EO-modified bisphenol F bis (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) Ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether Dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether , Ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, carbonate bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylate bisoxetane, 3- (3-methyl-3-oxetanemethoxy) propyltriethoxy Examples thereof include silane, 3- (3-ethyl-3-oxetanemethoxy) propyltrimethoxysilane, and oxetane silicone described in JP-A-6-16804. These oxetane compounds can be used alone or in combination of two or more.

  Commercially available oxetanyl compounds include 3-ethyl-3- (phenoxymethyl) oxetane (POX), di [1-ethyl (3-oxetanyl)] methyl ether (DOX), 3-ethyl-3- (2-Ethylhexyloxymethyl) oxetane (EHOX), 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane (TESOX), oxetanylsilsesquioxane (OX-SQ), phenol novolak And oxetane (PNOX-1009). These oxetane compounds may be used alone or in combination.

  The carbonate compound can be selected from known compounds having a carbonate group in the molecule. Especially, the carbonate type compound which has hardening expansibility is suitable at the point which can control hardening shrinkage and can provide the outstanding pattern formation property. Examples of typical curable expandable carbonate compounds include compounds represented by the formula (2).

In formula (2), examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms in R ^19a and R ^19b include alkyl groups such as methyl, ethyl, and propyl. Examples of the polyvalent hydrocarbon group having 1 to 10 carbon atoms in R ^19a include divalent hydrocarbon groups such as methylene, ethylene, ethylidene, propylene and propylidene; trivalent hydrocarbon groups such as methylidyne and ethylidene. And polyvalent hydrocarbon groups. The monovalent alkyl ether in R ^19a and R ^19b is, for example, an alkyloxy group such as methoxy or ethoxy; a cycloalkyloxy group such as cyclohexyloxy group; an R ^x —O— group such as phenyloxy group or benzyloxy group (R ^x is a monovalent hydrocarbon group). Examples of the monovalent alkyl ester include acetooxy. Examples of the polyvalent alkyl ether in R ^19a include —O—R ^y —O— groups (R ^y is a divalent hydrocarbon group) such as methylenedioxy and ethylenedioxy, and —R ^y —O. - group, -R ^y -O-R ^y - like group. The alkyl group or alkoxy group in R ^{20 to} R ²³ may have an oxygen atom, a halogen atom, or a substituent. The said substituent is not specifically limited unless the hardening of this invention is impaired, A well-known thing can be utilized.

Specific examples of the compound represented by the formula (2) include 2,2-dimethylpropyl carbonate (volume expansion coefficient 1.4%, etc.).

  In the present invention, a resin having a cationic polymerizable group in the side chain can also be used as the cationic polymerizable compound. According to the resin having a cationic polymerizable group in the side chain, the thick film can be easily formed by adjusting the viscosity of the resin composition. The resin composition having such properties can be preferably used particularly for the production of a diffractive condensing film. Examples of such compounds include (meth) acrylic resins such as (meth) acrylic resins having an epoxy group, (meth) acrylic resins having an oxetanyl group, and (meth) acrylic resins having a vinyl ether group. These can be produced by conventional methods.

  The cationically polymerizable compounds in the present invention can be used alone or in combination. In particular, since epoxy compounds, oxetane compounds, and vinyl ether compounds are all substrates and can be used as a solvent, the polymerization reaction can be carried out in a substantially solvent-free state without adding a separate solvent to the resin composition. It is preferably used in that it can be advanced.

[Radically polymerizable compound]
The radical polymerizable compound in the present invention is not particularly limited as long as it is a compound having a radical polymerizable functional group, and may be any of a monomer, an oligomer and a prepolymer. Examples of the radical polymerizable functional group include a (meth) acryloyl group and a vinyl group.

  Representative radical polymerizable compounds include (meth) acrylic compounds and styrene compounds, for example.

  Examples of (meth) acrylic compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate (meth) ) Acrylic acid alkyl esters, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprocactone-modified 2-hydroxyethyl (meth) acrylate and other (meth) acrylic having a hydroxyl group Acid esters, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxytriethyl Glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, (meth) acrylates such as methoxy polyethylene glycol (meth) acrylate, styrene and the like. Examples of the acrylic silane compound include γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropylmethyldiethoxysilane, and acryloxy. Examples include ethoxypropyltrimethoxysilane, acryloxyethoxypropyltriethoxysilane, acryloxydiethoxypropyltrimethoxysilane, and acryloxydiethoxypropyltriethoxysilane. As polyfunctional monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polyurethane diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane ethylene oxide modified triacrylate, Trimethylolpropane propylene oxide-modified triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and methacrylates corresponding to the above acrylate, mono-, di-, tri- of polybasic acid and hydroxyalkyl (meth) acrylate Or there are more polyesters, etc. It can be used in combination of two or more.

  Of these, (meth) acrylic compounds having at least an acid group and an unsaturated group in the molecule are preferred. Examples of the compound having an acid group and an unsaturated group include methacrylic acid, vinylphenol, and modified unsaturated carboxylic acid. The modified unsaturated carboxylic acid means a compound having a structure in which a chain is extended between an unsaturated group (double bond) and a terminal carboxyl group. For example, β-carboxyethyl (meth) acrylate ( Alkyl-modified unsaturated carboxylic acids such as (meth) acryloyloxyalkyl carboxylic acids such as (meth) acryloylalkyl carboxylic acids, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid A modified unsaturated carboxylic acid having an ester bond such as a lactone-modified unsaturated carboxylic acid; a modified unsaturated carboxylic acid having an ether bond;

  Of these, a modified unsaturated carboxylic acid having an ester bond such as a lactone-modified unsaturated carboxylic acid and a modified unsaturated carboxylic acid having an ether bond are preferably used. Further, a modified (meth) acrylic compound having an acid group is also preferably used, and a lactone-modified (meth) acrylic compound having an acid group, a modified (meth) acrylic compound having an acid group and an ether bond, and the like are particularly preferable.

（式中、Ｒ¹は水素原子又はメチル基を示し、Ｒ^a及びＲ^bはそれぞれ水素原子、メチル基、又はエチル基を示し、Ｒ^cは炭素数１〜１０の２価の脂肪族炭化水素、炭素数１〜６の２価の脂環式炭化水素基、ｐ−キシレン、又はフェニレンを示し、ｍは４〜８の整数、ｎは１〜１０の整数を示す） Examples of the lactone-modified (meth) acrylic compound having an acid group include a compound in which (meth) acrylic acid is lactone-modified, a lactone-modified product in which a terminal hydroxyl group is acid-modified with an acid anhydride, and the like. As typical examples of these lactone-modified unsaturated carboxylic acids, the former can be exemplified by the compounds represented by the following formula (a), and the latter can be exemplified by the compounds represented by the following formula (b).

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ^a and R ^b represent a hydrogen atom, a methyl group, or an ethyl group, respectively, and R ^c represents a divalent aliphatic hydrocarbon having 1 to 10 carbon atoms. And a divalent alicyclic hydrocarbon group having 1 to 6 carbon atoms, p-xylene, or phenylene, m is an integer of 4 to 8, and n is an integer of 1 to 10)

（式中、Ｒ¹は、水素原子又はメチル基を示し、Ｒ^a及びＲ^bは、同一又は異なって、水素原子、メチル基、エチル基、プロピル基、及びブチル基を示し、Ｒ^cは、炭素数１〜１０の２価の炭化水素基、炭素数１〜６の２価の脂環式炭化水素基、炭素数６〜２０の２価の芳香族性炭化水素基を示し、ｍ及びｎは１〜１０の整数を示す）
で表される化合物等を例示できる。 Examples of the modified (meth) acrylic compound having an acid group and an ether bond include the following formula (c)

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ^a and R ^b are the same or different and represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a butyl group, and R ^c represents A divalent hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic hydrocarbon group having 1 to 6 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, m and n Represents an integer of 1 to 10)
The compound etc. which are represented by these can be illustrated.

  These compounds having an acid group and an unsaturated group may contain two or more acid groups such as carboxylic acid such as maleic acid in the molecule. The compounds having an acid group and an unsaturated group can be used alone or in combination of two or more.

  In the present invention, a resin having a radical polymerizable group in the side chain can also be used as the radical polymerizable compound. According to the resin having a radical polymerizable group in the side chain, the thick film can be easily formed by adjusting the viscosity of the resin composition. The resin composition having such properties can be preferably used particularly for the production of a diffractive condensing film. Examples of such a compound include an epoxy resin having a (meth) acryloyl group. These can be produced by conventional methods.

  The radically polymerizable compound in the present invention can be used alone or in combination. Among these, since the (meth) acrylic compound can be used as a substrate as well as a solvent, the polymerization reaction can be allowed to proceed substantially in the absence of a solvent without adding a separate solvent to the resin composition. It is preferably used in terms of points.

  The heteropolymeric compound is a compound having both cationic polymerizability and radical polymerizability, specifically, a compound containing a cation polymerizable group and a radical polymerizable group in the molecule, and these (co) Polymer [oligomer, polymer] and the like are included. Typical examples of such heteropolymerizable compounds include cyclic ether group-containing (meth) acrylate compounds; vinyl ether group-containing (meth) acrylate compounds; and polymers thereof. These hetero-polymerizable compounds include, for example, a method of introducing a cationic polymerizable functional group into a radical polymerizable compound such as the above exemplified (meth) acrylic compound, and a (meth) acryloyl added to the above exemplified cationic polymerizable compound. It can be obtained by a method of introducing a radical polymerizable functional group such as a group, and a conventional method can be used.

  The cyclic ether group-containing (meth) acrylate compound includes an epoxy group-containing (meth) acrylate compound and an oxetanyl group-containing (meth) acrylate compound. Representative epoxy group-containing (meth) acrylate compounds include, for example, epoxy methacrylate such as 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl methacrylate, vinyl glycidyl ether, and the like. Typical oxetanyl group-containing (meth) acrylate compounds include oxetanyl methacrylate, and typical vinyl ether group-containing (meth) acrylate compounds include vinyl (meth) acrylate. Examples include vinyl ether group-containing (meth) acrylate compounds.

[Photocurable resin composition]
In the photocurable resin composition for nanoimprinting of the present invention, the content of the cationic polymerizable compound (the former) and the radical polymerizable compound (the latter) is, for example, 1/99 to 99/1 as the former / the latter (weight ratio). The ratio is preferably 10/90 to 95/5, more preferably 30/70 to 90/10, and particularly preferably 30/70 to 50/50. Thereby, hardening shrinkage | contraction can be suppressed more notably and the outstanding pattern shape can be obtained.

  In the photocurable resin composition for nanoimprinting of the present invention, the content of the heteropolymeric compound is, for example, 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of the cationic polymerizable compound and the radical polymerizable compound. Preferably it is 2-40 weight part, More preferably, it is 2-15 weight part. Thus, by containing a different polymerization compound, cure shrinkage is suppressed more notably and a fine pattern can be formed efficiently.

  A preferred embodiment of the present invention includes a photocurable resin composition containing a cationic polymerizable compound, a radical polymerizable compound, and a heteropolymeric compound. According to such a combination, since the film forming property can be improved, there is an advantage that a fine pattern can be accurately formed even on a thin film.

Preferred combinations are exemplified below in the order of (cationic polymerizable compound / radical polymerizable compound / heterogeneous polymerizable compound).
Cyclic ether compound / (meth) acrylic compound / cyclic ether group-containing (meth) acrylic compound,
Cyclic ether group-containing resin / (meth) acrylic compound / cyclic ether group-containing (meth) acrylic compound,
Cyclic ether compound / (meth) acryloyl group-containing resin / cyclic ether group-containing (meth) acrylic compound,
Epoxy compounds and oxetanyl compounds / (meth) acrylic compounds / cyclic ether group-containing (meth) acrylic compounds,
Vinyl ether compounds / (meth) acrylic compounds / cyclic ether group-containing (meth) acrylic compounds vinyl ether group-containing resins / (meth) acrylic compounds / cyclic ether group-containing (meth) acrylic compounds vinyl ether compounds / (meth) Acryloyl group-containing resin / cyclic ether group-containing (meth) acrylic compound cyclic ether compound and vinyl ether compound / (meth) acrylic compound / vinyl ether group-containing (meth) acrylic compound cyclic ether group-containing resin and vinyl ether compound / ( (Meth) acrylic compounds / vinyl ether group-containing (meth) acrylic compounds cyclic ether compounds and vinyl ether compounds / (meth) acryloyl group-containing resins / vinyl ether group-containing (meth) acrylic compounds epoxy compounds and vinyl ethers Product / (meth) acrylic compound / vinyl ether group-containing (meth) acrylic compound oxetanyl compound and vinyl ether compound / (meth) acrylic compound / vinyl ether group-containing (meth) acrylic compound carbonate compound and vinyl ether compound / ( (Meth) acrylic compounds / vinyl ether group-containing (meth) acrylic compounds

  The resin composition of the present invention may further contain a radiation-sensitive cationic polymerization initiator. Any radiation-sensitive cationic polymerization initiator can be used without particular limitation as long as it generates an acid upon irradiation with a known active energy ray. Examples thereof include sulfonium salts, iodonium salts, phosphonium salts, and pyridinium salts. be able to.

  Examples of the sulfonium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, bis (4- (diphenylsulfonio) -phenyl) sulfide-bis (hexafluorophosphate), bis (4- (diphenylsulfo). Nio) -phenyl) sulfide-bis (hexafluoroantimonate), 4-di (p-toluyl) sulfonio-4'-tert-butylphenylcarbonyl-diphenylsulfide hexafluoroantimonate, 7-di (p-toluyl) sulfonio 2-isopropylthioxanthone hexafluorophosphate, 7-di (p-toluyl) sulfonio-2-isopropylthioxanthone hexafluoroantimonate, and the like, and JP-A-6-184170 Publication, Hei 7-61964, JP-A No. 8-165290, JP-U.S. Patent No. 4,231,951, and aromatic sulfonium salts described in U.S. Patent No. 4,256,828 and the like.

  Examples of the iodonium salt include diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, JP-A-6-184170, US Pat. No. 4,256,828 and the like. And aromatic iodonium salts described in the above.

Examples of the phosphonium salt include tetrafluorophosphonium hexafluorophosphate, tetrafluorophosphonium hexafluoroantimonate, and aromatic phosphonium salts described in JP-A-6-157624.
Examples of the pyridinium salt include pyridinium salts described in Japanese Patent No. 2519480, Japanese Patent Laid-Open No. 5-222112, and the like.

The anion of the radiation-sensitive cationic polymerization initiator is preferably a radiation-sensitive cationic polymerization initiator that is a borate represented by SbF ₆ ⁻ or the above formula (3) from the viewpoint of improving the reactivity. More preferable examples of the borates represented by the formula (3) include tetrakis (pentafluorophenyl) borate.

  The sulfonium salt and iodonium salt can be easily obtained from the market. Examples of commercially available radiation-sensitive cationic polymerization initiators include UVI-6990 and UVI-6974 manufactured by Union Carbide, Adekaoptomer SP-170 and Adekaoptomer SP-172 manufactured by Asahi Denka Kogyo Co., Ltd. And iodonium salts such as PI 2074 from Rhodia and Irgacure 250 from Ciba.

  The addition amount of the radiation-sensitive cationic polymerization initiator is not particularly limited, but is preferably 0.1 to 15 parts by weight, more preferably 1 to 12 parts by weight with respect to 100 parts by weight of the epoxy resin.

  The resin composition of the present invention may further contain a radiation-sensitive radical polymerization initiator. Radiation sensitive radical polymerization initiators include benzoin, benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy 2-phenylacetophenone, 1,1-dichloroacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- ( Acetophenones such as 4-morpholinophenyl) -butan-1-one; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, etc. Traquinones; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-isopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenones such as benzophenone Xanthones; known and commonly used photopolymerization initiators such as 1,7-bis (9-acridinyl) heptane can be used alone or in combination of two or more thereof.

  These radiation-sensitive radical polymerization initiators include N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like. It can be used in combination with one or more known and commonly used photosensitizers such as secondary amines.

  For example, commercially available radiation-sensitive radical initiators include Irgacure® 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure® 500 (1-hydroxycyclohexyl phenyl ketone, benzophenone available from Ciba. ), And other photoinitiators of the Irgacure® type; Darocur® 1173, 1116, 1398, 1174 and 1020 (available from Merck) and the like. Suitable thermal initiators are inter alia organic peroxides in the form of diacyl peroxides, peroxydicarbonates, alkyl peresters, dialkyl peroxides, perketals, ketone peroxides and alkyl hydroperoxides. Specific examples of such thermal initiators are dibenzoyl peroxide, t-butyl perbenzoate and azobisisobutyronitrile.

  The resin composition of the present invention may contain a sensitizer. Examples of such a sensitizer include anthracene, phenothiazene, perylene, thioxanthone, and benzophenone thioxanthone. Further, as sensitizing dyes, thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes And pyrylium salt pigments.

  Among these, anthracene sensitizers, when used in combination with a radiation-sensitive cationic polymerization initiator (cationic curing catalyst), dramatically improve sensitivity and also have a radical polymerization initiation function. There is no need to use an initiator. For this reason, in the structure of the resin composition of this invention, there exists an advantage that a catalyst seed | species can be simplified.

  As specific anthracene compounds, dibutoxyanthracene, dipropoxyanthraquinone (Anthracure UVS-1331, 1221 manufactured by Kawasaki Kasei Co., Ltd.) and the like are effective.

  The content of the sensitizer is, for example, 0.01 to 20 parts by weight, preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the composition.

Nanoscale particles are added as necessary for the purpose of improving the refractive index of the cured product. In particular, according to the resin composition containing nanoscale particles, a diffractive condensing film having a high refractive index can be produced. Such nanoscale particles may be either organic particles or inorganic particles. Examples of such nanoscale particles include non-polymerizable silanes, polymerizable silanes, and polycondensates of polymerizable silanes. The non-polymerizable silane includes the following formula (I)
Si (X) ₄ (I)
(In the formula, X represents a hydrogen atom, a halogen atom, a hydrolyzable group or a hydroxyl group. However, four Xs may be the same or different.)
The compound etc. which are represented by these are included. The polymerizable silane includes the following formula (II)
(R ¹ ) _a (R ² ) _b Si (X) _(4-ab) (II)
Wherein R ¹ is a non-hydrolyzable group, R ² is an organic group having a functional group, X represents a hydrolyzable group or a hydroxyl group, and a and b are 0, 1, 2, 3 However, the sum (a + b) is either 1, 2, or 3, and a R ¹ , b R ² , and 4 X may be the same or different. May be)
The compound represented by these is included. The polymerized silane polycondensate may be either a homopolymer or a copolymer made of the same or different polymerizable silanes.

Examples of the halogen atom in X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrolyzable group for X include a hydrogen atom, an alkoxyl group such as C ₁ -C ₆ alkoxy such as methoxy, ethoxy, n-propoxy, isopropoxy and butoxy; C ₆ -C ₁₀ aryloxy such as phenoxy, etc. An acyloxy group such as acetoxy and propionyloxy; an alkylcarbonyl group such as C ₂ -C ₇ alkylcarbonyl such as acetyl; an amino group; one or more hydrogen atoms of the amino group are C ₁ -C ₁₂ alkyl ( particularly monoalkylamino group or a dialkylamino group, and the like substituted with C ₁ -C ₆ alkyl). The hydrolyzable group in X may have one or more conventional substituents such as a halogen atom and an alkoxy group.

Examples of the non-hydrolyzable group in R ¹ include alkyl such as C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl, pentyl, hexyl, cyclohexyl, etc. cycloalkyl; C ₆ ~ such as phenyl and naphthyl; alkynyl such as C ₂ -C ₆ alkynyl such as acetylenyl and propargyl; vinyl, 1-propenyl, 2-propenyl, and alkenyl, such as C ₂ -C ₆ alkenyl such as butenyl Aryl such as C ₁₀ aryl and the like are mentioned. The non-hydrolyzable group in R ¹ may have one or more conventional substituents such as a halogen atom and alkoxy.

Examples of the functional group of the organic group represented by R ² include acryloyloxy, methacryloyloxy, epoxy, oxetanyl, hydroxyl, ether, amino, monoalkylamino, dialkylamino, amide, carboxyl, mercapto, thioether, vinyl, cyano, halogen Aldehyde, alkylcarbonyl, sulfo and phosphate groups. These functional groups are preferably bonded to the silicon atom via an alkylene, alkenylene or arylene bridging group which may be interrupted by an oxygen or sulfur atom or a —NH— group. The bridging group is derived from, for example, the above alkyl, alkenyl or aryl groups. The bridging group for R ² preferably contains 1 to 18, in particular 1 to 8 carbon atoms.

  In the formula (II), a preferably has a value of 0, 1, or 2, b preferably has a value of 1 or 2, and the sum of (a + b) preferably has a value of 1 or 2. Have

  Among the non-polymerizable silanes represented by the formula (I), compounds in which X is a hydrolyzable group are preferable, and tetraalkoxysilanes such as tetraethoxysilane (TEOS) and tetramethoxysilane are particularly preferable. is there.

  Among polymerizable silanes represented by the formula (II), silanes having highly reactive unsaturated groups (double bonds) such as 3- (meth) acryloylpropyltrimethoxysilane; 3-glycidyloxypropyltri Epoxysilanes such as methoxysilane (GPTS) and 3-glycidyloxypropyltriethoxysilane are preferred. These unsaturated groups-containing silanes and epoxy silanes advance a polyaddition or polymerization reaction with the resin (A), the curable monomer (B), etc. via the unsaturated group or epoxy group in the molecule. This is advantageous in that the nanoscale particles can be fixed in the network structure formed by the cured resin.

The polycondensate of the polymerizable silane is a compound obtained by polycondensation reaction of the above-described polymerizable silane, and may be one in which a hydrolysis reaction or the like proceeds as necessary. The hydrolysis reaction and polycondensation reaction can be performed according to a known method such as a sol-gel method in the presence of an acidic condensation catalyst such as HCl or HNO ₃ as necessary.

  Nanoscale inorganic particles include oxides, sulfides, selenides, tellurides, halides, carbides, arsenides, antimonides, nitrides, phosphides, carbonates, carboxyls At least one selected from the group consisting of acid salts, phosphates, sulfates, silicates, titanates, zirconates, aluminates, stannates, lead salts and mixed oxides thereof Examples include nanoscale particles as a raw material.

Specific nanoscale inorganic particles can be appropriately selected from known ones, and those disclosed in, for example, WO 96/31572 can be used. Specific nanoscale inorganic particles include, for example, CaO, ZnO, CdO, SiO ₂ , TiO ₂ , ZrO ₂ , CeO ₂ , SnO ₂ , PbO, Al ₂ O ₃ , In ₂ O ₃ and La ₂ O _3. Oxides; sulfides such as CdS and ZnS; selenides such as GaSe, CdSe or ZnSe; tellurides such as ZnTe or CdTe; NaCl, KCl, BaCl ₂ , AgCl, AgBr, AgI, CuCl, CuBr Halides such as CdI ₂ or PbI ₂ ; Carbides such as CeC ₂ ; Arsenides such as AlAs, GaAs or CeAs; Antimonides such as InSb; BN, AlN, Si ₃ N ₄ or Ti ₃ N ₄ nitrides such as; GaP, InP, Zn ₃ phosphides such as P ₂ or _{Cd 3 P 2; Na 2 CO} 3, K 2 C Carboxylic acid salts, for example CH ₃ COONa and Pb (CH ₃ COO) ₄ acetates such as;; _3, CaCO _3, SrCO ₃ and BaCO carbonates such as ₃ phosphates; sulfates; silicates; titanates Zirconates; aluminates; stannates; lead salts, and conventional glass compositions whose composition preferably has a low coefficient of thermal expansion, such as SiO ₂ , TiO ₂ , ZrO ₂ and Al ₂ O ₃ Examples thereof include particles made of a corresponding mixed oxide or the like corresponding to a combination of components, ternary components or quaternary components.

As materials for the nanoscale inorganic particles other than the above, mixed oxides having a perovskite structure such as BaTiO ₃ or PbTiO ₃ are also suitable. In addition, organically modified inorganic particles such as granular polymethylsiloxanes, methacryloyl functionalized oxide particles and methylphosphoric acid salts may also be used.

These nanoscale particles can be produced by a known method such as a flame hydrolysis method, a flame pyrolysis method, or a plasma method described in, for example, International Publication No. 96/31572. As preferred nanoscale particles, nano-dispersed sols of stabilized colloidal inorganic particles can be used, and commercially available products include silica sol manufactured by BAYER, SnO ₂ sol manufactured by Goldschmidt, and manufactured by MERCK. Commercially available products such as TiO ₂ sols from Sisson, SiO ₂ , ZrO ₂ , A1 ₂ O ₃ and Sb ₂ O ₃ sols from Nissan Chemicals or Aerosil dispersions from DEGUSSA are available.

  Nanoscale particles can change their viscosity behavior by surface modification. The surface modification of the particles can be performed using a known surface modifier. As such a surface modifier, for example, a compound capable of interacting with a functional group present on the surface of the nanoscale particle such as a covalent bond or complex formation, or a compound capable of interacting with a polymer matrix is used. Can do. Examples of such surface modifiers include compounds having a functional group such as a carboxyl group, (primary, secondary, or tertiary) amino group, quaternary ammonium group, or carbonyl group in the molecule. Can be used. Such a surface modifier is usually a liquid under standard temperature and pressure conditions, and is composed of a low molecular organic compound having a carbon number in the molecule of, for example, 15 or less, preferably 10 or less, particularly preferably 8 or less. Is done. The molecular weight of the low molecular weight organic compound is, for example, 500 or less, preferably 350 or less, particularly 200 or less.

Preferred surface modifiers include, for example, formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, acrylic acid, methacrylic acid, crotonic acid, citric acid, adipic acid, succinic acid, glutaric acid, oxalic acid, malein acid and saturated or unsaturated mono- and polycarboxylic acids having 1 to 12 carbon atoms such as fumaric acid (preferably monocarboxylic acids); and C ₁ -C ₄ alkyl esters of these esters (preferably such as methyl methacrylate Amides; β-dicarbonyl compounds such as acetylacetone, 2,4-hexanedione, 3,5-heptanedione, acetoacetic acid and C ₁ -C ₄ alkylacetoacetic acids.

  The particle size of the nanoscale particles is usually about 1 to 200 nm, preferably 2 to 50 nm, particularly about 2 to 20 nm.

  Content of a nanoscale particle is 0.1-50 volume% with respect to the whole resin composition, Preferably it is 0.1-30 volume%, Especially 0.1-20 volume%. In the present invention, nanoscale particles are not necessarily used.

  The resin composition of the present invention may contain other components such as resins, oligomers and monomers other than those described above.

  Such other components include (poly) acrylic acid, (poly) methacrylic acid, (poly) acrylates, (poly) methacrylates, (poly) olefins, (poly) styrene, (poly) imides, (Poly) vinyl compounds, (poly) esters, (poly) arylates, (poly) carbonates, (poly) ethers, (poly) etherketones, (poly) sulfones, (poly) epoxides, fluorine Examples thereof include monomers, oligomers and polymers having one or more polymerizable functional groups in the molecule such as polymers, organo (poly) siloxanes, (poly) siloxanes and hetero (poly) siloxanes.

  Other components include (poly) vinyl chloride, (poly) vinyl alcohol, (poly) vinyl butyral, corresponding copolymers such as poly (ethylene-vinyl acetate), polyethylene terephthalate, polyoxymethylene, poly Examples thereof include ethylene oxide and polyphenylene oxide.

The resin composition of the present invention further comprises the following formula (III)
R ³ (X ¹ ) ₃ Si (III)
Wherein R ³ is a partially fluorinated or perfluorinated C ₂ -C ₂₀ -alkyl group and X ¹ is a C ₁ -C ₃ -alkoxy, methyl, ethyl group or chlorine.
The fluorosilane may be contained. By using the fluorosilane, it is possible to improve the peelability of the resin composition with respect to the nano stamper in the nanoimprint process. In particular, when a glass stamp or a silica glass stamp is used as the nano stamper, the resin composition containing the fluorosilane is preferably used.

The partially fluorinated alkyl group in R ³ means an alkyl group in which at least one hydrogen atom is replaced by a fluorine atom. Preferred R ³ groups are CF ₃ CH ₂ CH ₂ , C ₂ F ₅ CH ₂ CH ₂ , C ₄ F ₉ CH ₂ CH ₂ , n-C ₆ F ₁₃ CH ₂ CH ₂ , n-C ₈ F ₁₇ CH _{2. CH 2, n-C 10 F} 21 CH 2 CH 2 and _{i-C 3 F 7 O- (} CH 2) _3.

Commercially available fluorosilanes represented by the formula (III) include tridecafluoro-1,1,2,2-tetrahydrooctyl-1-triethoxysilane, CF ₃ CH ₂ CH ₂ SiCl ₂ CH ₃ , CF _{3 CH 2 CH 2 SiCl (CH 3} ) 2, CF 3 CH 2 CH 2 Si (CH 3) (OCH 3) 2, i-C 3 F 7 O- (CH 2) 3 SiCl 2 CH 3, n-C 6 _{F 13 CH 2 CH 2 SiCl 2} CH 3 and _{n-C 6 F 13 CH 2} CH 2 SiCl (CH 3) _2.

  The fluorosilane represented by the formula (III) is, for example, 0 to 3% by weight, preferably 0.05 to 3% by weight, more preferably 0.1 to 2.5% by weight, based on the entire resin composition. Particularly preferably, it is used at about 0.2 to 2% by weight.

  The resin composition of the present invention can be used for thick film processing with a thickness exceeding 50 μm. In order to increase the viscosity of the resin composition in order to form a thick film, a binder resin as a thickener may be added to the resin composition. A resin composition to which a binder resin has been added is preferably used as a resist for microstructuring of flat screens, holograms, waveguides, precision mechanical parts, and sensors.

  Examples of the binder resin include polymethacrylate ester or a partially hydrolyzed product thereof, polyvinyl acetate, or a hydrolyzed product thereof, polyvinyl alcohol, or a partially acetalized product thereof, triacetyl cellulose, polyisoprene, polybutadiene, polychloroprene, and silicone. Rubber, polystyrene, polyvinyl butyral, polychloroprene, polyvinyl chloride, polyarylate, chlorinated polyethylene, chlorinated polypropylene, poly-N-vinylcarbazole, or derivatives thereof, poly-N-vinylpyrrolidone, or derivatives thereof, polyarylate, Copolymer of styrene and maleic anhydride, or its half ester, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, acrylamide, acrylonitrile, ethylene , Propylene, vinyl chloride, and copolymers and at least one polymerizable component copolymerizable monomers groups such as vinyl acetate or mixtures thereof, are used.

  It is also possible to use an oligomer type curable resin as the binder resin. Examples thereof include epoxidized resins containing unsaturated groups such as epoxidized polybutadiene and epoxidized butadiene styrene block copolymer. Examples of the commercially available products include Epolide PB and ESBS manufactured by Daicel Chemical Industries. As the copolymerization type epoxy resin, for example, CP-50M, CP-50S, or glycidyl methacrylate manufactured by Nippon Oil & Fats Co., Ltd., which is a copolymer of glycidyl methacrylate and styrene, or a copolymer of glycidyl methacrylate, styrene, and methyl methacrylate. There are copolymers such as cyclohexylmaleimide. Other epoxidized resins having a special structure (for example, a copolymer of 3,4-epoxycyclohexylmethyl (meth) acrylate and styrene, a copolymer of 3,4-epoxycyclohexylmethyl (meth) acrylate, styrene and methyl methacrylate) And a cell top manufactured by Daicel Chemical Industries, Ltd.). In addition, novolak type epoxy resins (for example, obtained by reacting novolaks obtained by reacting phenols such as phenol, cresol, halogenated phenol and alkylphenol with formaldehyde in the presence of an acidic catalyst, and epichlorohydrin and / or methyl epichlorohydrin. As commercially available products such as EOCN-103, EOCN-104S, EOCN-1020, EOCN-1027, EPPN-201, BREN-S manufactured by Nippon Kayaku Co., Ltd., DEN-431 , DEN-439: manufactured by Dainippon Ink & Chemicals, Inc., N-73, VH-4150, etc.), bisphenol type epoxy resins (for example, bisphenols such as bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A) As a commercially available product such as a product obtained by reacting chlorophenols with epichlorohydrin or a product obtained by reacting a diglycidyl ether of bisphenol A with a condensate of the bisphenols with epichlorohydrin, Yuka Shell Co., Ltd. , Epicoat 1004, Epicoat 1002; DER-330, DER-337, etc. manufactured by Dow Chemical Co., Ltd.), trisphenol methane, tris cresol methane and other epichlorohydrin and / or methyl epichlorohydrin obtained as a commercial product thereof Nippon Kayaku Co., Ltd. EPPN-501, EPPN-502, etc.), tris (2,3-epoxypropyl) isocyanurate, biphenyldiglycidyl ether, and the like can also be used. These epoxy resins may be used alone or in combination.

The method for producing a fine structure of the present invention is characterized in that the above-mentioned photocurable resin composition for nanoimprint of the present invention is subjected to nanoimprint processing to obtain a fine structure. The method of the present invention more particularly,
(1) A step of forming a film comprising the resin composition of the present invention on a support,
(2) a step of transferring a pattern to the coating using a nano stamper; and (3) a step of curing the coating with the transferred pattern to obtain a fine structure.

  In the step (1), as the support to which the resin composition is applied, for example, glass, silica glass, film, plastic, silicon wafer or the like can be used. These supports may have an adhesion promoting coating formed on the surface. The adhesion promoting coating can be formed of an organic polymer that ensures sufficient wetting of the resin composition with respect to the support. Examples of the organic polymer for forming such an adhesion promoting film include aromatic compounds-containing polymers or copolymers containing novolaks, styrenes, (poly) hydroxystyrenes and / or (meth) acrylates, and the like. Is mentioned. The adhesion promoting film can be formed by applying a solution containing the organic polymer on a support by a known method such as spin coating.

  The resin composition for nanoimprinting can be applied by itself or as a solution in an organic solvent. The organic solvent is used to make a paste by diluting the composition, enabling an easy coating process, and then drying to form a film to enable contact exposure. Specific examples of such organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, carbitol, methylcarbitol, and butylcarbyl. Toluene, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butylcarby Acetic esters such as tall acetate, propylene glycol monomethyl ether acetate; ethanol, propanol, ethylene glycol Examples include alcohols such as coal and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These may be used alone or in combination of two or more. Can be used in combination.

  In the step (1), a film composed of the resin composition for nanoimprinting can be formed by applying the resin composition onto a support by a known method such as spin coating, slit coating, spray coating, or roller coating. . The viscosity of the coating (resin composition at the time of application) is preferably about 80 mPa · s to 10 Pa · s, preferably about 100 mPa · s to 5 Pa · s, and particularly preferably about 200 mPa · s to 1000 mPa · s. The thickness of the film of the resin composition for nanoimprint (film before curing) formed by the above method (narrowly defined nanoimprint) is, for example, about 0.01 to 1 μm, preferably about 0.01 to 0.5 μm.

  Further, in the step (1), the film made of the resin composition for nanoimprinting is formed by a method other than the above, in which the resin composition is poured onto a mold, a support is overlaid thereon, and pressed from the top surface. It is also possible to do. Such a method may be used particularly for the production of a diffractive condensing film. The thickness of the nanoimprint resin composition film (coating before curing) formed by the above method (broadly defined nanoimprint) is, for example, about 0.1 μm to 10 mm, preferably about 1 μm to 1 mm.

  The nano stamper used in the step (2) is a nano imprint transfer stamp having a transfer pattern formed of irregularities on the surface, and a stamper made of silicone, glass, silica glass, or the like can be used. Among these, the silicone rubber stamper is advantageous in that the resin separation after pattern transfer is good even when a resin composition not containing the fluorosilane of the formula (III) is used. Moreover, it is also possible to use the metal mold | die in which the fine pattern was formed as a nano stamper in this invention.

  In the transfer of the pattern in the step (2), the nano stamper placed on the film is pressed under a pressure of about 0.1 to 10 MPa, for example, for 5 to 300 seconds, preferably 20 to 100 seconds, particularly about 30 to 60 seconds. . The thickness of the film after pattern transfer is, for example, about 0.01 to 1 μm, preferably about 0.01 to 0.5 μm, in the case of a film formed by nanoimprint in a narrow sense. The thickness is about 0.1 μm to 10 mm, preferably about 1 μm to 1 mm.

  In the step (3), the curing treatment may be performed in a state where the nano stamper is allowed to stand on the film, or may be performed after removing the nano stamper. Preferably, as steps (2) and (3), a nanostamper is pressed on the film at a pressure of about 0.1 to 10 MPa for 5 to 300 seconds to transfer the pattern, and at the same time, heating or UV irradiation is applied to form the film. A step of curing to obtain a fine structure is provided. The thickness of the cured film after the curing treatment is, for example, about 0.01 to 1 μm, preferably about 0.01 to 0.5 μm, in the film formed by the nanoimprint in a narrow sense, and in the film formed by the nanoimprint in a broad sense, For example, it is about 0.1 μm to 10 mm, preferably about 1 μm to 1 mm.

  As a method for curing the coating, either heat curing by heating or UV curing by UV irradiation may be used, or both may be used in combination. For UV curing, a nano stamper having UV transparency is usually used. Examples of the thermosetting condition include a condition of heating at about 80 to 150 ° C. for about 1 to 10 minutes. Examples of the UV curing conditions include conditions for irradiating UV for about 5 to 20 minutes.

  After the coating is cured by a curing process, the nano stamper is removed as necessary to obtain an imprinted microstructure.

  When the microstructure thus obtained is investigated using a scanning electron microscope, not only the microstructure imprinted on the target substrate, but also an unstructured residual layer of a coating having a thickness of less than 30 nm remains. I understand that. For subsequent use in microelectronics, it is necessary to remove the residual layer in order to achieve a steep wall slope and a high aspect ratio (aspect ratio). For this reason, it is preferable to provide the process of etching a cured film as process (4) further.

In the step (4), the cured film can be etched by, for example, oxygen plasma or a CHF ₃ / O ₂ gas mixture.

  After etching, the resist coating can be removed with a conventional solvent such as, for example, tetramethylammonium hydroxide.

  Furthermore, desired physical properties can be imparted by performing appropriate treatment according to the type of the fine structure.

  According to the method of the present invention, mass production by the nanoimprint technique is possible, and further, shrinkage due to curing is suppressed, and a fine structure having a fine pattern can be efficiently produced. The fine structure thus obtained is extremely useful as, for example, a semiconductor material, a diffractive condensing film, a polarizing film, an optical waveguide, or a hologram.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Production Example 1
Nanoscale particle dispersion (E-1)
236.1 g (1 mol) of 3-glycidyloxypropyltrimethoxysilane (GPTS) was refluxed with 26 g (1.5 mol) of water for 24 hours. The formed methanol was removed at 70 ° C. by a rotary evaporator. Thus, a GPTS condensate was prepared.
Modified with 345 g of tetrahexylammonium hydroxide modified silica sol (SiO ₂ colloid, diameter of about 5 nm, concentration of about 30 wt% isopropanol solution, 2.4 mg of tetrahexyl ammonium hydroxide solution (concentration of 40 wt% aqueous solution) per gram of silica sol) ) Is added to the prepared GPTS condensate with stirring. The isopropanol was then removed in a rotary evaporator.
A nanoscale particle dispersion (E-1) sol was obtained by diluting with isopropoxyethanol until a nanoimprinting composition having a viscosity of about 300 mPa · s was obtained.

Production Example 2
A mixture of a resin having a cationically polymerizable group in the side chain and a cationically polymerizable compound, a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube, 3,4-cyclohexylmethyl-3, After introducing 350 g of 4-cyclohexanecarboxylate (CEL2021P manufactured by Daicel Chemical Industries) and raising the temperature to 95 ° C., 80 g of cyclomer A200 (manufactured by Daicel Chemical Industries), 3-ethyl-3- (meth) acryloylmethyloxetane ( manufactured by Toagosei Co., Ltd.) 20 g, methyl methacrylate 50g, and 2,2 '- was added dropwise azobis (2-methylbutyronitrile) (Nippon hydrazine Kogyo ABN-E) 30.3 g over both 3 hours. After dropping, the mixture was aged for 3 hours. Thereby, a resin solution having a molecular weight of 5300 was obtained.

Ａ−５：下記式で表される化合物（２−ジメチルプロピルカーボネート；ジメチルトリメチレンカーボネート） ダイセル化学工業社製 ＤＭＴＭＣ

ラジカル硬化性モノマー
Ｂ−１：メタクリル酸
Ｂ−２：アクリル酸ラクトン付加物／東亞合成社製 Ｍ５３００
Ｂ−３：メタクリル酸メチル
Ｂ−４：トリメチロールプロパントリアクリレート／ダイセルサイテック社製
Ｂ−５：テトラエチレングリコールジアクリレート／共栄社
開始剤
Ｃ−１：４−メチルフェニル［４−（１−メチルエチル）フェニルヨウドニウムテトラキス（ペンタフルオロフェニル）ボレート／ローデア製 ＰＩ２０７４
Ｃ−２：２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン／チバスペシャルティケミカルズ社製 Ｉｒｇａｃｕｒｅ６５１
増感剤
Ｄ−１：ジブトキシアントラセン／川崎化成 （ＤＢＡ）
ナノ粒子
Ｅ−１：製造例１で得られた分散液
溶剤
Ｇ−１：プロピレングリコールノモメチルエーテルアセテート／ダイセル化学工業社製ＭＭＰＧ−ＡＣ Examples 1-11 and Comparative Examples 1-3
(Examples 1 to 6, 10, 12 to 17, and 21 are described as reference examples.)
Coating Film Preparation Method Types and amounts of resin (A) and curable monomer (B) listed in Table 1, a mixture of a resin having a cationic polymerizable group in the side chain and a cationic polymerizable compound , a polymerization initiator (C ), Sensitizer (D), nanoscale particles (E) and solvent (G) were mixed in a flask to prepare a resin composition for nanoimprinting. Specific compounds of each component in Table 1 are shown below.
Cationic curable monomer A-1: 3,4-cyclohexylmethyl-3,4-cyclohexanecarboxylate / manufactured by Daicel Chemical Industries, Ltd. CEL2021P
A-2: Oxynorbornene divinyl ether / manufactured by Daicel Chemical Industries, Ltd. A-3: 3-ethyl-3-[(3-ethyloxetane-3-yl) methoxy] methyloxetane / OXT213, manufactured by Toagosei Co., Ltd.
A-4: Compound represented by the following formula (bicyclohexyldiepoxide; 3,4,3 ', 4'-diepoxybicyclohexyl) CEL8000 manufactured by Daicel Chemical Industries, Ltd.

A-5: Compound represented by the following formula (2-dimethylpropyl carbonate; dimethyltrimethylene carbonate) DMTMC manufactured by Daicel Chemical Industries, Ltd.

Radical curable monomer B-1: Methacrylic acid B-2: Acrylic acid lactone adduct / Toagosei Co., Ltd. M5300
B-3: Methyl methacrylate B-4: Trimethylolpropane triacrylate / Daicel Cytec B-5: Tetraethylene glycol diacrylate / Kyoeisha initiator C-1: 4-methylphenyl [4- (1-methylethyl ) Phenyliodonium tetrakis (pentafluorophenyl) borate / Rodea PI2074
C-2: 2,2-dimethoxy-1,2-diphenylethane-1-one / Irgacure 651 manufactured by Ciba Specialty Chemicals
Sensitizer D-1: Dibutoxyanthracene / Kawasaki Kasei (DBA)
Nanoparticle E-1: Dispersion solvent obtained in Production Example 1 G-1: Propylene glycol nomomethyl ether acetate / Daicel Chemical Industries, Ltd. MMPG-AC

  The obtained resin composition for nanoimprinting was spin-coated on a 4-inch silicon wafer pretreated with hexamethyldisilazane under the conditions of 3000 to 6000 rpm for 60 seconds to form a film having a thickness of 1 μm. In addition, about Example 5 using the resin composition containing a solvent, in order to remove a solvent after film formation, the drying process heated at about 95 degreeC for 5 minute (s) was performed. The layer thickness of the coating after drying was about 500 nm.

  The imprinting device is a computer-controlled tester (NM-0401 model manufactured by Myeongchang Kiko Co., Ltd.), which maintains the specified pressure for a specified time by programming loading, relaxation rate, heating temperature, etc. Is possible. Under the conditions described in Table 1 as Examples and Comparative Examples, nanoimprinting was performed using a nanostamper having a 200 nm line and space pattern.

  Next, a cured product having a fine pattern was obtained by applying a curing treatment by irradiation of UV radiation using the attached high-pressure mercury lamp while the nano stamper and the coating film were in contact with each other. In addition, the “peelability” of the resin composition with respect to the nano stamper was evaluated by the method described later. Moreover, "curing shrinkage" was evaluated by the method mentioned later about the obtained hardened material.

Thereafter, the remaining film is subjected to plasma etching using oxygen, and then dry-etched with CHF ₃ / O ₂ (25:10) to produce a semiconductor material in which a desired circuit pattern is formed on the silicon wafer. did. In addition, the “pattern shape” of the obtained semiconductor material was evaluated by the method described later.

(Evaluation method 1)
Coating properties In Examples 1 to 11 and Comparative Examples 1 to 3, the resin composition was spin-coated on a silicon wafer, then the surface state was observed, and the presence or absence of uniform coating film formation was observed. evaluated.
○: A uniform coating film was obtained.
Δ: The coating film was not uniform.
X: The repelling of the coating film was observed after spin coating.

Peelability In Examples 1-11 and Comparative Examples 1-3, after being cured by UV irradiation, the peelability when the nanostamper was peeled from the cured resin composition was evaluated according to the following criteria.
(Double-circle): It peeled easily by applying force to the imprint stamp.
○: Peeling was possible by applying force to the imprint stamp.
X: It was not able to peel.

Curing Shrinkage In the step of transferring the patterns in Examples 1 to 11 and Comparative Examples 1 to 3, after removing the nanostamper, the appearance of the formed pattern was visually observed using a scanning microscope, and the pattern edge condition, and Evaluation was made according to the following criteria from the viewpoint of the rectangle of the edge.
A: The pattern edge and the pattern end were kept rectangular.
Δ: Pattern edge and pattern edge were bent.
X: The pattern surface of both ends contracted and peeling occurred.

Pattern Shape In Examples 1 to 11 and Comparative Examples 1 to 3, patterns formed on a silicon wafer after dry etching were evaluated according to the following criteria.
A: Excellent pattern transfer was made on the silicon wafer.
○: A pattern was transferred onto the silicon wafer.
X: Pattern transfer could not be performed on the silicon wafer.

In Table 1, “*” in the evaluation results indicates that a cured product was not obtained (uncured) according to Comparative Examples 1 and 2.
As shown in Table 1, it was revealed that the resin composition for nanoimprinting of the present invention has excellent curability and little curing shrinkage.

Examples 12-22 and Comparative Examples 4-6
Production of Diffraction-type Condensing Film Resin (A), Curing Monomer (B), Heteropolymerizable Compound, Polymerization Initiator (C), Sensitizer (D) and Nano described in Table 2 The scale particle (E) was mixed to prepare a resin composition for nanoimprinting. In Table 2, each component is the same as Table 1.

As a nano stamper, a diffraction-type condensing film mold (material Ni-P, chevron-shaped pitch width 5 μm, height 5.7 μm, apex angle 45 degrees, lattice pattern size 2 cm long, 1 cm wide, manufactured by Toshiba Machine Co., Ltd.) The resin composition was hung on the diffraction type condensing film mold. A PET film (trade name “A4300”, manufactured by Toyobo Co., Ltd., film thickness: 75 μm) as a support is overlaid on the coating formed in this way, and further, a roller is run from above to planarize, and then exposure is performed. The resin composition was hardened by this. As the curing condition, an ultra-high pressure mercury lamp (USH-3502MA manufactured by Ushio Electric Co., Ltd., illuminance of 16 mW / cm ² ) was used, and exposure was performed with an integrated exposure amount of 1 J / cm ² . After completion of curing, the diffractive condensing film was peeled off from the mold, and this was used as a sample. In addition, the “release property” of the resin composition relative to the mold was evaluated by the method described later.

  About the diffraction type condensing film samples of Examples 12 to 22 and Comparative Examples 4 to 6 obtained as described above, the transferability, adhesion to the support, and the refractive index were evaluated by the methods described below. The results are summarized in Table 2.

(Evaluation method 2)
Release property The release property was evaluated by confirming the state when the diffractive condensing film was peeled from the mold. The evaluation criteria are as follows.
◎: Good ○: Slightly sticky ×: Sticky

Transferability Transferability was evaluated by confirming the apex angle of the chevron shape of each diffraction-type condensing film sample with a metal microscope. The evaluation criteria are as follows.
○: Good (vertical angle 45 degrees)
Δ: Insufficient transfer (vertical angle 40-44 degrees)
X: Untransferable As shown in Table 2, it was confirmed that the apex angle of the sample of Comparative Example 6 was narrower than the apex angle (45 degrees) of the mold.

Adhesiveness with support In accordance with JIS K5400, the adhesiveness between the support base film (PET film) and the resin composition was evaluated. That is, in each diffraction type condensing film sample, scratches that reach the base film with a razor are placed 11 by 20 mm vertically and horizontally to make 100 squares, and cellophane tape (25 mm wide, manufactured by Nichiban Co., Ltd.) is used as the lens. After making it adhere to the part and peeling off rapidly, it evaluated by the number of eyes of the peeled lens part. The evaluation criteria are as follows.
○: 90/100 or more remaining Δ: 60/100 or more remaining ×: less than 60/100 remaining

Refractive Index A UV cured product of the curable composition was prepared, and the refractive index of each cured product was measured using an refractometer.

In Table 2, “*” in the evaluation results indicates that cured products were not obtained (uncured) in Comparative Examples 4 and 5.
From Table 2, it was found that the resin composition for nanoimprinting of the present invention was excellent in curability and had little curing shrinkage. Further, it has been found that addition of nanoparticles shows a high refractive index and is effective as a diffraction type condensing film.

  Since the resin composition for nanoimprinting of the present invention can produce fine structures in large quantities with high accuracy and economically, precision mechanical parts such as semiconductor materials, diffractive condensing films, polarizing films, optical waveguides, holograms, etc. It is extremely useful in the field of

Claims (12)

A photocurable resin composition for nanoimprinting comprising a combination of a cationic polymerizable compound and a radical polymerizable compound,
The cationically polymerizable compound is represented by the following formula (1)

(Wherein R ^{1 to} R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group)
And a compound represented by the following formula (2)

Wherein R ^19a is the same or different and is a hydrogen atom, a monovalent or polyvalent hydrocarbon group having 1 to 10 carbon atoms, a monovalent or polyvalent alkyl ester, or a monovalent or polyvalent alkyl ether. R ^19b represents a hydrogen atom or an alkyl group, and R ^{20 to} R ²³ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and p represents an integer of 1 to 6. , M and n represent an integer of 0 to 3, and X, Y and Z represent an oxygen atom or a sulfur atom, provided that when p is 1, R ^19a is a hydrogen atom or a monovalent carbon atom having 1 to 10 carbon atoms. An alkyl group, a monovalent alkyl ester, or a monovalent alkyl ether, and when p is 2 or more, R ^19a is a single bond, a p-valent hydrocarbon group, a p-valent alkyl group or a p-valent alkoxy group. Indicate)
At least one selected from the group consisting of compounds represented by :
The radical polymerizable compound is represented by the following formula (a) or (b):

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ^a and R ^b represent a hydrogen atom, a methyl group, or an ethyl group, respectively, and R ^c represents a divalent aliphatic hydrocarbon having 1 to 10 carbon atoms. And a divalent alicyclic hydrocarbon group having 1 to 6 carbon atoms, p-xylene, or phenylene, m is an integer of 4 to 8, and n is an integer of 1 to 10)
A photocurable resin composition for nanoimprinting, which is a lactone-modified (meth) acrylic compound represented by: Further, as the radiation-sensitive cationic polymerization initiator, the anion moiety is SbF ₆ ^- or the following formula (3)

(Wherein, x1 to x4 represent integers of 0 to 5. However, the total value of x1 to x4 is 1 or more)
The resin composition of Claim 1 containing the radiation sensitive cationic polymerization initiator which is borates represented by these. Furthermore, the resin composition of Claim 1 or 2 containing an anthracene type sensitizer. In addition, as nanoscale particles, oxides, nitrides, phosphides, carbonates, carboxylates, phosphates, sulfates, silicates, titanates, zirconates, aluminates, tin The resin composition according to any one of claims 1 to 3, comprising nanoscale particles made of at least one selected from the group consisting of acid salts and lead acid salts. Hardened | cured material which consists of a resin composition of any one of Claims 1-4. The manufacturing method of the fine structure which gives a nanoimprint process to the resin composition of any one of Claims 1-4, and obtains a fine structure. (1) The process of forming the film which consists of a resin composition of any one of Claims 1-4 on a support body,
The method for producing a fine structure according to claim 6, comprising: (2) a step of transferring a pattern to the coating using a nano stamper; and (3) a step of obtaining a fine structure by curing the coating with the transferred pattern. . The method for producing a microstructure according to claim 7, wherein in the step (1), a film made of the resin composition is formed on a transparent support. The method for producing a microstructure according to claim 7 or 8, wherein a nano stamper made of at least one selected from silicone, glass, and silica glass is used in the step (2). Furthermore, (4) The manufacturing method of the microstructure of any one of Claims 7-9 including the process of etching a hardened film. The fine structure obtained with the manufacturing method of any one of Claims 6-10. The microstructure according to claim 11, which is a semiconductor material, a diffractive condensing film, a polarizing film, an optical waveguide, or a hologram.