JP5362186B2 - Resin composition for nanoimprint - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for a nano-imprint which can form a fine pattern precisely, efficiently, and stably and its cured product. <P>SOLUTION: The resin composition comprises a resin having radically reactive groups and acid groups on its side chains. For example, the product of the reaction between an acid group-containing (meth)acrylic resin (A) and a compound (B) having a radically reactive group and an epoxy group can be used as the resin. As the resin having the radically reactive groups and the acid groups, for example, the product of the reaction between an acid group-containing (meth)acrylic resin (A) and a compound (B) having a radically polymerizable group and an epoxy group can be used. A fine structure can be produced by a method including the process (1) for forming a coat by applying the photocurable resin composition for the nano-imprint, the process (2) of transferring the pattern to the coat by using a nano-stamper, and the process (3) of obtaining the fine structure by curing the coat to which the pattern is transferred. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a resin composition suitable for forming a fine pattern with high accuracy by nanoimprint processing, a method for producing a fine structure using the resin composition, and a fine structure produced by this method.

  Miniaturization of electronic components that require resolution down to the range of less than 1 μm has been achieved substantially by photolithography techniques. Higher resolution is being achieved by the development of ArF with a short exposure wavelength and its immersion technology, but from around 32 nm, the size of the resin used is approaching, and problems such as line edge roughness have become apparent. ing. In addition, the cost of photolithographic equipment such as masks, mask aligners and steppers is rapidly increasing to meet the increasing demands for resolution, wall tilt 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 refine the radiation using short-wavelength radiation such as electron beams and X-rays, but many problems remain from the viewpoint of productivity.

  In general, a liquid crystal display uses a plurality of functional films including a light guide plate, a prism sheet, a polarizing plate, an antireflection film and the like in order to obtain an excellent viewing angle and luminance. 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 the pattern form 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 efficiently and stably with high precision, and its hardened | cured material.

  As a result of intensive studies to achieve the above object, the inventors of the present invention can efficiently form a fine pattern by performing nanoimprint processing according to a resin composition containing a resin having a specific functional group. The present inventors have found that a fine structure can be produced in large quantities by nanoimprint processing using such a resin composition, which is extremely advantageous economically, and the present invention has been completed.

（式中、Ｒ¹は水素原子又はメチル基を示し、Ｒ²は炭素数１〜１０のアルキレン基を示す） That is, the present invention provides a nanoimprinting resin composition comprising a resin (A) having a radical reactive group and an acid group in the side chain, wherein the resin (A) is a (meth) acrylic ester (i- 1) an acid group-containing (meth) acrylic resin (i) which is a copolymer of an acid group and an unsaturated group-containing compound (i-2), and a compound (ii) having a radical polymerizable group and an epoxy group reaction products der with is, weight average molecular weight of the resin (a) is 2,000 to 15,000, a double bond equivalent of 400 to 1500, the compound having a radical polymerizable group and an epoxy group (ii) is, providing an alicyclic epoxy group-containing unsaturated compound der Ru nanoimprinting resin composition represented by the following formula. The acid value of the resin (A) may be 20 to 150 mgKOH / g.

(Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² is shows the alkylene group having 1 to 10 carbon atoms)

  The resin composition of the present invention may further contain a curable monomer (B) and a polymerization initiator (C). The resin composition of the present invention also has oxides, sulfides, selenides, tellurides, halides, carbides, arsenides, antimonides, nitriding as nanoscale particles (D). Products, phosphides, carbonates, carboxylates, phosphates, sulfates, silicates, titanates, zirconates, aluminates, stannates, lead salts and mixed oxides thereof Nanoscale particles made of at least one selected from the group consisting of 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 coating the resin composition of the present invention on a support to form a coating, (2) a step of transferring a pattern to the coating using a nano stamper, and ( 3) It includes a step of curing the film to which the pattern has been transferred to obtain a fine structure.

In the step (2), a nano stamper made of at least one selected from silicone, glass, and silica glass may be used. In the steps (2) and (3), the nanostamper is applied to the coating film at a pressure of 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 coating film. It may be a step of obtaining a fine structure by curing. The production method of the present invention may further include (4) a step of etching the cured film using CHF ₃ and / or O ₂ plasma.

The present invention provides a fine structure obtained by the production method of the present invention. Examples of the fine structure in the present invention include a semiconductor material, a diffractive condensing film, a polarizing film, an optical waveguide, or a hologram.
Moreover, in this specification, the resin composition for nanoimprints containing resin (A) which has a radical reactive group and an acid group in a side chain is also demonstrated. In the nanoimprint resin composition, the resin (A) having a radical reactive group and an acid group in the side chain includes an acid group-containing (meth) acrylic resin (i), a radical polymerizable group, and an epoxy group. It may be a reaction product with compound (ii).

  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 high 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.

  The resin composition for nanoimprinting of the present invention is characterized by containing a resin having a radical reactive group and an acid group in the side chain. By using such a resin, curing shrinkage is suppressed, and a fine pattern can be formed with high accuracy.

  As the resin having a radical reactive group and an acid group in the side chain in the present invention, for example, a resin such as a novolac resin, an acrylic resin, and a polyurethane resin is used as the main chain, and the radical reactive group is included in the side chain. Examples thereof include a resin into which an acid group has been introduced. Such a resin can be produced by a known method. In the present invention, the radical reactive group is a functional group having radical reactivity such as an unsaturated group (double bond or the like), and can be appropriately selected from known ones. Examples include an acryloyl group and a vinyl group, and a (meth) acryloyl group is particularly preferably used. Examples of the acid group in the present invention include a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and a carboxyl group is particularly preferably used.

  As a resin (A) having a radical reactive group and an acid group in a representative side chain, an acid group-containing (meth) acrylic resin (i) and a compound (ii) having a radical polymerizable group and an epoxy group Reaction products are mentioned. More specifically, it is a modified resin in which a compound having a radical polymerizable group and an epoxy group is added to a (meth) acrylic resin having an acid group in the side chain via a part of the acid group in the side chain. .

  The acid group-containing (meth) acrylic resin (i) is not particularly limited as long as it is a (meth) acrylic resin having an acid group in the side chain. For example, (meth) acrylic acid ester (i-1) and acid group And a copolymer of the compound (i-2) having an unsaturated group.

  Examples of (meth) acrylic acid ester (i-1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth). (Meth) acrylic acid alkyl esters such as acrylates; having hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprocactone modified 2-hydroxyethyl (meth) acrylate (Meth) acrylic acid esters; methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxytrie Glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, (meth) acrylates such as methoxy polyethylene glycol (meth) acrylate. Examples of the acrylic silane compound include γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropylmethyldiethoxysilane, and acryloxy. Examples include ethoxypropyltrimethoxysilane, acryloxyethoxypropyltriethoxysilane, acryloxydiethoxypropyltrimethoxysilane, and acryloxydiethoxypropyltriethoxysilane.

  Examples of the compound (i-2) having an acid group and an unsaturated group include (meth) acrylic 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) acryloyloxyalkylcarboxylic acid such as (meth) acryloylalkylcarboxylic acid, 2-acryloyloxyethylsuccinic acid, 2-acryloyloxyethylphthalic acid, 2-acryloyloxyethylhexahydrophthalic 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、Ｒ^１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).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ^a and R ^b each represent a hydrogen atom, a methyl group, or an ethyl group, 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、Ｒ^１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)

(In the formula, 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 is 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.

  The compound (i-2) 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 compound (i-2) having an acid group and an unsaturated group can be used alone or in combination of two or more.

  The acid group-containing (meth) acrylic resin (i) is obtained by polymerizing a (meth) acrylic acid ester (i-1) and a compound (i-2) having an acid group and an unsaturated group by a conventional method. Can be obtained. In the polymerization, other polymerizable components may be added. As the other polymerizable component, for example, a radical polymerizable compound is preferably used. Examples of the radical polymerizable compound include styrene, methylstyrene, hydroxystyrene, and the like, and hydroxystyrene is particularly preferable. As a preferred embodiment, an acid group-containing product obtained by polymerizing a (meth) acrylic acid ester (i-1), a compound (i-2) having an acid group and an unsaturated group, and a compound having radical polymerizability (Meth) acrylic resin (i) is mentioned.

  The compound (ii) having a radical polymerizable group and an epoxy group is not particularly limited as long as it is a compound having at least one radical polymerizable group and an epoxy group in the molecule. ) A compound having an unsaturated group such as an acryloyl group is preferably used. Examples of such a compound (ii) having a radical polymerizable group and an epoxy group include aliphatic hydrocarbons such as glycidyl (meth) acrylate, β-methylglycidyl methacrylate, epoxidized isoprenyl (meth) acrylate, and allyl glycidyl ether. Aliphatic epoxy group-containing unsaturated compounds such as group-containing (meth) acrylates; and alicyclic epoxy group-containing unsaturated compounds exemplified by the following formulas.

（式中、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２は炭素数１〜１０のアルキレン基を示し、Ｒ^３は炭素数１〜１０の炭化水素基を示し、ｋは０又は１〜１０の整数を示す）

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1 to 10 carbon atoms, R ³ represents a hydrocarbon group having 1 to 10 carbon atoms, and k represents 0 or 1 to 1) (Indicates an integer of 10)

  The resin (A) having a radical reactive group and an acid group in the side chain in the present invention includes, for example, an acid group-containing (meth) acrylic resin (i), a compound having a radical polymerizable group and an epoxy group (ii) Can be obtained by using a known method as a reaction for introducing an epoxy group into an acid group.

  The weight average molecular weight of the resin (A) having a radical reactive group and an acid group in the side chain is, for example, about 2000 to 50000, preferably about 2000 to 15000. When the weight average molecular weight is less than 2000, it is difficult to obtain an effect of suppressing curing shrinkage, and when it exceeds 50,000, the viscosity of the resin composition is remarkably increased and it is difficult to form a uniform film.

  The amount of radical reactive groups and acid groups in the side chain of the resin in the present invention can be measured by a conventional method. Specifically, the radical reactive group in the side chain of the resin can be quantified as the double bond equivalent of the resin, and the acid group can be quantified as the acid value of the resin. The double bond equivalent of the resin in the present invention is, for example, about 400 to 2000, preferably about 500 to 1500. If the double bond equivalent is less than 400, the shrinkage rate at the time of curing tends to be high, and if it exceeds 2000, the strength of the coating film after curing tends to decrease, which is not preferable. Moreover, the acid value of resin is about 20-150 mgKOH / g, for example, Preferably it is about 20-120 mgKOH / g. If the acid value is less than 20 mgKOH / g, the adhesion of the resin composition to the laminate (substrate or the like) tends to be lowered, and if it exceeds 120 KOH / g, the water resistance tends to be inferior.

  The resin composition of the present invention may further contain other components such as a curable monomer (B), a polymerization initiator (C), a photosensitizer, and nanoscale particles (D).

  The curable monomer (B) is used for the purpose of promoting photocurability and reducing the viscosity of the composition. For example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 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, di Pentaerythritol hexaacrylate and each methacrylate corresponding to the above acrylate DOO acids, mono- and polybasic acids with hydroxyalkyl (meth) acrylate -, di -, tri - like or more polyester can be exemplified. These curable monomers can be used alone or in combination of two or more.

  Although content of a curable monomer (B) is not specifically limited, For example, it is about 60 to 95 weight% with respect to the whole resin composition.

  As the polymerization initiator (C), those known and commonly used as light or thermal polymerization initiators can be used. Typical photopolymerization initiators include, for example, benzoin / benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and 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 and the like 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; 1,7-bis (9-acridinyl) heptane and the like. These polymerization initiators can be used alone or in combination of two or more.

  Typical thermal polymerization initiators are, for example, organic peroxides in the form of diacyl peroxides, peroxydicarbonates, alkyl peresters, dialkyl peroxides, perketals, ketone peroxides and alkyl hydroperoxides. Specific examples of these thermal polymerization initiators include dibenzoyl peroxide, t-butyl perbenzoate, and azobisisobutyronitrile.

  Commercially available polymerization initiators (C) include, for example, Irgacure (registered trademark) 184 (1-hydroxycyclohexyl phenyl ketone) and Irgacure (registered trademark) 500 (1-hydroxy) available from Ciba as photopolymerization initiators. Cyclohexyl phenyl ketone, benzophenone), and other photoinitiators of the Irgacure® type; Darocur® 1173, 1116, 1398, 1174 and 1020 (available from Merck).

  Although content of a polymerization initiator (C) is not specifically limited, For example, it is about 0.1-20 weight% with respect to the whole resin composition.

  The photosensitizer is preferably used in combination with a photopolymerization initiator. As the photosensitizer, those commonly used as photosensitizers can be used. For example, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethyl is used. And tertiary amines such as aminobenzoate, triethylamine, and triethanolamine. These photosensitizers can be used alone or in combination of two or more.

  Although content of a photosensitizer is not specifically limited, For example, it is about 0.1 to 5 weight% with respect to the whole resin composition.

The nanoscale particles (D) 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 (D), a diffractive condensing film having a high refractive index can be produced. Such nanoscale particles (D) 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 ³⁶ ) _a (R ³⁷ ) _b Si (X) _(4-ab) (II)
(In the formula, R ³⁶ is a non-hydrolyzable group, R ³⁷ 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 ³⁶ , b R ³⁷ , 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; a C ₆ -C ₁₀ aryloxy such as phenoxy, etc. An aryloxy group such as acetoxy and propionyloxy; an alkylcarbonyl group such as C ₂ -C ₇ alkylcarbonyl such as acetyl; and the like. The hydrolyzable group in X may have one or more conventional substituents such as a halogen atom and alkoxy.

Non-hydrolyzable groups for R ³⁶ include, for example, 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; alkenyl such as C ₂ -C ₆ alkenyl such as vinyl, 1-propenyl, 2-propenyl and butenyl; alkynyl such as C ₂ -C ₆ alkynyl such as acetylenyl and propargyl; C ₆ such as phenyl and naphthyl; aryl such as such as C ₁₀ aryl and the like. The non-hydrolyzable group for R ³⁶ 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 ³⁷ 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 of R ³⁷ preferably contains 1-18, in particular 1-8 carbon atoms.

  In 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) is preferably a value of 1 or 2. Have

  Of the non-polymerizable silanes represented by the formula (I), compounds in which X is a hydrolyzable group are preferable, and tetraalkoxysilanes such as traethoxysilane (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) acryloyloxypropyltrimethoxysilane; 3-glycidyloxypropyl Epoxysilanes such as trimethoxysilane (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 or basic condensation catalyst such as HCl, HNO ₃ or NH 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, for _{example, CaO, ZnO, CdO, SiO} 2, TiO 2, ZrO 2, CeO 2, SnO 2, PbO, etc. _{Al 2 O 3, In 2 O} 3 and _La 2 _{O 3} sulfides such as CdS and ZnS;; oxides of GaSe, selenides such as CdSe or ZnSe; ZnTe or tellurides such as _{CdTe; NaCl, KCl, BaC1 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 P ₂ or Cd ₃ P ₂ Carbonates such as Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , SrCO ₃ and BaCO ₃ ; carboxylates such as acetates such as CH ₃ COONa and Pb (CH ₃ COO) ₄ ; phosphoric acid Salts; Sulfates; Silicates; Titanates; Zirconates; Aluminates; Stinates; Leadates, and conventional glass compositions whose composition preferably has a low coefficient of thermal expansion, such as SiO ₂ , Examples thereof include particles made of a corresponding mixed oxide or the like corresponding to a combination of two, three or four components of TiO ₂ , ZrO ₂ and Al ₂ O ₃ .

As materials for 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 colloidal sols of stabilized colloidal inorganic particles can be used, and commercially available products include silica sols manufactured by BAYER, SnO ₂ sols manufactured by Goldschmidt, and manufactured by MERCK. Commercially available products such as TiO ₂ sols from Nissan Chemicals, 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 s); acetylacetone, 2,4-hexanedione, 3,5-heptane-dione, beta-dicarbonyl compounds such as acetoacetic acid and _C 1 -C ₄ alkyl acetoacetate such like.

  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) acrylamides, (poly) methacrylamides, (poly) carbamide , (Poly) olefins, (poly) styrene, (poly) amides, (poly) imides, (poly) vinyl compounds, (poly) esters, (poly) arylates, (poly) carbonates, ( Such as poly) ethers, (poly) etherketones, (poly) sulfones, (poly) epoxides, fluoropolymers, organo (poly) siloxanes, (poly) siloxanes and hetero (poly) siloxanes Monomers, oligomers, polymers and the like having one or more polymerizable functional groups in the molecule are exemplified.

  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 ³⁸ (X ¹ ) ₃ Si (III)
Wherein R ³⁸ is a partially fluorinated or perfluorinated C ₂ -C ₂₀ -alkyl;
X ¹ is C ₁ -C ₃ -alkoxy, methyl, ethyl 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 at R ^38, means an alkyl group in which at least one hydrogen atom is replaced by fluorine atoms. Preferred groups R ³⁸ 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 formula (III) include tridecafluoro-1,1,2,2-tetrahydrooctyl-1-triethoxysilane, CF ₃ CH ₂ CH ₂ SiCl ₂ CH ₃ , and 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, it is used at about 0.2 to 2% by weight.

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 liquid on the support by a known method such as spin coating so as to contain the organic polymer.

  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, then drying to form a film, and enabling 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 film (the film before curing) of the resin composition for nanoimprint formed by the above method (nanoimprint in a broad sense) 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 100 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 film formed by nanoimprint in a narrow sense, and in the film formed by nanoimprint in a broad sense, For example, it 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 the nano stamper is removed. Preferably, as 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 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, the thickness is about 0.1 μm to 10 mm, preferably about 1 μm to 1 mm.

  As a method for curing the coating, either a thermal curing process by heating or a UV curing process 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 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. In addition, Example 6 shall be described as a reference example.

Production Example 1
Resin solution containing a resin having a radical reactive group and an acid group in the side chain (A-1)
Stirrer, thermometer, reflux condenser, a 2L separable flask equipped with a dropping funnel and a nitrogen inlet tube, propylene glycol monomethyl ether (manufactured by Daicel Chemical Industries, Ltd. MMPG) introducing 250 g, after raising the temperature to 110 ° C., Aronix M5300 (manufactured by Toagosei Co., Ltd.) 152 g, methacrylic acid 109 g, methyl methacrylate 78 g, MMPG 230 g and t-butylperoxy 2-ethylhexanoate (Nippon Yushi Co., Ltd., trade name “Perbutyl O”) 37.3 g together for 3 hours It was dripped over. It was synthesized trunk polymer having a carboxyl Shi Le group was aged 3 hours after dropping. Next, 231 g of 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Chemical Industries, trade name “Cyclomer A200”), 2.3 g of triphenylphosphine, and 1.0 g of methylhydroquinone are added to the trunk polymer solution. The reaction was carried out at 0 ° C. for 10 hours. The reaction was carried out under a mixed atmosphere of air / nitrogen. As a result, a cured resin solution (A-1) having an acid value of 50 KOH-mg / g, a double bond equivalent (resin weight per 1 mol of unsaturated groups) of 450, and a weight average molecular weight of 9,200 was obtained.

Production Example 2
Resin solution containing a resin having a radical reactive group and an acid group in the side chain (A-2)
Stirrer, thermometer, reflux condenser, a 2L separable flask equipped with a dropping funnel and a nitrogen inlet tube, propylene glycol monomethyl ether (manufactured by Daicel Chemical Industries, Ltd. MMPG) introducing 300 g, after raising the temperature to 110 ° C., methacrylic 151 g of acid, 110 g of methyl methacrylate, 200 g of MMPG, and 28.7 g of t-butyl peroxy 2-ethylhexanoate (Perbutyl O manufactured by NOF Corporation) were added dropwise over 3 hours. It was synthesized trunk polymer having a carboxyl Shi Le group and aged 4 hours after dropping. Next, 239 g of 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Chemical Industries, trade name “Cyclomer A200”), 2.4 g of triphenylphosphine, and 1.0 g of methylhydroquinone are added to the above-mentioned trunk polymer solution. The reaction was carried out at 0 ° C. for 10 hours. The reaction was carried out under a mixed atmosphere of air / nitrogen. As a result, a cured resin solution (A-2) having an acid value of 50 KOH-mg / g, a double bond equivalent (resin weight per 1 mol of unsaturated groups) 381, and a weight average molecular weight of 8,700 was obtained.

Production Example 3
Nanoscale particle dispersion (D-1)
236.1g accession Li acryloyloxy propyl trimethoxysilane (1 mol) (GPTS), and refluxed for 24 hours with water 26 g (1.5 mol). The formed methanol was removed at 70 ° C. by a rotary evaporator.
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 GPTS condensate thus prepared with stirring. The isopropanol is then removed in a rotary evaporator.
A nanoscale particle dispersion (D-1) sol was obtained by diluting with isopropoxyethanol until a nanoimprinting composition having a viscosity of about 300 mPa · s was obtained.

Production Example 4
Nanoscale particle dispersion (D-2)
A nanoscale particle dispersion (D-2) prepared by changing to zirconium oxide (ZrO ₂ average particle diameter 20 nm, concentration of about 5 wt% methyl ethyl ketone dispersion manufactured by Kitamura Chemical Industry Co., Ltd.) instead of the silica sol of Production Example 3 was obtained. It was.

Examples 1-6, Comparative Example 1
Manufacture of semiconductor material Nanoimprint by mixing resin (A), curable monomer (B), polymerization initiator (C) and nanoscale particles (D) of the types and amounts described in Table 1 in a spin coater A resin composition was prepared. Specific compounds of each component in Table 1 are shown below.
Resin A-1, A-2: resin monomer was used in each Production Example 1 and 2 B-1: trimethyl Chi triacrylate (manufactured by Kyoeisha)
B-2: Tetraethylene glycol diacrylate (manufactured by Kyoeisha)
B-3: N-methylpyrrolidone (Wako Pure Chemical Industries, Ltd.)
Initiator C-1: Irgacure 651 (manufactured by Chiba)
Solvent: Propylene glycol methyl ether acetate (manufactured by Daicel Chemical Industries)
Nanoparticles D-1, D-2: Particles used in Production Examples 3 and 4, respectively

  The obtained nanoimprinting resin composition 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 0.5 μm. In addition, “applicability” was evaluated by the method described later for the state of the surface of the film coated with the resin composition. In addition, about Examples 1-3 and 6 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 minutes was given. The layer thickness of the coating after drying was about 500 nm.

  The imprinting device is a computer-controlled tester (manufactured by Myeongchang Kiko Co., Ltd., trade name “NM-0401 model”), which specifies the specified pressure by programming the loading, relaxation rate, heating temperature, etc. It is possible to maintain the time. 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 nanostamper 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), thereby producing 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 6 and Comparative Example 1, after the resin composition was spin-coated on a silicon wafer, the surface condition was observed, the presence or absence of uniform coating film formation was observed, and the following criteria were evaluated. .
○: A uniform coating film was obtained.
X: The repelling of the coating film was observed after spin coating.

Peelability In Examples 1 to 6 and Comparative Example 1, after curing by UV irradiation, the peelability when the nanostamper was peeled from the cured resin composition was evaluated according to the following criteria.
○: It was easily peeled off by applying force to the imprint stamp.
X: It could not be easily peeled off.

Curing shrinkage In the process of transferring the patterns in Examples 1 to 6 and Comparative Example 1, after removing the nano stamper, the appearance of the formed pattern was visually observed using a scanning microscope, and the state of the pattern edge and the edge Evaluation was made according to the following criteria from the viewpoint of a rectangle.
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 6 and Comparative Example 1, the pattern formed on the silicon wafer after dry etching was evaluated according to the following criteria.
○: A pattern was transferred onto the silicon wafer.
X: Pattern transfer could not be performed on the silicon wafer.

  Since Examples 1-6 from Table 1 are excellent in applicability | paintability compared with the comparative example 1, and are excellent in dry etching tolerance, a favorable pattern shape can be provided as a fine structure.

Examples 7-12, Comparative Example 2
Manufacture of diffraction type condensing film For type of nanoimprint, mixing resin (A), curable monomer (B), polymerization initiator (C) and nanoscale particles (D) of the types and amounts described in Table 2 A resin composition was prepared. 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. Here, about Examples 7-9 and 12 using the resin composition containing a solvent, in order to remove a solvent after film formation, the drying process (prebaking) heated at about 95 degreeC for 5 minute (s) was performed. 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 conditions, an ultra-high pressure mercury lamp (USH-3502MA, Ushio Electric Co., Ltd., model USH-3502MA, illuminance 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 6 to 12 and Comparative Example 2 obtained as described above, the transferability, the adhesion to the support, and the refractive index were evaluated by the methods described later. 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 × ・ ・ ・ Stuck

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 ... transfer impossible As shown in Table 2, it was confirmed that the apex angle of the sample of Comparative Example 2 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 appe refractometer.

  As shown in Table 2, it was found that Examples 7 to 12 using the resin composition containing the resin (A) had little curing shrinkage and excellent transferability. In addition, it was found that the system containing nanoparticles has 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 (11)

A resin composition for nanoimprinting comprising a resin (A) having a radical reactive group and an acid group in the side chain,
The acid group-containing (meth) acrylic resin (i) in which the resin (A) is a copolymer of a (meth) acrylic acid ester (i-1) and a compound (i-2) having an acid group and an unsaturated group ) And a compound (ii) having a radical polymerizable group and an epoxy group ,
The resin (A) has a weight average molecular weight of 2000 to 15000 and a double bond equivalent of 400 to 1500,
The resin composition for nanoimprinting, wherein the compound (ii) having the radical polymerizable group and the epoxy group is an alicyclic epoxy group-containing unsaturated compound represented by the following formula .

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkylene group having 1 to 10 carbon atoms) The resin composition according to claim 1 , wherein an acid value of the resin (A) is 20 to 150 mgKOH / g. Furthermore, the resin composition of Claim 1 or 2 containing a curable monomer (B) and / or a polymerization initiator (C). Furthermore, as nanoscale particles (D), oxides, sulfides, selenides, tellurides, halides, carbides, arsenides, antimonides, nitrides, phosphides, carbonic acid At least selected from the group consisting of salts, carboxylates, phosphates, sulfates, silicates, titanates, zirconates, aluminates, stannates, leadates and mixed oxides thereof The resin composition according to any one of claims 1 to 3 , comprising nanoscale particles made of one material. Hardened | cured material formed by hardening | curing the resin composition as described in any one of Claims 1-4 . The manufacturing method of the fine structure which gives a nano structure to the resin composition in any one of Claims 1-4 by giving a nanoimprint process. (1) The process of forming the film which consists of a resin composition in 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 by pressing a nano stamper on the film; and (3) a step of curing the film to which the pattern is transferred to obtain a fine structure. . The method for producing a microstructure according to claim 7 , 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 fine structure of Claim 7 or 8 including the process of etching a hardened film. Any of the microstructure obtained by the manufacturing method according to the preceding claims 6-9. The fine structure according to claim 10, which is a semiconductor material, a diffractive condensing film, a polarizing film, an optical waveguide, or a hologram.