JP2010087165A - Hardening composition for nanoimprinting, hardened material using this and its manufacturing method, and member for liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hardening composition for nanoimprinting lithography, having a low viscosity and a high transcription pattern accuracy, and excellent in a mechanical strength. <P>SOLUTION: The hardening composition for optical nanoimprinting includes at least one type of (meta) acrylate compound and an antioxidant. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a curable composition used for optical nanoimprint, a cured product and a method for producing the same, and a liquid crystal display member using the cured product and a method for producing the same.

  Two types of nanoimprint methods have been proposed: a thermal nanoimprint using a thermoplastic resin as a material to be processed (Non-Patent Document 1) and a case of using a curable composition for optical nanoimprint lithography (Non-Patent Document 2). . In the case of thermal nanoimprint, the mold is pressed onto a polymer resin heated to a temperature higher than the glass transition temperature, and the mold is released after cooling to transfer the microstructure to the resin on the substrate. Since it can be applied to various resin materials and glass materials, it is expected to be applied in various fields. For example, Patent Document 1 and Patent Document 2 disclose a nanoimprint method in which a nanopattern is formed at low cost using a thermoplastic resin.

  On the other hand, in the optical nanoimprint method in which light is irradiated through a transparent mold and the curable composition for nanoimprint is photocured, imprinting at room temperature becomes possible. Recently, new developments such as a nanocasting method combining the advantages of both and a reversal imprint method for producing a three-dimensional laminated structure have been reported.

  In such a nanoimprint method, the following applied technologies have been proposed. The first technique is to apply high-precision alignment and high integration to the fabrication of high-density semiconductor integrated circuits and fabrication of liquid crystal display transistors in place of conventional lithography. . The second technique is the case where the molded shape (pattern) itself has a function and can be applied as various nanotechnology element parts or structural members. Examples include various micro / nano optical elements, Examples include high-density recording media, optical films, and structural members in flat panel displays. As other techniques, there is a technique in which a laminated structure is constructed by simultaneous integral molding of a micro structure and a nano structure, or simple interlayer alignment, and is applied to manufacture of μ-TAS and a biochip. In recent years, efforts to put nanoimprinting methods into practical use for these applications, including the aforementioned technologies, have become active.

  First, an application example of the first technique for creating a high-density semiconductor integrated circuit will be described. 2. Description of the Related Art In recent years, semiconductor integrated circuits have been miniaturized and integrated, and photolithography apparatuses have been improved in accuracy as a pattern transfer technique for realizing the fine processing. On the other hand, the use of a nanoimprint lithography technique (optical nanoimprint method) proposed as a technique for performing fine pattern formation at low cost has been studied. For example, Patent Document 1 below discloses a nanoimprint technique in which a silicon wafer is used as a stamper and a fine structure of 25 nm or less is formed by transfer. Along with this trend, in order to apply nanoimprint lithography to the production of semiconductor integrated circuits, studies on properties such as mold-resin peelability and pattern transfer accuracy have begun to become active. On the other hand, studies for improving the releasability of the mold from the resin, pattern transfer accuracy, substrate adhesion, etc., and applying nanoimprint lithography to the fabrication of semiconductor integrated circuits are starting to become active.

  Next, an application example of nanoimprint lithography to a flat display such as a liquid crystal display (LCD) or a plasma display (PDP) in the second technique will be described. With the trend toward larger and higher definition LCD substrates and PDP substrates, optical nanoimprint lithography has recently attracted attention as an inexpensive lithography that replaces conventional photolithography methods used in the manufacture of thin film transistors (TFTs) and electrode plates. Therefore, it has become necessary to develop a photo-curable resist that replaces the etching photoresist used in the conventional photolithography method. In addition, application of optical nanoimprint lithography is also being studied for transparent protective film materials used as structural members for LCDs, spacers for defining cell gaps in liquid crystal displays, and the like. Unlike the etching resist, such a resist for a structural member is finally left in the display, and is sometimes referred to as “permanent resist” or “permanent film”.

  As a permanent film to which a conventional photolithography technology is applied, for example, a protective film provided on a TFT substrate of a liquid crystal panel or a step between each layer of red (R), green (G), and blue (B) is reduced. Examples include a protective film provided on the color filter in order to impart resistance to high-temperature processing during sputtering of the ITO film. In the formation of these protective films (permanent films), the uniformity of the coating film, adhesion to the substrate, high light transmittance after heat treatment exceeding 200 ° C., planarization characteristics, solvent resistance, scratch resistance Various characteristics such as these are required.

  In the field of spacers used in liquid crystal displays, photocurable compositions comprising a resin, a photopolymerizable monomer and a photopolymerization initiator are generally widely used in conventional photolithography methods. The spacer generally forms a pattern having a size of about 10 μm to 20 μm by photolithography using a photocurable composition on the color filter substrate after forming the color filter or after forming the color filter protective film. It is formed by heat curing by post-baking. The spacer used in such a liquid crystal display is required to have high mechanical characteristics against external pressure, hardness, developability, pattern transfer accuracy, adhesion and the like. For this reason, development of the photocurable composition suitable for formation of permanent films (permanent resist), such as a transparent protective film and a spacer using a nanoimprint method, is calculated | required.

  Although the required characteristics of materials used for optical nanoimprint lithography are often different depending on the application to which they are applied, the demands on process characteristics are common regardless of the application. For example, the main requirement items shown in Non-Patent Document 3 below are applicability, substrate adhesion, low viscosity (usually <5 mPa · s), peelability, low cure shrinkage, fast curability, and the like. . The key to material design is how to control these required characteristics and balance them. In addition, since the required characteristics are greatly different between the process material and the permanent film, the material needs to be developed according to the process and application.

  As described above, the main technical problems as a permanent film include pattern accuracy, adhesion, transparency after heat treatment exceeding 200 ° C., high mechanical properties (strength against external pressure), scratch resistance, and flattening properties. There are many problems such as solvent resistance and reduction of outgas during heat treatment. Even when the curable composition for optical nanoimprint is applied as a permanent film, it is important to provide uniformity of the coating film, transparency after heat treatment, and scratch resistance, as in the case of conventional resists using acrylic resins. It is. Among these, an example (Patent Document 3) in which a fluorine-containing surfactant is added is an example of realizing high pattern accuracy by improving mold releasability.

  At the same time, as a problem peculiar to the curable composition for optical nanoimprint, in addition to the above-mentioned problem, it is necessary to ensure the fluidity of the resist to the concave portion of the mold and to reduce the viscosity without using a solvent or a small amount of solvent. It can be easily peeled off from the mold after photocuring and adhesion to the mold does not occur. That is, the technical difficulty of designing the curable composition for optical nanoimprint is further increased.

As described above, although various materials are disclosed for the curable composition for optical nanoimprint, there is no sufficient design guideline for the curable composition suitable for producing a permanent film. It is.
US Pat. No. 5,772,905 US Pat. No. 5,956,216 JP 2006-310565 A S.Chou et al.:Appl.Phys.Lett.Vol.67,3114 (1995) M.Colbun et al,: Proc.SPIE, Vol. 3676,379 (1999) Latest resist material handbook, P1, 103-104 (2005, published by the Information Organization)

  The present invention has been accomplished in view of the above circumstances, and an object thereof is to provide a curable composition for optical nanoimprint lithography excellent in photocurability, particularly a composition suitable for a permanent film such as a flat panel display. And In particular, an object is to provide a composition having excellent mechanical strength while having low viscosity and high transfer pattern accuracy.

As a result of intensive studies by the inventors of the present invention based on the above problems, it has been found that the above problems can be solved by the following means.
(1) A curable composition for optical nanoimprint, comprising at least one (meth) acrylate compound represented by the following general formula (1) and an antioxidant.

（一般式（１）中、Ｘは単結合、または、置換若しくは無置換のメチレン基を表し、Ｒは、それぞれ、水素原子またはメチル基を表す。）
（２）下記一般式（１）で表される（メタ）アクリレート化合物を少なくとも１種と、他の重合性モノマーと、酸化防止剤とを含む、光ナノインプリント用硬化性組成物。

(In the general formula (1), X represents a single bond or a substituted or unsubstituted methylene group, and R represents a hydrogen atom or a methyl group, respectively.)
(2) A curable composition for optical nanoimprint, comprising at least one (meth) acrylate compound represented by the following general formula (1), another polymerizable monomer, and an antioxidant.

（一般式（１）中、Ｘは単結合、または、置換若しくは無置換のメチレン基を表し、Ｒは、それぞれ、水素原子またはメチル基を表す。）
（３）ポリエーテル構造を有する重合性モノマーの含量が組成物中５質量％以下である、（２）に記載の光ナノインプリント用硬化性組成物。
（４）前記重合性モノマーとして、芳香環を有する重合性モノマーを含む、（２）または（３）に記載の光ナノインプリント用硬化性組成物。
（５）前記重合性モノマーとして、非共役二重結合を有する重合性モノマーを含む、（２）〜（４）のいずれか１項に記載の光ナノインプリント用硬化性組成物。
（６）前記重合性モノマーとして、ケイ素含有化合物を含む、（２）〜（５）のいずれかに記載の光ナノインプリント用硬化性組成物。
（７）前記酸化防止剤が、ヒンダードフェノール系、チオエーテル系およびヒンダードアミン系から選択される、（１）〜（６）のいずれか１項に記載の光ナノインプリント用硬化性組成物。
（８）永久膜用である、（１）〜（７）のいずれか１項に記載の光ナノインプリント用硬化性組成物。
（９）（１）〜（８）のいずれか１項に記載の光ナノインプリント用硬化性組成物を硬化させた硬化物。
（１０）（９）に記載の硬化物を含むことを特徴とする液晶表示装置用部材。
（１１）（１）〜（８）のいずれか１項に記載の光ナノインプリント用硬化性組成物を用いることを特徴とする、硬化物の製造方法。
（１２）（１）〜（８）のいずれか１項に記載の光ナノインプリント用硬化性組成物を基板上に塗布してパターンを形成する工程と、前記パターンにモールドを押圧する工程と、前記モールドを押圧したパターンに光照射する工程とを含む硬化物の製造方法。
（１３）さらに、前記光が照射されたパターンを加熱する工程を含む、（１２）に記載の硬化物の製造方法。

(In the general formula (1), X represents a single bond or a substituted or unsubstituted methylene group, and R represents a hydrogen atom or a methyl group, respectively.)
(3) The curable composition for optical nanoimprints according to (2), wherein the content of the polymerizable monomer having a polyether structure is 5% by mass or less in the composition.
(4) The curable composition for optical nanoimprints according to (2) or (3), which contains a polymerizable monomer having an aromatic ring as the polymerizable monomer.
(5) The curable composition for optical nanoimprints according to any one of (2) to (4), comprising a polymerizable monomer having a non-conjugated double bond as the polymerizable monomer.
(6) The curable composition for optical nanoimprints according to any one of (2) to (5), which contains a silicon-containing compound as the polymerizable monomer.
(7) The curable composition for optical nanoimprints according to any one of (1) to (6), wherein the antioxidant is selected from hindered phenols, thioethers, and hindered amines.
(8) The curable composition for optical nanoimprints according to any one of (1) to (7), which is for a permanent film.
(9) Hardened | cured material which hardened the curable composition for optical nanoimprints of any one of (1)-(8).
(10) A member for a liquid crystal display device comprising the cured product according to (9).
(11) A method for producing a cured product, wherein the curable composition for optical nanoimprints according to any one of (1) to (8) is used.
(12) A step of applying a curable composition for optical nanoimprinting according to any one of (1) to (8) on a substrate to form a pattern, a step of pressing a mold against the pattern, And a step of irradiating the pattern pressing the mold with light.
(13) The method for producing a cured product according to (12), further including a step of heating the pattern irradiated with the light.

  According to the present invention, it has become possible to provide a curable composition for nanoimprint lithography which has low viscosity and high transfer pattern accuracy and excellent mechanical strength.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

The present invention is described in detail below. In the present specification, (meth) acrylate represents acrylate and methacrylate, (meth) acryl represents acryl and methacryl, and (meth) acryloyl represents acryloyl and methacryloyl. The monomer in the present invention is a compound having a mass average molecular weight of 1,000 or less, distinguished from oligomers and polymers. In the present specification, the functional group refers to a group involved in polymerization.
The nanoimprint referred to in the present invention refers to pattern transfer having a size of about several μm to several tens of nm, and it goes without saying that the nanoimprint is not limited to a nano-order.

 The curable composition for optical nanoimprint lithography of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) has a low viscosity before curing, and has an excellent ability to form a fine uneven pattern. Can do. Moreover, after hardening, it is excellent in mechanical strength. Furthermore, it can be set as the film physical property which was comprehensively excellent in other points. Therefore, the composition of the present invention can be widely used for optical nanoimprint lithography.

That is, the composition of the present invention can have the following characteristics when used in optical nanoimprint lithography.
(1) Since the solution fluidity at room temperature is excellent, the composition easily flows into the cavity of the mold recess, and the atmosphere is difficult to be taken in. Residues hardly remain after curing.
(2) The cured film after curing has excellent pattern accuracy, excellent mechanical properties, excellent adhesion between the coating film and the substrate, and excellent peelability between the coating film and the mold. Since stringing does not occur on the surface of the coating film to cause surface roughness, a good pattern can be formed.
(3) Since it is excellent in coating uniformity, it is suitable for the field of coating / microfabrication on large substrates.

 For example, the composition of the present invention can be used for semiconductor integrated circuits and liquid crystal display device members that have been difficult to develop (particularly, thin film transistors for liquid crystal displays, protective films for liquid crystal color filters, spacers, and other liquid crystal display device members). For other applications such as plasma display panel partition materials, flat screens, micro electromechanical systems (MEMS), sensor elements, optical disks, high-density memory disks, etc., Optical components such as diffraction grating relief holograms, nanodevices, optical devices, optical films and polarizing elements, organic transistors, color filters, overcoat layers, pillar materials, rib materials for liquid crystal alignment, microlens arrays, immunoassay chips, DNA Separation chip, microreactor, nanobio device It can be widely applied to the production of chairs, optical waveguides, optical filters, photonic liquid crystals, and the like.

 The viscosity of the composition of the present invention will be described. The viscosity in the present invention means a viscosity at 25 ° C. unless otherwise specified. In the composition of the present invention, the viscosity at 25 ° C. of the composition excluding the solvent is 10 mPa · s or less, preferably 3 to 18 mPa · s, more preferably 4 to 10 mPa · s. By setting the viscosity of the composition of the present invention to 10 mPa · s or less, even when a mold having a fine concavo-convex pattern is brought into close contact with the composition, the composition flows into the cavity of the concave portion of the mold, and the atmosphere is taken in. Since it becomes difficult to cause a bubble defect, it is difficult to cause a bubble defect, and a residue hardly remains after photocuring in the mold convex portion.

  The composition of the present invention contains a (meth) acrylate compound represented by the general formula (1) and an antioxidant, and preferably further contains another polymerizable monomer.

((Meth) acrylate compound represented by general formula (1))
The composition of the present invention contains at least one (meth) acrylate compound represented by the general formula (1). By including the (meth) acrylate compound represented by the general formula (1), the viscosity of the composition can be lowered, and the pattern accuracy and mechanical strength of the cured product of the composition can be improved. Furthermore, it becomes possible to improve flexibility.

（一般式（１）中、Ｘは単結合、または、置換若しくは無置換のメチレン基を表し、Ｒは、それぞれ、水素原子またはメチル基を表す。）

(In the general formula (1), X represents a single bond or a substituted or unsubstituted methylene group, and R represents a hydrogen atom or a methyl group, respectively.)

Examples of the substituent when X is a substituted methylene group include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group, and an alkyl group is preferable. The number of carbon atoms of the substituent is preferably 3 or less.
X is preferably a single bond or an unsubstituted methylene group, and more preferably a single bond.
From the viewpoints of viscosity and photocurability, R is preferably a hydrogen atom, and more preferably all three Rs are hydrogen atoms.

 Among the (meth) acrylate compounds represented by the general formula (1), glycerol tri (meth) acrylate is particularly preferable.

  The addition amount of the (meth) acrylate compound represented by the general formula (1) is preferably 45% by mass or less, and 40% by mass or less of the polymerizable monomer contained in the composition of the present invention. Is more preferable. By setting it as such a range, it becomes possible to make the viscosity of the composition obtained low. On the other hand, in order to improve the mechanical strength of the cured film obtained by curing the composition of the present invention, the content is preferably 15% by mass or more, and more preferably 20% by mass or more.

(Other polymerizable monomers)
The composition of the present invention can contain other polymerizable monomers. Such a polymerizable monomer is added for the purpose of improving various properties of the composition, imparting properties, etc., but the composition of the present invention has a content of polymerizable monomer having a polyether structure in the composition. The content is preferably at most mass%, more preferably at most 3 mass%. By setting it as such a content, the mechanical strength of the cured film formed by hardening | curing the composition of this invention can be improved more.
Examples of the polymerizable monomer used in the present invention include (meth) acrylate. By adopting (meth) acrylate, light / thermosetting can be further improved. Examples of the polymerizable monomer used in the present invention include at least one of a polymerizable monomer having an aromatic ring, a polymerizable monomer having a non-conjugated bond, and a silicon-containing compound. Chemical resistance can be improved by including a polymerizable monomer containing an aromatic ring. By including a polymerizable monomer having a non-conjugated bond, the viscosity can be further reduced. By including the silicon-containing compound, it is possible to further improve the substrate adhesion and mold releasability.
More specifically, the composition of the present invention is used in combination with a polymerizable monomer having one ethylenically unsaturated bond-containing group (monofunctional polymerizable unsaturated monomer) for the purpose of reducing the composition viscosity. It is preferable. Specifically, 2-acryloyloxyethyl phthalate, 2-acryloyloxy 2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (Meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acrylic acid dimer, benzyl (meth) acrylate, butanediol mono (meth) acrylate Rate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, ethylene oxide modified (hereinafter referred to as “EO”) cresol (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) ) Acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclohentanyl (meth) acrylate, dicyclo Pentanyloxyethyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate Methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, Nonylphenoxy polypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, epichlorohydrin (hereinafter referred to as “ECH”) modified phenoxy acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol ( (Meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene Glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, tert-butyl (meta ) Acrylate, tribromophenyl (meth) acrylate, EO-modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate, p-isopropenylphenol, styrene, α-methylstyrene, acrylonitrile and vinylcarbazole.

Furthermore, it is also preferable to use a polyfunctional polymerizable unsaturated monomer having two or more ethylenically unsaturated bond-containing groups as another polymerizable monomer.
Examples of the bifunctional polymerizable unsaturated monomer having two ethylenically unsaturated bond-containing groups that can be preferably used in the present invention include diethylene glycol monoethyl ether (meth) acrylate and dimethylol dicyclopentane di (meth) acrylate. , Di (meth) acrylated isocyanurate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, EO modified 1,6-hexanediol di (meth) acrylate, ECH modified 1,6-hexanediol di (meth) acrylate, allyloxypolyethylene glycol acrylate, 1,9-nonanediol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, Denatured bi Phenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, ECH modified hexahydrophthalic acid diacrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO modified Neopentyl glycol diacrylate, propylene oxide (hereinafter referred to as “PO”) modified neopentyl glycol diacrylate, caprolactone modified hydroxypivalate ester neopentyl glycol, stearic acid modified pentaerythritol di (meth) acrylate, ECH modified phthalic acid di ( (Meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol-tetramethylene glycol) Cole) di (meth) acrylate, polyester (di) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ECH-modified propylene glycol di (meth) acrylate, silicone di (meth) acrylate, triethylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, EO modified Tripropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate, dipropylene glycol di (meth) acrylate, divinylethyl Examples are renurea and divinylpropyleneurea.

  Among these, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, and the like are particularly preferably used in the present invention.

  In the composition of the present invention, for the purpose of further increasing the crosslinking density, a polyfunctional oligomer or polymer having a molecular weight larger than that of the other polyfunctional polymerizable monomer can be blended within the range of achieving the object of the present invention. . Examples of the polyfunctional oligomer having radical photopolymerization include various acrylate oligomers such as polyester acrylate, polyurethane acrylate, and polyepoxy acrylate.

 As another polymerizable monomer used in the present invention, a compound having an oxirane ring can also be employed. Examples of the compound having an oxirane ring include polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, polyglycidyl ethers of aromatic polyols, and aromatics. Mention may be made, for example, of hydrogenated compounds of polyglycidyl ethers of polyols, urethane polyepoxy compounds and epoxidized polybutadienes. These compounds can be used alone or in combination of two or more thereof.

  Examples of the epoxy compound that can be preferably used include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S. Diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin tri Aliphatic polyvalents such as glycidyl ether, trimethylolpropane triglycidyl ether, ethylene glycol, propylene glycol, glycerin Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to alcohol; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; phenol , Cresol, butylphenol, or monoglycidyl ethers of polyether alcohol obtained by adding alkylene oxide to these; glycidyl esters of higher fatty acids, and the like.

  Among these components, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol Diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and neopentyl glycol diglycidyl ether are preferred.

  Examples of commercially available products that can be suitably used as the glycidyl group-containing compound include UVR-6216 (manufactured by Union Carbide), glycidol, AOEX24, cyclomer A200 (manufactured by Daicel Chemical Industries, Ltd.), Epicoat 828, Epicoat 812, and Epicoat. 1031, Epicoat 872, Epicoat CT508 (above, manufactured by Yuka Shell Co., Ltd.), KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2720, KRM-2750 (above, Asahi Denka Kogyo Co., Ltd.) ) Made). These can be used alone or in combination of two or more.

  The production method of these compounds having an oxirane ring is not limited. For example, Maruzen KK Publishing, 4th edition Experimental Chemistry Course 20 Organic Synthesis II, page 213, 1992, Ed. By Alfred Hasfner, The chemistry of cyclic compounds-Small Ring Heterocycles part3 Oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, Adhesion, Vol. 29, No. 12, 32, 1985, Yoshimura, Adhesion, Vol. 30, No. 5, 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, Japanese Patent Application Laid-Open No. 11-1000037, Japanese Patent No. 2906245, Japanese Patent No. 2926262 and the like can be synthesized.

As another polymerizable monomer used in the present invention, a vinyl ether compound may be used in combination.
The vinyl ether compound may be appropriately selected. For example, 2-ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, diethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1 , 3-propanediol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, tetra Ethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol Vinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, trimethylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether, pentaerythritol triethylene vinyl ether, Examples include pentaerythritol tetraethylene vinyl ether, 1,1,1-tris [4- (2-vinyloxyethoxy) phenyl] ethane, bisphenol A divinyloxyethyl ether, and the like.

  These vinyl ether compounds can be obtained, for example, by the method described in Stephen C. Lapin, Polymers Paint Color Journal. 179 (4237), 321 (1988), that is, the reaction of a polyhydric alcohol or polyhydric phenol with acetylene, or They can be synthesized by the reaction of a polyhydric alcohol or polyhydric phenol and a halogenated alkyl vinyl ether, and these can be used singly or in combination of two or more.

 Moreover, a styrene derivative can also be employ | adopted as another polymerizable monomer used by this invention. Examples of the styrene derivative include p-methoxystyrene, p-methoxy-β-methylstyrene, p-hydroxystyrene, and the like.

 Other examples of styrene derivatives that can be used in combination with the monofunctional polymer of the present invention include styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, Examples thereof include p-methoxy-β-methylstyrene, p-hydroxystyrene, etc. Examples of vinylnaphthalene derivatives include 1-vinylnaphthalene, α-methyl-1-vinylnaphthalene, β-methyl-1-vinyl. Naphthalene, 4-methyl-1-vinylnaphthalene, 4-methoxy-1-vinylnaphthalene and the like can be mentioned.

 In addition, trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, perfluorobutyl-hydroxypropyl ( Use compounds containing fluorine atoms such as (meth) acrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, etc. Can do.

 As another polymerizable monomer used in the present invention, propenyl ether and butenyl ether can be blended. For example, 1-dodecyl-1-propenyl ether, 1-dodecyl-1-butenyl ether, 1-butenoxymethyl-2-norbornene, 1-4-di (1-butenoxy) butane, 1,10-di (1-butenoxy) Decane, 1,4-di (1-butenoxymethyl) cyclohexane, diethylene glycol di (1-butenyl) ether, 1,2,3-tri (1-butenoxy) propane, propenyl ether propylene carbonate, and the like can be suitably applied.

 The other polymerizable monomer used in the present invention is preferably included in the composition in the range of 10 to 90% by mass, and more preferably in the range of 50 to 85% by mass. When two or more kinds of polymerizable monomers are included, the total amount of each polymerizable monomer is preferably within the above range.

(Antioxidant)
The composition of the present invention contains an antioxidant. The antioxidant used for this invention contains 0.01-10 mass% in all the compositions, for example, Preferably it is 0.2-5 mass%. When using 2 or more types of antioxidant, the total amount becomes the said range.
The antioxidant suppresses fading caused by heat or light irradiation and fading caused by various oxidizing gases such as ozone, active oxygen, NO _x , SO _x (X is an integer). By adding an antioxidant, coloring of the cured film can be prevented, and reduction in film thickness due to decomposition can be reduced. In addition, in the present invention, the mechanical strength and pattern accuracy of the cured film can be improved. Furthermore, the viscosity of the composition can be kept low. Examples of such antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates, Examples include thiourea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like. Of these, hindered phenol-based antioxidants, thioether-based antioxidants, and hindered amine-based antioxidants are particularly preferred from the viewpoint of coloring of the cured film and reduction in film thickness.

  As commercially available products of antioxidants, Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Geigy Co., Ltd.), Antigene P, 3C, FR, Smither S, Smither GA80 (manufactured by Sumitomo Chemical), ADK STAB AO70, AO80, AO503 (made by ADEKA Co., Ltd.) etc. are mentioned, These may be used independently and may be used in mixture.

(Photopolymerization initiator)
A photopolymerization initiator is used in the composition of the present invention. The photoinitiator used for this invention contains 0.1-15 mass% in all the compositions, for example, Preferably it is 0.2-12 mass%, More preferably, it is 0.3-10 mass %. When using 2 or more types of photoinitiators, the total amount becomes the said range.
It is preferable that the ratio of the photopolymerization initiator is 0.1% by mass or more because sensitivity (fast curability), resolution, line edge roughness, and coating film strength tend to be improved. On the other hand, when the ratio of the photopolymerization initiator is 15% by mass or less, the light transmittance, the colorability, the handleability and the like tend to be improved, which is preferable. So far, various addition amounts of preferred photopolymerization initiators and / or photoacid generators have been studied for ink jet compositions and dye display / color pigment compositions for liquid crystal display color filters. No preferred amount of photopolymerization initiator and / or photoacid generator added to the curable composition for nanoimprints is reported. That is, in a system containing dyes and / or pigments, these may act as radical trapping agents, affecting the photopolymerizability and sensitivity. In consideration of this point, the amount of the photopolymerization initiator added is optimized in these applications. On the other hand, in the composition of the present invention, the dye and / or pigment is not an essential component, and the optimum range of the photopolymerization initiator is different from that in the field of an ink jet composition or a liquid crystal display color filter composition. There is.

  As the photopolymerization initiator used in the present invention, one that has activity with respect to the wavelength of the light source to be used is blended, and one that generates appropriate active species is used. Moreover, only one type of photopolymerization initiator may be used, or two or more types may be used.

  As the radical photopolymerization initiator used in the present invention, for example, a commercially available initiator can be used. Examples of these include Irgacure® 2959 (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, Irgacure (available from Ciba). (Registered trademark) 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure (registered trademark) 500 (1-hydroxycyclohexyl phenyl ketone, benzophenone), Irgacure (registered trademark) 651 (2,2-dimethoxy-1,2-diphenylethane- 1-one), Irgacure® 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1), Irgacure® 907 (2-methyl-1 [4- Methylthiophenyl] -2-morpholinop Lopan-1-one, Irgacure® 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2,4 , 4-trimethyl-pentylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone), Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide) 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Irgacure® OXE01 (1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- ( O-benzoyloxime), Darocur (registered) Standard) 1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Darocur (R) 1116, 1398, 1174 and 1020, CGI242 (ethanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide), Lucirin TPO available from BASF -L (2,4,6-trimethylbenzoylphenylethoxyphosphine oxide), ESACURE 1001M (1- [4-benzoylphenylsulfanyl] phenyl] -2-methyl-2- (4-methyl), available from ESACUR Nippon Siebel Hegner Phenyls Honyl) propan-1-one, N-1414 Adeka optomer (registered trademark) N-1414 (carbazole phenone system), Adeka optomer (registered trademark) N-1717 (acridine system) available from Asahi Denka Co., Ltd. Adekaoptomer (registered trademark) N-1606 (triazine type), TFE-triazine (2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1 manufactured by Sanwa Chemical Co., Ltd.) , 3,5-triazine), TME-triazine (2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5, manufactured by Sanwa Chemical Co., Ltd.) -Triazine), MP-triazine (2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine) manufactured by Sanwa Chemical, Midori Chemical TAZ-113 (2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), TAZ-108 (2- (3 , 4-dimethoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine), benzophenone, 4,4'-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzoyl-4'- Methyl diphenyl sulfide, 4-phenylbenzophenone, ethyl Michler's ketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, thioxa Nton ammonium salt, benzoin, 4,4'-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetophenone, diethoxyacetophenone and dibenzosuberone , Methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoyl biphenyl, 4-benzoyl diphenyl ether, 1,4-benzoylbenzene, benzyl, 10-butyl-2-chloroacridone, [4- (methylphenylthio) Phenyl] phenylmethane), 2-ethylanthraquinone, 2,2-bis (2-chlorophenyl) 4,5,4 ′, 5′-tetrakis (3,4,5-trimethoxyphenyl) 1,2′-biimidazole, 2,2-bis (o-chlorophenyl) 4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, tris (4-dimethylaminophenyl) methane, ethyl -4- (dimethylamino) benzoate, 2- (dimethylamino) ethyl benzoate, butoxyethyl-4- (dimethylamino) benzoate, and the like.

  The light for initiating polymerization of the present invention includes not only light having a wavelength in the region of ultraviolet light, near ultraviolet light, far ultraviolet light, visible light, infrared light, or electromagnetic waves, but also radiation. For example, microwave, electron beam, EUV, and X-ray are included. Laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used. The light may be monochromatic light (single wavelength light) that has passed through an optical filter, or may be light with a plurality of different wavelengths (composite light). The exposure can be multiple exposure, and after the pattern is formed for the purpose of increasing the film strength and etching resistance, the entire surface can be further exposed.

  The photopolymerization initiator used in the present invention needs to be selected in a timely manner with respect to the wavelength of the light source to be used, but is preferably one that does not generate gas during mold pressurization / exposure. When the gas is generated, the mold is contaminated, so the mold must be frequently cleaned, or the curable composition for nanoimprinting of the present invention is deformed in the mold and deteriorates the transfer pattern accuracy. Cause problems. For those that do not generate gas, the mold is less likely to be contaminated, the frequency of cleaning the mold is reduced, and the curable composition for nanoimprinting of the present invention is less likely to be deformed in the mold, so the transfer pattern accuracy is less likely to deteriorate. It is preferable from the viewpoint.

(Surfactant)
The composition of the present invention may contain a surfactant. The surfactant used in the present invention contains, for example, 0.001 to 5% by mass, preferably 0.002 to 4% by mass, and more preferably 0.005 to 3% by mass in the entire composition. It is. When using 2 or more types of surfactant, the total amount becomes the said range. If the surfactant is less than 0.001 in the composition, the effect of coating uniformity is insufficient. On the other hand, if it exceeds 5% by mass, the mold transfer characteristics are deteriorated, which is not preferable.
The surfactant preferably contains at least one of a fluorine-based surfactant, a silicone-based surfactant, and a fluorine / silicone-based surfactant. Both the fluorine-based surfactant and the silicone-based surfactant or fluorine -It is more preferable to include a silicone-based surfactant, and it is more preferable to include a fluorine-silicone-based surfactant.
Here, the fluorine / silicone surfactant refers to one having both requirements of a fluorine surfactant and a silicone surfactant.
By using such a surfactant, the composition of the present invention can be applied to a silicon wafer for manufacturing a semiconductor device, a glass square substrate for manufacturing a liquid crystal device, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, and tantalum. Striations and scale-like patterns (such as alloy films, silicon nitride films, amorphous silicone films, tin oxide-doped indium oxide (ITO) films, tin oxide films, etc.) The purpose is to solve the problem of poor coating such as uneven drying of the resist film), and the fluidity of the composition into the cavity of the mold recess is improved, the peelability between the mold and the resist is improved, and between the resist and the substrate It becomes possible to improve the adhesion and to lower the viscosity of the composition.

Examples of the nonionic fluorosurfactant used in the present invention include trade names Florard FC-430 and FC-431 (Sumitomo 3M), trade names Surflon “S-382” (Asahi Glass Co., Ltd.), EFTOP “ EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 "(manufactured by Tochem Products), trade names PF-636, PF-6320, PF-656, PF-6520 ( All are OMNOVA), brand names FT250, FT251, DFX18 (all manufactured by Neos Co., Ltd.), brand names Unidyne DS-401, DS-403, DS-451 (all manufactured by Daikin Industries, Ltd.) ), Trade names Megafuk 171, 172, 173, 178K, 178A, F780F (all manufactured by Dainippon Ink & Chemicals, Inc.) Examples of nonionic silicon-based surfactants include the trade name SI-10 series, Pionine D6315 (both manufactured by Takemoto Yushi Co., Ltd.), Megafuck Paintad 31 (manufactured by Dainippon Ink & Chemicals, Inc.), KP -341 (manufactured by Shin-Etsu Chemical Co., Ltd.).
Examples of fluorine / silicone surfactants used in the present invention include trade names X-70-090, X-70-091, X-70-092, X-70-093 (all Shin-Etsu Chemical Co., Ltd.). Manufactured), and trade names Megafuk R-08 and XRB-4 (all manufactured by Dainippon Ink & Chemicals, Inc.).

  The surfactant used in the composition of the present invention is preferably a nonionic (nonionic) surfactant from the viewpoint of voltage holding ratio.

Other components In addition to the above-described components, the composition of the present invention may include a release agent, an ultraviolet absorber, a light stabilizer, an anti-aging agent, a plasticizer, an adhesion promoter, a thermal polymerization initiator, a colorant, Elastomer particles, photoacid proliferators, photobase generators, basic compounds, flow regulators, antifoaming agents, dispersants and the like may be added.

  For the purpose of further improving the peelability, a release agent can be arbitrarily blended in the composition of the present invention. Specifically, it is added for the purpose of enabling the mold pressed against the layer of the composition of the present invention to be peeled cleanly without causing the resin layer to become rough or take off the plate. Examples of the release agent include conventionally known release agents such as silicone-based release agents, polyethylene wax, amide wax, solid wax such as Teflon powder (Teflon is a registered trademark), fluorine-based compounds, phosphate ester-based compounds, etc. Can also be used. Moreover, these mold release agents can be adhered to the mold.

  Silicone release agents have particularly good releasability from the mold when combined with the above-mentioned photocurable resin used in the present invention, and the phenomenon of taking a plate is difficult to occur. The silicone release agent is a release agent having an organopolysiloxane structure as a basic structure, for example, unmodified or modified silicone oil, polysiloxane containing trimethylsiloxysilicate, silicone acrylic resin, and the like. It is also possible to apply a silicone leveling agent generally used in hard coat compositions.

The modified silicone oil is obtained by modifying the side chain and / or terminal of polysiloxane, and is classified into a reactive silicone oil and a non-reactive silicone oil. Examples of the reactive silicone oil include amino modification, epoxy modification, carboxyl modification, carbinol modification, methacryl modification, mercapto modification, phenol modification, one-end reactivity, and different functional group modification. Examples of the non-reactive silicone oil include polyether modification, methylstyryl modification, alkyl modification, higher fatty ester modification, hydrophilic special modification, higher alkoxy modification, higher fatty acid modification, and fluorine modification.
Two or more of the above-described modification methods can be performed on one polysiloxane molecule.

  The modified silicone oil is preferably compatible with the composition components. In particular, when using a reactive silicone oil that is reactive with other coating film forming components blended as necessary in the composition, it is chemically bonded in the cured film obtained by curing the composition of the present invention. Therefore, since it is fixed, problems such as adhesion inhibition, contamination, and deterioration of the cured film are unlikely to occur. In particular, it is effective for improving the adhesion with the vapor deposition layer in the vapor deposition step. In addition, in the case of silicone modified with a photocurable functional group such as (meth) acryloyl-modified silicone or vinyl-modified silicone, it is excellent in characteristics after curing because it is crosslinked with the composition of the present invention.

Polysiloxane containing trimethylsiloxysilicic acid is easy to bleed out on the surface and has excellent releasability, excellent adhesion even when bleeded out to the surface, and excellent adhesion to metal deposition and overcoat layer This is preferable.
The said mold release agent can be added only in 1 type or in combination of 2 or more types.

When a release agent is added to the composition of the present invention, it is preferably added in a proportion of 0.001 to 10% by mass in the total amount of the composition, more preferably in a range of 0.01 to 5% by mass. preferable. If the ratio of a mold release agent is less than the said range, the peelable improvement effect of a mold and the curable composition layer for optical nanoimprint lithography will become inadequate. On the other hand, if the ratio of the release agent exceeds the above range, the surface of the coating film may be rough due to repelling during coating of the composition, or the substrate itself and the adjacent layer in the product, for example, the adhesion of the vapor deposition layer It is not preferable from the viewpoint of inhibiting the properties and causing film breakage or the like during transfer (film strength becomes too weak).
When the ratio of the release agent is 0.01% by mass or more, the effect of improving the peelability between the mold and the curable composition layer for photo nanoimprint lithography is sufficient. On the other hand, if the ratio of the release agent is within the above range of 10% by mass, the problem of surface roughness of the coating film due to repelling during coating of the composition is unlikely to occur, and the substrate itself and adjacent layers in the product, It is preferable in that it hardly inhibits the adhesion of the deposited layer and hardly causes film breakage or the like (film strength becomes too weak) during transfer.

  In the composition of the present invention, an organic metal coupling agent may be blended in order to improve the heat resistance, strength, or adhesion to the metal vapor deposition layer of the surface structure having a fine concavo-convex pattern. In addition, the organometallic coupling agent is effective because it has an effect of promoting the thermosetting reaction. As the organometallic coupling agent, for example, various coupling agents such as a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and a tin coupling agent can be used.

  Examples of the silane coupling agent used in the composition of the present invention include vinyl silanes such as vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane; γ-methacryloxypropyltrimethoxysilane An epoxy silane such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane; N-β- (aminoethyl)- aminosilanes such as γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; and Other sila Examples of the coupling agent include γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, and γ-chloropropylmethyldiethoxysilane.

  Examples of titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) Titanate, tetra (2,2-diallyloxymethyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl Titanate, isopropyl isostearoyl diacryl titanate, isop Pirutori (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- aminoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

  Examples of the zirconium coupling agent include tetra-n-propoxyzirconium, tetra-butoxyzirconium, zirconium tetraacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethyl acetoacetate, zirconium butoxyacetylacetonate bis. (Ethyl acetoacetate) and the like.

  Examples of the aluminum coupling agent include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, ethylacetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), alkylacetate Acetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethyl acetoacetate), aluminum tris (acetylacetoacetate) and the like can be mentioned.

  The said organometallic coupling agent can be arbitrarily mix | blended in the ratio of 0.001-10 mass% in solid content whole quantity of the curable composition for optical nanoimprint lithography. By setting the ratio of the organometallic coupling agent to 0.001% by mass or more, there is a tendency to be more effective in improving heat resistance, strength, and adhesion with the vapor deposition layer. On the other hand, it is preferable that the ratio of the organometallic coupling agent is 10% by mass or less because the stability of the composition and the deficiency in film formability can be suppressed.

  As a commercial item of an ultraviolet absorber, Tinuvin P, 234, 320, 326, 327, 328, 213 (above, manufactured by Ciba Geigy Co., Ltd.), Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350 400 (above, manufactured by Sumitomo Chemical Co., Ltd.). It is preferable to mix | blend an ultraviolet absorber arbitrarily in the ratio of 0.01-10 mass% with respect to the whole quantity of the curable composition for optical nanoimprint lithography.

  Commercially available light stabilizers include Tinuvin 292, 144, 622LD (above, manufactured by Ciba Geigy Co., Ltd.), Sanol LS-770, 765, 292, 2626, 1114, 744 (above, manufactured by Sankyo Kasei Kogyo Co., Ltd.) Etc. The light stabilizer is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the composition.

  Examples of commercially available anti-aging agents include Antigene W, S, P, 3C, 6C, RD-G, FR, and AW (manufactured by Sumitomo Chemical Co., Ltd.). The anti-aging agent is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the composition.

  A plasticizer can be added to the composition of the present invention in order to adjust adhesion to the substrate, flexibility of the film, hardness, and the like. Specific examples of preferred plasticizers include, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, dimethyl adipate, diethyl adipate , Di (n-butyl) adipate, dimethyl suberate, diethyl suberate, di (n-butyl) suberate and the like, and a plasticizer can be optionally added at 30% by mass or less in the composition. Preferably it is 20 mass% or less, More preferably, it is 10 mass% or less. In order to obtain the effect of adding a plasticizer, 0.1% by mass or more is preferable.

  An adhesion promoter may be added to the composition of the present invention in order to adjust adhesion to the substrate. Adhesion promoters include benzimidazoles and polybenzimidazoles, lower hydroxyalkyl-substituted pyridine derivatives, nitrogen-containing heterocyclic compounds, urea or thiourea, organophosphorus compounds, 8-oxyquinoline, 4-hydroxypteridine, 1,10-phenanthroline 2,2'-bipyridine derivatives, benzotriazoles, organophosphorus compounds and phenylenediamine compounds, 2-amino-1-phenylethanol, N-phenylethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-ethylethanol Amines and derivatives, benzothiazole derivatives, and the like can be used. The adhesion promoter in the composition is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. The addition of the adhesion promoter is preferably 0.1% by mass or more in order to obtain the effect.

  When hardening the composition of this invention, a thermal-polymerization initiator can also be added as needed. Preferred examples of the thermal polymerization initiator include peroxides and azo compounds. Specific examples include benzoyl peroxide, tert-butyl-peroxybenzoate, azobisisobutyronitrile, and the like.

  The composition of the present invention may contain a photobase generator as necessary for the purpose of adjusting the pattern shape, sensitivity, and the like. For example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) Oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitro Benzyloxycarbonyl) pyrrolidine, hexaamminecobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,6-dimethyl-3,5- Diacetyl-4 Preferred examples include (2′-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4- (2 ′, 4′-dinitrophenyl) -1,4-dihydropyridine, and the like. It is done.

  A colorant may be optionally added to the composition of the present invention for the purpose of improving the visibility of the coating film. As the colorant, pigments and dyes used in UV inkjet compositions, color filter compositions, CCD image sensor compositions, and the like can be used as long as the object of the present invention is not impaired. As the pigment that can be used in the present invention, conventionally known various inorganic pigments or organic pigments can be used. Examples of inorganic pigments are metal compounds such as metal oxides and metal complex salts. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony And metal complex oxides. Organic pigments include CIPigment Yellow 11, 24, 31, 53, 83, 99, 108, 109, 110, 138, 139,151, 154, 167, CIPigment Orange 36, 38, 43, CIPigment Red 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, CIPigment Violet 19, 23, 32, 39, CIPigment Blue 1, 2, 15, 16, 22, 60, 66, CIPigment Green 7, 36 37, CIPigment Brown 25, 28, CIPigment Black 1, 7 and carbon black. The colorant is preferably blended at a ratio of 0.001 to 2% by mass with respect to the total amount of the composition.

In the composition of the present invention, elastomer particles may be added as optional components for the purpose of improving mechanical strength, flexibility and the like.
The elastomer particles that can be added as an optional component to the composition of the present invention preferably have an average particle size of 10 nm to 700 nm, more preferably 30 to 300 nm. For example, polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer, styrene / butadiene copolymer, styrene / isoprene copolymer, ethylene / propylene copolymer, ethylene / α-olefin copolymer, ethylene / α-olefin / Particles of elastomer such as polyene copolymer, acrylic rubber, butadiene / (meth) acrylic ester copolymer, styrene / butadiene block copolymer, styrene / isoprene block copolymer. Further, core / shell type particles in which these elastomer particles are coated with a methyl methacrylate polymer, a methyl methacrylate / glycidyl methacrylate copolymer or the like can be used. The elastomer particles may have a crosslinked structure.

  Examples of commercially available elastomer particles include Resin Bond RKB (manufactured by Resinas Kasei Co., Ltd.), Techno MBS-61, MBS-69 (manufactured by Techno Polymer Co., Ltd.), and the like.

  These elastomer particles can be used alone or in combination of two or more. The content of the elastomer component in the composition of the present invention is preferably 1 to 35% by mass, more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass.

  A basic compound may be optionally added to the composition of the present invention for the purpose of suppressing curing shrinkage and improving thermal stability. Examples of the basic compound include amines, nitrogen-containing heterocyclic compounds such as quinoline and quinolidine, basic alkali metal compounds, basic alkaline earth metal compounds, and the like. Among these, amine is preferable from the viewpoint of compatibility with the photopolymerization monomer, for example, octylamine, naphthylamine, xylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, dimethylaniline, quinuclidine, tributylamine, tributylamine, and the like. Examples include octylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine, hexamethylenetetramine, and triethanolamine.

 A chain transfer agent may be added to the composition of the present invention in order to improve photocurability. Specifically, 4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 1,3,5-triazine-2,4,6 (1H, 3H , 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate).

(Organic solvent)
In the composition of the present invention, the content of the organic solvent is preferably 3% by mass or less in the entire composition. That is, since the composition of the present invention preferably contains a specific monofunctional or bifunctional monomer as a reactive diluent, the organic solvent for dissolving the components of the composition of the present invention must always be contained. Absent. In addition, if an organic solvent is not included, a baking process for the purpose of volatilization of the solvent is not necessary, so that there is a great merit that it is effective for simplifying the process. Therefore, in the composition of the present invention, the content of the organic solvent is preferably 3% by mass or less, more preferably 2% by mass or less, and it is particularly preferable not to contain it. As described above, the composition of the present invention does not necessarily contain an organic solvent. However, in the case of dissolving a compound that does not dissolve in the reactive diluent as the composition of the present invention, or when finely adjusting the viscosity. Any of these may be added. The organic solvent that can be preferably used in the composition of the present invention is a solvent generally used in curable compositions for nanoimprints and photoresists, which dissolves and uniformly disperses the compound used in the present invention. It is not particularly limited as long as it is sufficient and does not react with these components.

  Examples of the organic solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; methyl cellosolve Ethylene glycol alkyl ether acetates such as acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; propylene glycol Propylene glycol alkyl ether acetates such as rumethyl ether acetate and propylene glycol ethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2 Ketones such as pentanone and 2-heptanone; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2- Methyl hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, acetic acid Chill, methyl lactate, and the like esters such as lactic acid esters such as ethyl lactate.

Further, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. A high boiling point solvent can also be added. These may be used alone or in combination of two or more.
Among these, methoxypropylene glycol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, methyl isobutyl ketone, 2-heptanone and the like are particularly preferable.

(surface tension)
The composition of the present invention preferably has a surface tension in the range of 18 to 30 mN / m, and more preferably in the range of 20 to 28 mN / m. By setting it as such a range, the effect of improving surface smoothness is acquired.

(amount of water)
In addition, the water content at the time of preparation of the composition of the present invention is preferably 2.0% by mass or less, more preferably 1.5% by mass, and still more preferably 1.0% by mass or less. By making the water content at the time of preparation 2.0% by mass or less, the storage stability of the composition of the present invention can be made more stable.

(Preparation)
The composition of the present invention can be prepared as a solution by mixing each of the above components and then filtering with a filter having a pore size of 0.05 μm to 5.0 μm, for example. The mixing / dissolution of the curable composition for nanoimprint is usually performed in the range of 0 ° C to 100 ° C. Filtration may be performed in multiple stages or repeated many times. Moreover, the filtered liquid can be refiltered. Materials used for filtration can be polyethylene resin, polypropylene resin, fluororesin, nylon resin, etc., but are not particularly limited.

[Curing film]
Next, the cured film of the present invention (in particular, a fine uneven pattern) using the composition of the present invention will be described. In the present invention, the composition of the present invention can be applied and cured to form the cured film of the present invention.

  Further, by applying the composition of the present invention on a substrate or a support and exposing, curing, and drying (baking) the layer made of the composition as necessary, permanent layers such as overcoat layers and insulating films can be obtained. A film can also be produced.

  In permanent films (resist for structural members) used in liquid crystal displays (LCDs), it is possible to avoid contamination of metal or organic ionic impurities in the resist as much as possible so as not to hinder the operation of the display. Preferably, the concentration is usually 1000 ppm or less, preferably 100 ppm or less.

  Permanent films (resist for structural members) used for liquid crystal displays (LCDs) are bottled in containers such as gallon bottles and coated bottles after manufacture, and are transported and stored. In this case, the purpose is to prevent deterioration. The interior of the container may be replaced with inert nitrogen or argon. Further, at the time of transportation and storage, the room temperature may be used, but the temperature may be controlled in the range of −20 ° C. to 0 ° C. in order to prevent the permanent film from being deteriorated. Of course, it is necessary to shield from light at a level where the reaction does not proceed.

[Components for liquid crystal display devices]
Further, the cured product of the present invention can be preferably applied as a semiconductor integrated circuit, a recording material, or a liquid crystal display member, more preferably a liquid crystal display member, and an etching resist such as a flat panel display. It is particularly preferable to apply as

[Method for producing cured film]
Below, the manufacturing method of the cured film using the composition of this invention is described.
The composition of the present invention is preferably cured by light or light and heat. Specifically, a pattern forming layer comprising at least the composition of the present invention is applied on a substrate or a support, and the solvent is dried to form a layer (pattern forming layer) comprising the composition of the present invention. A receptor is prepared, a mold is pressed against the surface of the pattern receiving layer of the pattern receiver, a process of transferring the mold pattern is performed, and the fine uneven pattern forming layer is cured by light irradiation and heating. Usually, light irradiation and heating are performed a plurality of times. Nanoimprint lithography according to the method for producing a cured film of the present invention can be laminated and multiple patterned, and can be used in combination with ordinary thermal imprint.

  The cured product of the present invention is generally well-known coating methods such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spin coating, slit scanning. It can be formed by applying the composition of the present invention by a method or the like. The film thickness of the layer comprising the composition of the present invention is 0.05 μm to 30 μm, although it varies depending on the application used. Further, the composition of the present invention may be applied multiple times.

  The substrate or support for applying the composition of the present invention is quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG Polymer substrates such as polyester film, polycarbonate film, polyimide film, TFT array substrate, PDP electrode plate, glass and transparent plastic substrate, conductive substrate such as ITO and metal, insulating substrate, silicone, silicone nitride, poly There are no particular restrictions on semiconductor fabrication substrates such as silicone, silicone oxide, and amorphous silicone. The shape of the substrate may be a plate shape or a roll shape.

  The light for curing the composition of the present invention is not particularly limited, and examples thereof include high energy ionizing radiation, light or radiation having a wavelength in the region of near ultraviolet, far ultraviolet, visible, infrared or the like. As the high-energy ionizing radiation source, for example, an electron beam accelerated by an accelerator such as a cockcroft accelerator, a handagraaf accelerator, a linear accelerator, a betatron, or a cyclotron is industrially most conveniently and economically used. However, radiation such as γ rays, X rays, α rays, neutron rays, proton rays emitted from radioisotopes or nuclear reactors can also be used. Examples of the ultraviolet ray source include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a solar lamp. The radiation includes, for example, microwaves and EUV. Also, laser light used in semiconductor microfabrication such as LED, semiconductor laser light, or 248 nm KrF excimer laser light or 193 nm ArF excimer laser can be suitably used in the present invention. These lights may be monochromatic light, or may be a plurality of lights having different wavelengths (mixed light).

During exposure is preferably in the range of exposure intensity of ^{1mW / cm 2 ~50mW / cm 2} . By making the exposure time 1 mW / cm ² or more, the exposure time can be shortened so that productivity is improved, and by making the exposure time 50 mW / cm ² or less, deterioration of the properties of the permanent film due to side reactions can be suppressed. It tends to be preferable. The exposure amount is preferably in the range of 5 mJ / cm ^{2 to} 1000 mJ / cm ² . If it is less than 5 mJ / cm ² , the exposure margin becomes narrow, photocuring becomes insufficient, and problems such as adhesion of unreacted substances to the mold tend to occur. On the other hand, if it exceeds 1000 mJ / cm ² , the permanent film may be deteriorated due to decomposition of the composition.
Further, during exposure, in order to prevent inhibition of radical polymerization by oxygen, an inert gas such as nitrogen or argon may be flowed to control the oxygen concentration to less than 100 mg / L.

  As heat which hardens the composition of the present invention, 150-280 ° C is preferred and 200-250 ° C is more preferred. Moreover, as time to provide heat, 5 to 60 minutes are preferable and 15 to 45 minutes are more preferable.

Next, the molding material that can be used in the present invention will be described. In optical nanoimprint lithography using the composition of the present invention, it is necessary to select a light transmissive material for at least one of the molding material and / or the substrate. In photoimprint lithography applied to the present invention, a curable composition for nanoimprint is applied on a substrate, a light-transmissive mold is pressed, light is irradiated from the back of the mold, and the curable composition for nanoimprint is applied. Harden. Alternatively, the nanoimprint curable composition can be applied on a light-transmitting substrate, pressed against the mold, and irradiated with light from the back surface of the mold to cure the nanoimprint curable composition.
The light irradiation may be performed in a state where the mold is attached, or may be performed after the mold is peeled off, but in the present invention, it is preferably performed in a state where the mold is adhered.

As the mold that can be used in the present invention, a mold having a pattern to be transferred is used. The mold can form a pattern according to the desired processing accuracy by, for example, photolithography, electron beam drawing, or the like, but the mold pattern forming method is not particularly limited in the present invention.
The light-transmitting mold material used in the present invention is not particularly limited as long as it has predetermined strength and durability. Specifically, a light transparent resin such as glass, quartz, PMMA, and polycarbonate resin, a transparent metal vapor-deposited film, a flexible film such as polydimethylsiloxane, a photocured film, and a metal film are exemplified.

  The non-light transmissive mold material used in the case of using the transparent substrate of the present invention is not particularly limited as long as it has a predetermined strength. Specific examples include ceramic materials, deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicone, silicone nitride, polysilicon, silicone oxide, and amorphous silicone. There are no particular restrictions. The shape may be either a plate mold or a roll mold. The roll mold is applied particularly when continuous transfer productivity is required.

  The mold used in the present invention may be a mold that has been subjected to a release treatment in order to improve the releasability between the composition of the present invention and the mold. Those having been treated with a silane coupling agent such as silicone or fluorine, for example, commercially available mold release agents such as those manufactured by Daikin Industries, Optool DSX, Sumitomo 3M, Novec EGC-1720, etc., can also be suitably used.

  When performing photoimprint lithography using the method for producing a cured film of the present invention, it is usually preferred that the mold pressure be 10 atm or less. Setting the mold pressure to 10 atm or less is preferable because the mold and the substrate are less likely to be deformed and the pattern accuracy tends to be improved, and since the pressure is low, the apparatus can be reduced. The mold pressure is preferably selected in a region where the mold transfer uniformity can be ensured within a range where the residual film of the composition of the present invention on the mold convex portion is reduced.

In the present invention, the light irradiation in the photoimprint lithography may be sufficiently larger than the irradiation amount necessary for curing. The amount of irradiation necessary for curing is determined by examining the consumption of unsaturated bonds of the curable composition for nanoimprints and the tackiness of the cured film.
In the photoimprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually room temperature, but the light irradiation may be performed while heating in order to increase the reactivity. As a pre-stage of light irradiation, if it is kept in a vacuum state, it is effective in preventing bubbles from being mixed, suppressing the decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the curable composition for nanoimprinting. You may do it. In the present invention, the preferable degree of vacuum is 10 ⁻¹ Pa to normal pressure.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[Example 1]
(Preparation of curable composition for nanoimprint)
Polymerizable monomer R-3 (20 mass%), polymerizable monomer S-1 (20 mass%), polymerizable monomer S-2 (30 mass%), polymerizable monomer T-1 (30 mass%), photopolymerization Initiator P-1 (0.5% by mass relative to the polymerizable monomer), antioxidant A-1 (1.5% by mass relative to the polymerizable monomer) and antioxidant A-2 (based on the monomer) 0.5% by mass), surfactant W-1 (0.1% by mass with respect to the monomer) and surfactant W-2 (0.04% by mass with respect to the monomer) were added to the nanoimprint of Example 1. A curable composition was prepared.

(Curing by light irradiation)
The composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm. The spin-coated coated base film was set in a nanoimprint apparatus using an ORC high pressure mercury lamp (lamp power 2000 mW / cm ² ) as a light source. Next, as a mold, polydimethylsiloxane having a 10 μm line / space pattern and a groove depth of 4.0 μm (“SILPOT184” manufactured by Toray Dow Corning Co., Ltd., cured at 80 ° C. for 60 minutes) ) Was used. After the inside of the apparatus was evacuated (vacuum degree: 10 Torr, about 1.33 kPa), the mold was pressed against the substrate, and nitrogen purge (1.5 atm: mold pressing pressure) was performed to replace the inside of the apparatus with nitrogen. This was exposed from the back surface of the mold under the conditions of an illuminance of 10 mW / cm ² and an exposure amount of 240 mJ / cm ² . After the exposure, the mold was released to obtain a resist pattern.

(Curing by heating)
The resist pattern obtained by exposure by the above method was completely cured by heating in an oven at 230 ° C. for 30 minutes.

[Example 2]
Polymerizable monomer R-1 (25% by mass), polymerizable monomer R-2 (5% by mass), polymerizable monomer S-1 (30% by mass), polymerizable monomer T-1 (40% by mass), photopolymerization Initiator P-1 (1% by mass relative to the polymerizable monomer), antioxidant A-1 (1.5% by mass relative to the polymerizable monomer) and antioxidant A-3 (based on the polymerizable monomer) 0.5 wt%), surfactant W-1 (0.1 wt% based on polymerizable monomer) and surfactant W-2 (0.04 wt% based on polymerizable monomer) were added. The curable composition for nanoimprinting of Example 2 was prepared.
Similarly to Example 1, curing by light irradiation and curing by heating were performed to obtain a resist pattern.

[Examples 3 to 7]
In the same manner as in Example 1, curable compositions for nanoimprints of Examples 3 to 7 were prepared, and cured by light irradiation and cured by heating to obtain a resist pattern.

[Comparative Example 1]
A composition of Comparative Example 1 was prepared in the same manner except that T-1 was replaced with T-2 in Example 1, and a resist pattern was obtained.

[Comparative Example 2]
The composition of Comparative Example 2 was prepared in the same manner as in Example 1 except that the antioxidant was removed, and a resist pattern was obtained.

[Comparative Example 3]
In Example 1, the composition of Comparative Example 3 was prepared by replacing T-1 with T-2 and suppressing the amount of T-2 added so that the composition viscosity was 10 mPa · s or less. Obtained.

[Comparative Example 4]
Using the composition 1 described in Examples of JP-A-2006-310565, the same operation as in Example 1 was performed to obtain a resist pattern.

  The compositions of Examples and Comparative Examples are shown below.

<Monofunctional monomer>
R-1: benzyl acrylate (Biscoat # 160, manufactured by Osaka Organic Chemical Co., Ltd.)
R-2: (3-Methyl-3-oxetanyl) methyl acrylate (Biscoat OXE10, manufactured by Osaka Organic Chemical Industry)
R-3: 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical)
R-4: 2-methyl-2-adamantyl acrylate (adamantate MA, manufactured by Idemitsu Kosan)

<Bifunctional monomer>
S-1: Neopentyl glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd.)
S-2: Acrylic acid-2-acryloyloxy-3-allyloxy-propyl ester structural formula

以下の合成方法により合成した。
アリルグリシジルエーテル（東京化成製、品番Ａ０２２１）５００ｇとアクリル酸（東京化成製、品番Ａ０１４１）３３１．５ｇをテトラ−ｎ−ブチルアンモニウムブロミド１４．０ｇ（東京化成製、品番Ｔ００５４）存在下で反応させて得られる生成物にトリエチルアミン（和光純薬製、品番２０２−０２０４６）５７０．５ｇとアクリル酸クロリド（東京化成製、品番Ａ０１４７）４７１．０ｇを作用させてＳ−２の粗生成物を得た。得られた粗生成物を減圧蒸留（３．７ｍｍＨｇ、１２５℃）にて精製し、Ｓ−２を６５６ｇ得た。

It was synthesized by the following synthesis method.
500 g of allyl glycidyl ether (Tokyo Chemical Industry, product number A0221) and 331.5 g of acrylic acid (Tokyo Chemical Industry, product number A0141) were reacted in the presence of 14.0 g of tetra-n-butylammonium bromide (product number T0054). The product thus obtained was reacted with 570.5 g of triethylamine (manufactured by Wako Pure Chemicals, product number 202-02046) and 471.0 g of acrylic acid chloride (manufactured by Tokyo Chemical Industry, product number A0147) to obtain a crude product of S-2. . The obtained crude product was purified by distillation under reduced pressure (3.7 mmHg, 125 ° C.) to obtain 656 g of S-2.

S-3: Tetra (ethylene glycol) diacrylate (Light acrylate 4EG-A, manufactured by Kyoeisha Chemical)

<Trifunctional monomer>
T-1: Grecerol triacrylate structural formula

以下の合成方法により合成した。
グリセロール（和光純薬製、品番０７５−００６１６）１５．０ｇにトリエチルアミン（和光純薬製、品番２０２−０２０４６）６２．６ｇとアクリル酸クロリド（東京化成製、品番Ａ０１４７）５３．１ｇを作用させて得られる粗生成物をシリカゲルカラムクロマトグラフィーにより精製し、Ｔ−１を１８．１ｇ得た。

It was synthesized by the following synthesis method.
63.1 g of triethylamine (manufactured by Wako Pure Chemicals, product number 202-02046) and 53.1 g of acrylic acid chloride (manufactured by Tokyo Chemical Industry, product number A0147) are reacted with 15.0 g of glycerol (manufactured by Wako Pure Chemicals, product number 075-00616). The resulting crude product was purified by silica gel column chromatography to obtain 18.1 g of T-1.

T-2: Trimethylolpropane triacrylate (Aronix M-309, manufactured by Toagosei Co., Ltd.)

<Antioxidant>
A-1: Sumilizer GA80 (Sumitomo Chemical Co., Ltd., hindered phenol type)
A-2: ADK STAB AO503 (manufactured by Adeka Japan Co., Ltd., thioether type)
A-3: Irganox 1035FF (Ciba, hindered phenol + thioether system)
A-4: ADK STAB LA-57 (Adeka Japan Co., Ltd., hindered amine system)
A-5: TINUVIN 144 (Ciba, hindered amine + hindered phenol)

<Photopolymerization initiator>
P-1: 2,4,6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (Lucirin TPO-L, manufactured by BASF)
P-2: Irgacure 651 (Ciba)

<Nonionic surfactant>
W-1: Non-fluorinated surfactant (manufactured by Takemoto Yushi Co., Ltd., Pionin D6315)
W-2: Fluorosurfactant (manufactured by Dainippon Ink and Chemicals, Megafac F780F)
W-3: Fluorosurfactant (Dainippon Ink & Chemicals, Megafac R08)

<Evaluation of optical nanoimprint lithography>
About each of the composition of the said Example and comparative example, it measured and evaluated in accordance with the following evaluation method.

<Evaluation of composition viscosity>
The viscosity of the composition (before curing) was measured at 25 ± 0.2 ° C. using a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd.
The rotation speed during measurement is 100 rpm for 0.5 mPa · s to less than 5 mPa · s, 50 rpm for 5 mPa · s to less than 10 mPa · s, 20 rpm for 10 mPa · s to less than 30 mPa · s, and 30 mPa · s to less than 60 mPa · s. Were performed at 10 rpm, and classified and evaluated as follows according to the viscosity range.
A: 10 mPa · s or less B: 10 mPa · s or more and less than 18 mPa · s C: 18 mPa · s or more

<Observation of pattern accuracy>
The shape of the resist pattern created above was observed with a scanning electron microscope or an optical microscope and evaluated as follows.
A: Almost the same as the pattern of the original plate that is the basis of the pattern shape of the mold. B: There is a portion that is partially different from the pattern shape of the original plate that is the basis of the pattern shape of the mold (the range of the original pattern is less than 10%). C: There is a part (a range of 10% or more and less than 20% of the pattern of the original plate) that is partly different from the original pattern shape of the mold pattern shape. D: Clearly different from the original pattern of the mold pattern shape. Or the film thickness of the pattern differs from the original pattern by 20% or more.

<Mechanical strength>
As an index of mechanical strength, an elastic recovery rate indicating responsiveness when a load was applied to the resist pattern prepared above was evaluated.
The elastic recovery rate is a value obtained by the following equation.
(Elastic recovery rate) = (Maximum displacement during loading-Displacement after unloading) / (Maximum displacement during loading) x 100 [%]
Load-unloading was performed with a microhardness meter using a flat table indenter, and the load was 100 mN. The value of the elastic recovery rate at this time was evaluated as follows.
A: 60% or more B: 50% or more and less than 60% C: less than 50%

  The measurement results are shown in the following table.

  Examples 1 to 7 showed good results for any of the viscosity of the composition, the pattern accuracy of the cured product, and the mechanical strength. The composition of Comparative Example 1 was higher in viscosity than the composition of the present invention, resulting in poor pattern accuracy. The composition of the comparative example 2 was a result that mechanical strength was inferior compared with the composition of this invention. It is presumed that this is probably because the suppression of decomposition and degradation of the cured film by the antioxidant is not given. The composition of Comparative Example 3 was a result that the mechanical strength was inferior to that of the composition of the present invention. The composition of Comparative Example 4 was higher in viscosity than the composition of the present invention, resulting in poor pattern accuracy and mechanical strength. That is, it is understood that a composition for nanoimprinting excellent in any of viscosity, pattern accuracy and mechanical strength can be obtained by using the (meth) acrylate compound represented by the general formula (1) and the antioxidant in combination. It was.

  According to the present invention, it has become possible to provide a curable composition for nanoimprint lithography which has low viscosity and high transfer pattern accuracy and excellent mechanical strength.

Claims (13)

A curable composition for optical nanoimprint, comprising at least one (meth) acrylate compound represented by the following general formula (1) and an antioxidant.

(In the general formula (1), X represents a single bond or a substituted or unsubstituted methylene group, and R represents a hydrogen atom or a methyl group, respectively.) A curable composition for optical nanoimprinting, comprising at least one (meth) acrylate compound represented by the following general formula (1), another polymerizable monomer, and an antioxidant.

(In the general formula (1), X represents a single bond or a substituted or unsubstituted methylene group, and R represents a hydrogen atom or a methyl group, respectively.) The curable composition for optical nanoimprints according to claim 2, wherein the content of the polymerizable monomer having a polyether structure is 5% by mass or less in the composition. The curable composition for optical nanoimprint according to claim 2 or 3, comprising a polymerizable monomer having an aromatic ring as the polymerizable monomer. The curable composition for optical nanoimprints according to any one of claims 2 to 4, comprising a polymerizable monomer having a non-conjugated double bond as the polymerizable monomer. The curable composition for optical nanoimprints according to any one of claims 2 to 5, comprising a silicon-containing compound as the polymerizable monomer. The curable composition for optical nanoimprints according to any one of claims 1 to 6, wherein the antioxidant is selected from a hindered phenol type, a thioether type, and a hindered amine type. The curable composition for optical nanoimprints according to any one of claims 1 to 7, which is used for a permanent film. Hardened | cured material which hardened the curable composition for optical nanoimprints of any one of Claims 1-8. A member for a liquid crystal display device, comprising the cured product according to claim 9. The manufacturing method of hardened | cured material characterized by using the curable composition for optical nanoimprints of any one of Claims 1-8. The process which forms the pattern by apply | coating the curable composition for optical nanoimprints of any one of Claims 1-8 on a board | substrate, the process which presses a mold to the said pattern, The pattern which pressed the said mold The manufacturing method of the hardened | cured material including the process of irradiating light. Furthermore, the manufacturing method of the hardened | cured material of Claim 12 including the process of heating the pattern irradiated with the said light.