JP2008202022A - Curable composition for optical nanoimprint lithography and pattern forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel curable composition for an optical nano imprint lithography having excellent photocurability. <P>SOLUTION: The curable composition for an optical nano imprint lithography contains 35-99 mass% of a polymerizable unsaturated monomer, 0.1-15 mass% of a photopolymerization initiator, 0.001-5 mass% of at least one selected from the group consisting of a fluorine-based surfactant, a silicone-based surfactant and a fluorine-silicone-based surfactant, and 0.1-50 mass% of inorganic oxide fine particles. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a curable composition for optical nanoimprint lithography and a pattern forming method using the same.

  The nanoimprint method is a mechanical development that develops embossing technology, which is well-known in optical disc production, and presses a mold master (generally called a mold, stamper, or template) with an uneven pattern on a resist. This is a technology that precisely deforms and transfers fine patterns. Once a mold is made, it is economical because nanostructures can be easily and repeatedly molded, and it is a nano-processing technology that has few harmful wastes and emissions, so in recent years it has been expected to be applied in various fields. Yes.

 Two types of nanoimprint methods have been proposed: a case where a thermoplastic resin is used as a material to be processed (Non-Patent Document 1) and a case where a curable composition for optical nanoimprint lithography is used (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. Patent Documents 1 and 2 disclose a nanoimprint method for forming a nanopattern 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 optical nanoimprint lithography 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 applications are considered. The first is when the molded shape itself has a function and can be applied as various nanotechnology element parts or structural members. Various micro / nano optical elements, high-density recording media, optical films, flat panels Examples include structural members in displays. The second is to construct a laminated structure by simultaneous integral molding of the microstructure and nanostructure and simple interlayer alignment, and to apply it to the production of μ-TAS and biochips. The third is to apply high-precision alignment and high integration to the production of high-density semiconductor integrated circuits and the production of liquid crystal display transistors in place of conventional lithography. In recent years, efforts to put nanoimprinting methods into practical use for these applications have become active.

As an application example of the nanoimprint method, first, an application example for producing 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. However, the processing method has approached the wavelength of the light source for light exposure, and the lithography technology has also approached its limit. Therefore, in order to advance further miniaturization and higher accuracy, an electron beam drawing apparatus, which is a kind of charged particle beam apparatus, has been used in place of lithography technology. Unlike the batch exposure method in pattern formation using a light source such as i-line or excimer laser, pattern formation using an electron beam takes a method of drawing a mask pattern. The exposure (drawing) takes time and the pattern formation takes time. For this reason, as the degree of integration increases dramatically, such as 256 mega, 1 giga, and 4 giga, the pattern formation time is also greatly increased, and there is a concern that the throughput is significantly inferior. Therefore, in order to increase the speed of the electron beam drawing apparatus, development of a collective figure irradiation method in which various shapes of masks are combined and irradiated with an electron beam collectively to form an electron beam with a complicated shape is underway. . However, while miniaturization of the pattern is promoted, the electron beam drawing apparatus must be enlarged, and a mechanism for controlling the mask position with higher accuracy is required. It was happening.
On the other hand, nanoimprint lithography, which has been proposed as a technique for performing fine pattern formation at low cost, has been proposed. For example, Patent Documents 1 and 3 disclose a nanoimprint technique in which a silicon wafer is used as a stamper and a fine structure of 25 nanometers or less is formed by transfer.
Patent Document 4 discloses a composite composition using nanoimprint applied to the field of semiconductor microlithography. On the other hand, studies to apply nanoimprint lithography to semiconductor integrated circuit fabrication such as micro mold fabrication technology, mold durability, mold fabrication cost, mold releasability from resin, imprint uniformity and alignment accuracy, inspection technology, etc. It started 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) will be described.
With the trend toward larger LCDs and PDP substrates and higher definition, optical nanoimprint lithography has recently attracted attention as an inexpensive lithography that can replace 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.
Further, as a structural member such as an LCD, application of optical nanoimprint lithography to a transparent protective film material described in Patent Document 5 and Patent Document 6 or a spacer described in Patent Document 6 is also being studied. Unlike the etching resist, such a resist for a structural member is finally left in the display, and is therefore referred to as a permanent resist or a permanent film.

 A permanent film to which conventional photolithography is applied will be described. Unlike the etching resist, the permanent film is an element that is left as it is on a semiconductor element, a recording medium, a flat display panel, or the like. For example, as a transparent protective film material for a color filter used for a liquid crystal panel, conventionally, a transparent protective film is formed by a process using a photocurable resin such as a siloxane polymer, a silicone polyimide, an epoxy resin, an acrylic resin, or a thermosetting resin. It was formed (Patent Literature 7, Patent Literature 8). When forming a protective film by photolithography, characteristics such as coating film uniformity, substrate adhesion, high light transmittance after heat treatment exceeding 200 ° C., planarization characteristics, solvent resistance, scratch resistance, etc. are also required. Is done.

 A spacer that defines a cell gap in a liquid crystal display is also a kind of permanent film. In conventional photolithography, a photocurable composition comprising a resin, a photopolymerizable monomer, and an initiator has been widely used ( Patent Document 9). The spacer is required to have performance such as high mechanical characteristics against external pressure, hardness, developability, pattern accuracy, and adhesion.

 However, until now, no preferred composition of a transparent protective film used in the nanoimprint method or a photocurable composition for forming a spacer has been disclosed.

  Furthermore, with regard to coating film uniformity, demands for various parts such as coating film thickness uniformity and dimensional uniformity due to higher resolution, film thickness, and shape have become stricter as the substrate size increases. . Conventionally, in the field of manufacturing liquid crystal display devices using a small glass substrate, a method of spinning after dropping at the center has been used as a resist coating method (Non-patent Document 3). Although the coating method that spins after dropping in the center can provide good coating uniformity, for example, in the case of a large substrate of 1 m square class, the amount of resist that is shaken off during spinning (during spinning) and discarded becomes considerably large. In addition, problems such as cracking of the substrate due to high-speed rotation and securing of tact time occur. Furthermore, since the coating performance in the method of spinning after dropping in the center depends on the rotational speed at the time of spinning and the amount of resist applied, a general-purpose motor that can obtain the required acceleration when it is applied to a fifth-generation substrate that is further enlarged. However, when such a motor is specially ordered, there is a problem that the cost of parts increases. In addition, even if the substrate size and the apparatus size are increased, the required performance in the coating process, such as coating uniformity ± 3%, tact time 60 to 70 seconds / sheet, etc., is not substantially changed. It has become difficult to meet demands other than coating uniformity. Under such circumstances, a resist coating method using a discharge nozzle method has been proposed as a new resist coating method applicable to large substrates after the fourth generation substrate, particularly the fifth generation substrate and beyond. The discharge nozzle type resist coating method is a method in which a photoresist composition is applied to the entire coated surface of a substrate by relatively moving the discharge nozzle and the substrate. For example, a plurality of nozzle holes are arranged in a row. A method of using a discharge nozzle having a discharge port and a slit-like discharge port and capable of discharging a photoresist composition in a band shape has been proposed. There has also been proposed a method of adjusting the film thickness by applying a photoresist composition to the entire surface of a substrate applied by a discharge nozzle method and then spinning the substrate. Therefore, in order to replace the conventional photolithography resist with the nanoimprint composition and apply it to the field of manufacturing these liquid crystal display elements, the coating uniformity on the substrate is important.

  For positive photoresists used in semiconductor integrated circuit fabrication and liquid crystal display fabrication, pigment dispersed photoresists for color filter fabrication, etc., fluorine-based and / or silicone-based surfactants are added, and coating properties, specifically, substrates It is known to solve the problem of poor coating such as striations and scale-like patterns (unevenness of drying of resist film) that occur during top coating (Patent Documents 10 to 12). Also disclosed is the addition of fluorine-based surfactants and silicone-based surfactants to solventless photocurable compositions to improve the wear and coating properties of protective films such as compact disks and magneto-optical disks. (Patent Documents 12 to 15). Similarly, Patent Document 16 discloses that a nonionic fluorosurfactant is added in order to improve the ink ejection stability of the inkjet composition. Furthermore, Patent Document 17 discloses that 1% of a polymerizable unsaturated double bond-containing surfactant is used when embossing a painting composition coated with a thick film with a brush, brush, bar coater or the like with a hologram processing mold. As described above, an example in which 3% or more is preferably added to improve the water swellability of the cured film is disclosed. As described above, a technique for improving the coating property by adding a surfactant to a protective film such as a positive photoresist, a pigment-dispersed photoresist for producing a color filter, or a magneto-optical disk is a known technique. In addition, as seen in the above examples of inkjet and painting compositions, there is also a technique for adding a surfactant to a solventless photocurable resin and adding the surfactant to improve the properties in each application. It is known. Patent Document 18 discloses an example in which a photocurable resin containing a fluorosurfactant is used as an etching resist using a photo-nanoimprint method for the production of a semiconductor integrated circuit.

 However, a method for improving the substrate coatability of a photocurable nanoimprint resist composition that does not contain pigments, dyes, and organic solvents used for the permanent film has not been known.

 In optical nanoimprinting, it is necessary to improve the fluidity of the composition into the cavity of the mold recess, improve the mold releasability, improve the releasability between the mold and the resist, and between the resist and the substrate. It is necessary to improve the adhesion. It has been difficult to achieve both fluidity, peelability and adhesion.

The prior art relating to optical nanoimprinting, which is an application range of the present invention, will be described in more detail. In optical nanoimprint lithography, a liquid curable composition for optical nanoimprint lithography is dropped on a substrate such as a silicon wafer, quartz, glass, film or other material such as a ceramic material, a metal, or a polymer. After applying with a film thickness of several μm, pressing and pressing a mold having fine irregularities with a pattern size of about several tens of nm to several tens of μm, and curing the composition by light irradiation in the pressurized state, A method of releasing the mold from the coating film to obtain a transferred pattern is common. For this reason, in the case of optical nanoimprint lithography, at least one of the substrate and the mold needs to be transparent for the convenience of light irradiation. Usually, light is irradiated from the mold side, and an inorganic material such as quartz or sapphire, a light-transmitting resin, or the like is often used as the mold material.
The optical nanoimprint method is (1) no heating / cooling process is required and high throughput is expected compared to the thermal nanoimprint method. (2) Since the liquid composition is used, imprinting at low pressure is possible. Major advantages include (3) no dimensional change due to thermal expansion, (4) the mold is transparent and easy to align, and (5) a robust three-dimensional crosslinked body is obtained after curing. It is done. It is particularly suitable for semiconductor micromachining applications where alignment accuracy is required and for micromachining applications in the field of flat panel displays.

  Another feature of the optical nanoimprint method is that the resolution does not depend on the light source wavelength as compared with ordinary optical lithography. Therefore, expensive devices such as a stepper and an electron beam drawing device are also used for fine processing on the nanometer order. The feature is not required. On the other hand, the optical nanoimprint method requires an equal-magnification mold, and since the mold and the resin are in contact, there are concerns about the durability and cost of the mold.

 In this way, to apply a thermal and / or optical nanoimprint method and imprint a micrometer or nanometer size pattern over a large area, uniformity of pressing pressure and flatness of the master (mold) are required. In addition to this, it is necessary to control the fluidity of the composition into the cavity of the mold recess and the behavior of the composition flowing out by being pressed.

Molds used in optical nanoimprint lithography can be manufactured from various materials such as metals, semiconductors, ceramics, SOG (Spin On Glass), or certain plastics. For example, a flexible polydimethylsiloxane mold having a desired microstructure described in Patent Document 19 has been proposed. In order to form a three-dimensional structure on one surface of the mold, various lithography methods can be used depending on the size of the structure and the specifications for its resolution. Electron beam and x-ray lithography are typically used for structure dimensions below 300 nm. Direct laser exposure and UV lithography are used for larger structures.
For optical nanoimprinting, the releasability between the mold and the curable composition for photonanoimprint lithography is important. The surface treatment of the mold and the mold, specifically, hydrogenated silsesquioxane or fluorinated ethylene propylene copolymer Attempts have been made to solve the adhesion problem using a mold.

  Here, the photocurable resin used for optical nanoimprint lithography will be described. Photocurable resins applied to nanoimprints are roughly classified into radical polymerization types and ionic polymerization types, or their hybrid types, depending on the reaction mechanism. Although any composition can be imprinted, a radical polymerization type having a wide selection range of materials is generally used (Non-Patent Document 4). As the radical polymerization type, a composition containing a monomer (monomer) or oligomer having a vinyl group or (meth) acryl group capable of radical polymerization and a photopolymerization initiator is generally used. When irradiated with light, radicals generated by the photopolymerization initiator attack the vinyl group, and chain polymerization proceeds to form a polymer. When a bifunctional or higher polyfunctional monomer or oligomer is used as a component, a crosslinked structure is obtained. Non-Patent Document 5 discloses a composition that can be imprinted at low pressure and room temperature by using a low-viscosity UV curable monomer.

The characteristics of the material used for optical nanoimprint lithography will be described in detail. The required characteristics of materials vary depending on the application to be applied, but the demands for process characteristics are common regardless of the application. For example, main requirements shown in Non-Patent Document 6 are applicability, substrate adhesion, low viscosity (<5 mPa · s), peelability, low cure shrinkage, fast curability, and the like. In particular, it is known that there is a strong demand for a low-viscosity material in applications that require low-pressure imprinting and reduction of the remaining film ratio. On the other hand, when the required characteristics are listed for each application, there are, for example, a refractive index and light transmittance for an optical member, and an etching resistance and a remaining film thickness reduction for an etching resist. The key to material design is how to control these required properties and balance them. At least the process material and the permanent film have different required characteristics, so the material must be developed according to the process and application. As a material applied to such optical nanoimprint lithography, Non-Patent Document 6 discloses a photocurable material having a viscosity of about 60 mPa · s (25 ° C.). Similarly, Non-Patent Document 7 discloses a fluorine-containing photosensitive resin whose viscosity is 14.4 mPa · s whose main component is monomethacrylate and whose peelability is improved.
As described above, regarding the composition used in optical nanoimprinting, although there is a description of a demand for viscosity, there has been no report on a material design guideline for adapting to each application.

  An example of a photocurable resin that has been applied to optical nanoimprint lithography will be described. Patent Document 20 and Patent Document 21 disclose examples of embossing using a photocurable resin containing a polymer having an isocyanate group for producing a relief hologram or a diffraction grating. Patent Document 23 discloses a curable composition for optical nanoimprint lithography for imprinting that contains a polymer, a photopolymerization initiator, and a viscosity modifier.

 Patent Document 24 discloses a pattern forming method using a fluorine-containing curable material in order to improve releasability from a mold.

  Non-Patent Document 8 includes (1) a functional acrylic monomer, (2) a functional acrylic monomer, and (3) a photocurable radical polymerizable composition or a photocurable composition obtained by combining a functional acrylic monomer and a photopolymerization initiator. An example in which a photocationic polymerizable composition containing an epoxy compound and a photoacid generator is applied to nanoimprint lithography to examine thermal stability and mold releasability is disclosed.

  Non-Patent Document 9 describes a technique for improving problems such as peelability between a photocurable resin and a mold, film shrinkage after curing, and low sensitivity due to photopolymerization inhibition in the presence of oxygen (1). A curable composition for optical nanoimprint lithography comprising a functional acrylic monomer, (2) a functional acrylic monomer, a silicone-containing monofunctional acrylic monomer, and a photopolymerization initiator is disclosed.

  In Non-Patent Document 10, a photocurable nanoimprint lithography curable composition containing a monofunctional acrylic monomer, a silicone-containing monofunctional monomer, and a photopolymerization initiator is formed on a silicone substrate, and the surface-treated mold is used for photonanoimprinting. It is disclosed that defects after molding in lithography are reduced.

In Non-Patent Document 11, a curable composition for optical nanoimprint lithography containing a silicone monomer, a trifunctional acrylic monomer, and a photopolymerization initiator is formed on a silicone substrate, and high resolution and uniform coating are achieved by SiO ₂ mold. A composition having excellent properties is disclosed.

  Non-Patent Document 12 discloses an example in which a 50 nm pattern size is formed by a cationic polymerizable composition in which a specific vinyl ether compound and a photoacid generator are combined. Although it is characterized by a low viscosity and a high curing rate, it is stated that template peelability is an issue.

However, as shown in Non-Patent Documents 8 to 12, although various photocurable resins in which an acrylic monomer, an acrylic polymer, and a vinyl ether compound having different functional groups are applied to optical nanoimprint lithography have been disclosed, No guidance on material design such as preferred types, optimal monomer types, monomer combinations, optimal monomer or resist viscosities, preferred resist solution properties, improved resist coatability is disclosed. Therefore, a preferable composition for widely applying the composition to optical nanoimprint lithography applications is not known, and a satisfactory optical nanoimprint resist composition has never been proposed so far.
In the compositions of Non-Patent Documents 11 and 12 in which the composition is described, there are low-viscosity compositions, but both of them are photocured to form a pattern and subsequently subjected to heat treatment, the transmittance of the cured film Is low (colored) and has insufficient hardness, and cannot be practically used as a permanent film. The composition is not known.

Non-Patent Documents 13 and 14 propose an inorganic / organic hybrid material composed of a mixture of silica sol treated with a photofunctional cross-linking material, (meth) acrylic monomer, and photopolymerization initiator, and reports its application to optical nanoimprint lithography. Has been. Non-Patent Documents 13 and 14 report that it is possible to perform patterning up to a line width of 600 nm as an example of a pattern formation example of a 200 nm line of an imprint material or a mold material. However, there are problems such as insufficient releasability from the mold and insufficient hardness of the cured film, which are not always satisfactory.
In addition, some of the compositions of Non-Patent Documents 13 and 14 are low-viscosity, but both of them are photocured to form a pattern and subsequently have a low transmittance (colored) when cured. ) Also, the hardness is insufficient. In particular, a composition that is practically usable as a permanent film is not known.

Patent Document 24 discloses a hard coat composition containing a surface-treated colloidal silica, a specific (meth) acrylic monomer, a leveling agent, and a photopolymerization initiator, and has film hardness and low curing shrinkage. Although the application to the optical disk made compatible is reported, in these compositions, the peeling property from the mold and the substrate coating property were insufficient, and the application to the optical nanoimprint lithography was difficult. Furthermore, after photocuring, the transmittance when heat-treated is low (colored) and cannot be used as a permanent film.
As described above, a resist composition that can be practically used as a permanent film and that can be applied with the optical nanoimprint method has not been proposed so far.

The main technical issues as a permanent film are pattern accuracy, adhesion, transparency after heat treatment exceeding 200 ° C, high mechanical properties (strength against external pressure), scratch resistance, flattening properties, solvent resistance, heating There are many problems such as reduction of outgas during processing. When applying a curable composition for optical nanoimprint lithography for optical nanoimprint as a permanent film, as with conventional resists using acrylic resin,
It is important to provide (1) coating film uniformity, (2) transparency after heat treatment, and (3) scratch resistance.

At the same time, in addition to the above points (1) to (3), it is necessary to consider the following viewpoints (4) and (5) as a curable composition for optical nanoimprint lithography. The difficulty level becomes higher.
(4) Ensure resist fluidity in mold recesses and require low viscosity without solvent or use of a small amount of solvent. (5) After photocuring, easily peel off from mold and mold. Although various materials have been disclosed for curable compositions for optical nanoimprint lithography for nanoimprints, they have been known for use in inkjet compositions and protective films for magneto-optical disks. The curable composition for optical nanoimprint lithography used as a composition or an etching resist has a common part with the curable composition for optical nanoimprint lithography used for a permanent film, but is subjected to high-temperature heat treatment, mechanical It differs greatly in terms of strength, etc., inkjet, magneto-optical disk protective film, etching If the photo-curable resin applied for resist use is applied as it is as a resist for a permanent film, it is difficult to obtain a product that can withstand practicality such as transparency and solvent resistance.

US Pat. No. 5,772,905 US Pat. No. 5,956,216 US Pat. No. 5,259,926 JP 2005-527110 Gazette JP 2005-197699 A Japanese Patent Laying-Open No. 2005-301289 JP 2000-39713 A JP-A-6-43643 Japanese Patent Laid-Open No. 2004-240241 Japanese Patent Laid-Open No. 7-230165 JP 2000-181055 A JP 2004-94241 A JP-A-4-149280 JP-A-7-62043 JP 2001-93192 A JP 2005-8759 A JP 2003-165930 A JP 2007-84625 A International Publication WO99 / 22849 Pamphlet JP 2004-59820 A JP 2004-59822 A US Publication No. 2004/110856 JP 2006-114882 A JP 2000-143924 A

S. Chou et al .: Appl. Phys. Lett. Vol. 67, 3114 (1995) M. Colbun et al,: Proc.SPIE, Vol. 3676,379 (1999) Electronic Journal 121−123 No.8 (2002) F.Xu et al.:SPIE Microlithography Conference, 5374,232 (2004) D.J.Resnick et al .: J.Vac.Sci.Technol.B, Vol.21, No.6,2624 (2003) The latest resist material handbook, P1, 103-104 (2005, published by Information Organization) CM Publishing: Development and application of nanoimprint P159-160 (2006) N. Sakai et al .: J. Photopolymer Sci. Technol. Vol. 18, No. 4, 531 (2005) M. Stewart et al .: MRS Buletin, Vol. 30, No. 12, 947 (2005) T. Beiley et al .: J. Vac. Sci. Technol. B18 (6), 3572 (2000) B. Vratzov et al .: J. Vac. Sci. Technol. B21 (6), 2760 (2003) E.K.Kim et al .: J.Vac.Sci.Technol, B22 (1), 131 (2004) Proc.SPIE Int.Soc.Opt.Eng., Vol.6151, No.Pt2,61512F (2006) Science and industry, Vol.80, No.7,322 (2006)

  The present invention has been accomplished in view of the above circumstances, and an object thereof is to provide a novel curable composition for optical nanoimprint lithography having excellent photocurability. In particular, an object is to provide a composition that is comprehensively excellent in terms of photocurability, adhesion, peelability, residual film properties, pattern shape, coatability, and etching suitability. Another object of the present invention is to provide a composition having excellent residual film properties, light transmittance, scratch resistance and other mechanical properties and solvent resistance when used as a permanent film such as a protective film or a spacer.

（一般式（Ｉ）中、Ｒ¹¹は水素原子またはメチル基を表し、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵は、それぞれ、水素原子、メチル基、エチル基、ブロピル基、ブチル基、メトキシ基、エトキシ基を表す。ｎ１は１または２、ｍ１は、０、１、２のいずれかを表す。Ｚ¹¹は、メチレン基、酸素原子、−ＮＨ−基を表し、２つのＺ¹¹は互いに異なっていてもよい。Ｗ¹¹は−Ｃ（＝Ｏ）−または−ＳＯ₂−を表す。Ｒ¹²とＲ¹³およびＲ¹⁴とＲ¹⁵は、それぞれ、互いに結合して環を形成してもよい。）
一般式（ＩＩ）

（一般式（ＩＩ）中、Ｒ²¹は水素原子またはメチル基を表し、Ｒ²²、Ｒ²³、Ｒ²⁴およびＲ²⁵は、それぞれ、水素原子、メチル基、エチル基、ブロピル基、ブチル基、ハロゲン原子、メトキシ基、エトキシ基を表す。Ｒ²²とＲ²³およびＲ²⁴とＲ²⁵は、それぞれ、互いに結合して環を形成してもよい。ｎ２は１、２、３のいずれかであり、ｍ２は、０、１、２のいずれかを表す。Ｙ²¹はメチレン基または酸素原子を表す。）
一般式（ＩＩＩ）

（一般式（ＩＩＩ）中、Ｒ³²、Ｒ³³、Ｒ³⁴およびＲ³⁵は、それぞれ、水素原子、メチル基、エチル基、ブロピル基、ブチル基、ハロゲン原子、メトキシ基、エトキシ基を表す。ｎ３は１、２、３のいずれかであり、ｍ３は、０、１、２のいずれかを表す。Ｘ³¹は−Ｃ（＝Ｏ）−、メチレン基、エチレン基を表し、２つのＸ³¹は互いに異なっていてもよい。Ｙ³²は、メチレン基または酸素原子を表す。）
一般式（ＩＶ）

（一般式（ＩＶ）中、Ｒ⁴¹は水素原子またはメチル基を表す。Ｒ⁴²およびＲ⁴³は、それぞれ、水素原子、メチル基、エチル基、ブロピル基、ブチル基、ハロゲン原子、メトキシ基、エトキシ基を表す。Ｗ⁴¹は、単結合、結合無し、または−Ｃ（＝Ｏ）−を表す。ｎ４は２、３、４のいずれかを表す。Ｘ⁴²は−Ｃ（＝Ｏ）−、−Ｃ＝Ｃ−、−Ｃ＝Ｎ−、またはメチレン基を表し、それぞれのＸ⁴²は同一でも異なっていてもよい。Ｍ⁴¹は炭素数が１〜４の炭化水素連結基、酸素原子または窒素原子を表し、それぞれのＭ⁴¹は同一でも異なっていてもよい。）
一般式(Ｖ）

（一般式（Ｖ）中、Ｒ⁵¹は水素原子またはメチル基を表す。Ｚ⁵²は酸素原子、−ＣＨ＝Ｎ−またはメチレン基を表す。Ｗ⁵²はメチレン基または酸素原子を表す。Ｙ⁵²は単結合または−Ｃ（Ｃ＝Ｏ）−を表す。Ｙ⁵³は単結合または−Ｃ（Ｃ＝Ｏ）−を表す。Ｒ⁵⁴およびＲ⁵⁵は、それぞれ、水素原子、メチル基、エチル基、ブロピル基、ブチル基、ハロゲン原子、メトキシ基、エトキシ基を表し、Ｒ⁵⁴とＲ⁵⁵は互いに結合して環を形成してもよい。Ｘ⁵¹は単結合もしくは結合なしでよい。ｍ５は０、１、２のいずれかである。Ｗ⁵²、Ｚ⁵²、Ｒ⁵⁴、Ｒ⁵⁵のうち少なくとも一つは酸素原子または窒素原子を含む。）
一般式（ＶＩ)

（一般式（ＶＩ）中、Ｒ⁶¹は水素原子またはメチル基、Ｒ⁶²およびＲ⁶³は、それぞれ、水素原子、メチル基、エチル基、ヒドロキシエチル基、プロピル基、（ＣＨ₃）₂Ｎ−（ＣＨ₂）_m6−（ｍ６は１、２または３）、ＣＨ₃ＣＯ−（ＣＲ⁶⁴Ｒ⁶⁵）_p6−（Ｒ⁶⁴およびＲ⁶⁵は、それぞれ、水素原子またはメチル基を表し、ｐ６は１、２または３のいずれかである。）、（ＣＨ₃）₂−Ｎ−（ＣＨ₂）_p6−（ｐ６は１、２または３のいずれかである。）。但し、該一般式（ＶＩ）中の−ＮＲ⁶²（Ｒ⁶³）の部分が、−Ｎ＝Ｃ＝Ｏ基であってもよい。またＲ⁶²およびＲ⁶³は同時に水素原子になることはない。またＸ⁶は−ＣＯ−、−ＣＯＣＨ₂−、−ＣＯＣＨ₂ＣＨ₂−、−ＣＯＣＨ₂ＣＨ₂ＣＨ₂−、−ＣＯＯＣＨ₂ＣＨ₂−のいずれかである。）
一般式(ＶＩＩ)

（一般式(ＶＩＩ)中、Ｒ⁷¹およびＲ⁷²は、それぞれ、水素原子またはメチル基であり、Ｒ⁷³は水素原子、メチル基またはエチル基を表す。）
一般式(ＶＩＩＩ)

（一般式（ＶＩＩＩ）中、Ｒ⁸¹は水素原子、メチル基またはヒドロキシメチル基を表す。Ｒ⁸²、Ｒ⁸³、Ｒ⁸⁴、Ｒ⁸⁵は、それぞれ、水素原子、水酸基、メチル基、エチル基、ヒドロキシメチル基、ヒドロキシエチル基、プロピル基およびブチル基を表し、Ｒ⁸²、Ｒ⁸³、Ｒ⁸⁴およびＲ⁸⁵の少なくとも２つが互いに結合して環を形成してもよい。Ｗ⁸¹はメチレン基、−ＮＨ−、−Ｎ（ＣＨ₃）−、−Ｎ（Ｃ₂Ｈ₅）−である。Ｗ⁸²は単結合または、−Ｃ（＝Ｏ）−を表す。Ｗ⁸²が単結合の場合、Ｒ⁸²、Ｒ⁸³、Ｒ⁸⁴およびＲ⁸⁴は、いずれも、水素原子でない。ｎ７は０から８の整数を表す。）。
（６）（１）〜（５）のいずれか１項に記載の組成物であって、さらに、少なくとも１個のエチレン性不飽和結合を有する部位、ならびに、シリコーン原子および／またはリン原子を含有する第２の重合性不飽和単量体を、前記重合性不飽和単量体中０．１質量％以上含む（１）〜（５）のいずれか１項に記載の組成物。
（７）無機酸化物微粒子がコロイダルシリカである、（１）〜（６）のいずれか１項に記載の組成物。
（８）コロイダルシリカが表面処理されたコロイダルシリカである、（７に記載の組成物。
（９）コロイダルシリカが反応性（メタ）アクリレート基を有する化合物で表面処理されたコロイダルシリカである、（８）に記載の組成物。
（１０）酸化防止剤を含有する（１）〜（９）のいずれか１項に記載の組成物。
（１１）（１）〜（１０）のいずれか１項に記載の組成物であって、２５℃における粘度が２５ｍＰａ・ｓ以下である、（１）〜（１０）のいずれか１項に記載の組成物。
（１２）（１）〜（１１）のいずれか１項に記載の組成物を塗布する工程、光透過性モールドを基板上のレジスト層に加圧し、前記塗布した組成物を変形させる工程、モールド裏面または基板裏面より光を照射し、塗膜を硬化し、所望のパターンに嵌合するレジストパターンを形成する工程、光透過性モールドを塗膜から脱着する工程を含むパターン形成方法。 As a result of intensive studies by the inventors based on the above problems, it has been found that the above problems can be solved by the following means.
(1) 35 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 15% by mass of a photopolymerization initiator, at least one of a fluorine-based surfactant, a silicone-based surfactant, and a fluorine / silicone-based surfactant A curable composition for optical nanoimprint lithography comprising 0.001 to 5 mass% of seeds and 0.1 to 50 mass% of inorganic oxide fine particles.
(2) The composition according to (1), wherein the polymerizable unsaturated monomer has at least one of a site having an ethylenically unsaturated bond in the molecule, an oxygen atom, a nitrogen atom, and a sulfur atom. The photo-nanoimprint containing at least 15% by mass of a monofunctional polymerizable unsaturated monomer containing a moiety having a functional group and 48 to 99% by mass of the polymerizable unsaturated monomer A curable composition for lithography.
(3) The composition according to (2), comprising at least one compound selected from the following (a), (b) and (c) as a monofunctional polymerizable unsaturated monomer.
(A) a polymerizable unsaturated monomer having a portion having an ethylenically unsaturated bond in one molecule and an aliphatic cyclic portion containing a hetero atom (b) a portion having an ethylenically unsaturated bond in one molecule; A polymerizable unsaturated monomer having a —C (═O) — bond and an NR bond (R is a hydrogen atom or a methyl group) (c) a site having an ethylenically unsaturated bond in one molecule and 6 carbon atoms Polymerizable unsaturated monomer having alicyclic moiety of ˜12 (4) The heteroatom of the monofunctional polymerizable unsaturated monomer of (a) is any one of oxygen atom, nitrogen atom and sulfur atom The composition according to (3), which is a seed or more.
(5) The monofunctional polymerizable unsaturated monomer according to any one of (2) to (4), wherein the monofunctional polymerizable unsaturated monomer is at least one selected from the following general formulas (I) to (VIII): Composition.
Formula (I)

(In the general formula (I), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, respectively. Group represents an ethoxy group, n1 represents 1 or 2, m1 represents any of 0, 1, and 2. Z ¹¹ represents a methylene group, an oxygen atom, and an —NH— group, and two Z ¹¹ represent each other W ¹¹ represents —C (═O) — or —SO ₂ —, R ¹² and R ^13, and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. .)
Formula (II)

(In the general formula (II), R ²¹ represents a hydrogen atom or a methyl group, and R ²² , R ²³ , R ²⁴ and R ²⁵ represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, respectively. Each of R ²² and R ²³ and R ²⁴ and R ²⁵ may be bonded to each other to form a ring, n2 is any one of 1, 2, and 3; m2 represents any of 0, 1, and 2. Y ²¹ represents a methylene group or an oxygen atom.)
Formula (III)

(In the general formula (III), R ³² , R ³³ , R ³⁴ and R ³⁵ represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group and an ethoxy group, respectively. Is any one of 1, 2, and 3, and m3 represents either 0, 1, or 2. X ³¹ represents —C (═O) —, a methylene group, or an ethylene group, and two X ³¹ represent Y ³² represents a methylene group or an oxygen atom.
Formula (IV)

(In the general formula (IV), R ⁴¹ represents a hydrogen atom or a methyl group. R ⁴² and R ⁴³ represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group, and an ethoxy group, respectively. W ⁴¹ represents a single bond, no bond, or —C (═O) —, n4 represents 2, 3, or 4. X ⁴² represents —C (═O) —, — C = C-, -C = N-, or a methylene group, and each X ⁴² may be the same or different, M ⁴¹ is a hydrocarbon linking group having 1 to 4 carbon atoms, an oxygen atom or a nitrogen atom And each M ⁴¹ may be the same or different.)
General formula (V)

(In the general formula (V), R ⁵¹ represents a hydrogen atom or a methyl group. Z ⁵² represents an oxygen atom, —CH═N— or a methylene group. W ⁵² represents a methylene group or an oxygen atom. Y ⁵² represents Represents a single bond or —C (C═O) —, Y ⁵³ represents a single bond or —C (C═O) —, and R ⁵⁴ and R ⁵⁵ represent a hydrogen atom, a methyl group, an ethyl group, or a propyl, respectively. A group, a butyl group, a halogen atom, a methoxy group or an ethoxy group, R ⁵⁴ and R ⁵⁵ may be bonded to each other to form a ring, X ⁵¹ may be a single bond or no bond, m5 is 0, 1 Or at least one of W ⁵² , Z ⁵² , R ⁵⁴ , and R ⁵⁵ contains an oxygen atom or a nitrogen atom.)
Formula (VI)

(In the general formula (VI), R ⁶¹ is a hydrogen atom or a methyl group, R ⁶² and R ⁶³ are a hydrogen atom, a methyl group, an ethyl group, a hydroxyethyl group, a propyl group, (CH ₃ ) ₂ N— ( CH ₂ ) _m6 — (m6 is 1, 2 or 3), CH ₃ CO— (CR ⁶⁴ R ⁶⁵ ) _p6 — (R ⁶⁴ and R ⁶⁵ each represents a hydrogen atom or a methyl group, and p6 is 1, 2; Or ( ₃ )), (CH ₃ ) ₂ —N— (CH ₂ ) _p6 — (p6 is 1, 2 or 3), provided that in general formula (VI) The moiety of —NR ⁶² (R ⁶³ ) may be a —N═C═O group, R ⁶² and R ⁶³ do not simultaneously become a hydrogen atom, and X ⁶ represents —CO— or —COCH. _{2 -, - COCH 2 CH 2} -, - COCH 2 CH 2 CH 2 -, - COOCH 2 CH 2 - is either )
Formula (VII)

(In general formula (VII), R ⁷¹ and R ⁷² are each a hydrogen atom or a methyl group, and R ⁷³ represents a hydrogen atom, a methyl group, or an ethyl group.)
General formula (VIII)

(In the general formula (VIII), R ⁸¹ represents a hydrogen atom, a methyl group or a hydroxymethyl group. R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ are a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, a hydroxy group, respectively. Represents a methyl group, a hydroxyethyl group, a propyl group and a butyl group, and at least two of R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ may be bonded to each other to form a ring, W ⁸¹ represents a methylene group, —NH _{-, - N (CH 3)} -, - N (C 2 H 5) - .W 82 is a single bond or, -C (= O) - when .W ⁸² representing a single bond, R ^82, R ⁸³ , R ⁸⁴ and R ⁸⁴ are not hydrogen atoms, and n7 represents an integer of 0 to 8.
(6) The composition according to any one of (1) to (5), further comprising a site having at least one ethylenically unsaturated bond, and a silicone atom and / or a phosphorus atom The composition according to any one of (1) to (5), wherein the second polymerizable unsaturated monomer is 0.1% by mass or more in the polymerizable unsaturated monomer.
(7) The composition according to any one of (1) to (6), wherein the inorganic oxide fine particles are colloidal silica.
(8) The composition according to (7), wherein the colloidal silica is a surface-treated colloidal silica.
(9) The composition according to (8), wherein the colloidal silica is colloidal silica surface-treated with a compound having a reactive (meth) acrylate group.
(10) The composition according to any one of (1) to (9), comprising an antioxidant.
(11) The composition according to any one of (1) to (10), wherein the viscosity at 25 ° C. is 25 mPa · s or less. Composition.
(12) A step of applying the composition according to any one of (1) to (11), a step of applying pressure to a resist layer on a substrate and deforming the applied composition, a mold A pattern forming method including a step of irradiating light from the back surface or the back surface of the substrate, curing the coating film, forming a resist pattern that fits into a desired pattern, and desorbing the light transmissive mold from the coating film.

  According to the present invention, when used as an etching resist, it is possible to provide a composition that is comprehensively excellent in terms of photocurability, adhesion, peelability, residual film properties, pattern shape, coatability, and etching suitability. It was. In addition, when used as a permanent film, it has become possible to obtain a composition that is comprehensively excellent in mechanical properties such as residual film properties, light transmittance, and scratch resistance, and solvent resistance.

  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 this specification, meth (acrylate) represents acrylate and methacrylate, meth (acryl) represents acryl and methacryl, and meth (acryloyl) represents acryloyl and methacryloyl. Moreover, in this specification, a monomer and a monomer are the same. 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. That is, it goes without saying that the present invention is not limited to nano-order imprints.

 The curable composition for optical nanoimprint lithography of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) has, for example, high light transmittance before curing, the ability to form a fine uneven pattern, and suitability for coating. In addition to excellent processing suitability, after curing, sensitivity (fast curing), resolution, line edge roughness, film strength, mold release, residual film properties, etching resistance, low cure shrinkage In general, excellent coating properties can be obtained in terms of substrate adhesion or 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 mechanical properties, excellent adhesion between the coating film and the substrate, and excellent peeling properties between the coating film and the mold. Since pulling does not cause surface roughness, a good pattern can be formed.
(3) The volume shrinkage after photocuring is small and the mold transfer characteristics are excellent, so that an accurate formability of a fine pattern is possible.
(4) Since it is excellent in coating uniformity, it is suitable for the field of coating / microfabrication on large substrates.
(5) Since the photocuring speed of the film is high, the productivity is high.
(6) Since it is excellent in etching processing accuracy, etching resistance, etc., it can be suitably used as an etching resist for substrate processing of semiconductor devices and transistors,
(7) It is excellent in resist releasability after etching and does not produce a residue, so that it can be suitably used as an etching resist.
(8) Since it has high mechanical properties such as light transmittance, residual film property, scratch resistance, and solvent resistance, it can be suitably used as various permanent films.
And the like.

 For example, the composition of the present invention can be suitably applied to fine processing applications such as semiconductor integrated circuits and liquid crystal display thin film transistors, liquid crystal color filter protective films, spacers, and the like, which have been difficult to develop until now. Bulkhead materials for plasma display panels, flat screens, micro electromechanical systems (MEMS), sensor elements, optical recording media such as high-density memory disks, optical components such as diffraction grating relief holograms, nanodevices, optical devices, optical Film, polarizing element, organic transistor, color filter, overcoat layer, pillar material, rib material for liquid crystal alignment, microlens array, immunoassay chip, DNA separation chip, microreactor, nanobiodevice, optical waveguide, optical filter, photonic Production of liquid crystal Can be widely applied to.

 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. The composition of the present invention has a viscosity at 25 ° C. of preferably 25 mPa · s or less, more preferably 20 mPa · s or less, and further preferably 3 to 18 mPa · s. By setting such a viscosity, it is possible to impart the ability to form a fine concavo-convex pattern before curing, coating suitability and other processing suitability. After curing, resolution, line edge roughness, residual film properties, substrate adhesion Alternatively, excellent coating film properties can be imparted in other respects. By setting the viscosity of the composition of the present invention to 3 mPa · s or more, there is a tendency that problems of substrate coating suitability and a decrease in mechanical strength of the film hardly occur. Specifically, by setting the viscosity to 3 mPa · s or more, it is preferable that unevenness on the surface is generated during the application of the composition or the composition can be prevented from flowing out of the substrate during the application. On the other hand, by setting the viscosity of the composition of the present invention to 25 mPa · s or less, even when a mold having a fine concavo-convex pattern is adhered to the composition, the composition also flows into the cavity of the concave portion of the mold, and the atmosphere Is less likely to be taken in, so that it is difficult to cause bubble defects, and it is difficult for residues to remain after photocuring in the mold convex portion.

  The composition of the present invention comprises 35 to 99% by weight of a polymerizable unsaturated monomer, 0.1 to 15% by weight of a photopolymerization initiator, a fluorine surfactant, a silicone surfactant and a fluorine / silicone surfactant. At least one of 0.001 to 5% by mass and 0.1 to 50% by mass of inorganic oxide fine particles.

Polymerizable unsaturated monomer Preferably, the composition of the present invention comprises a polymerizable unsaturated monomer as a site having an ethylenically unsaturated bond in the molecule, and at least an oxygen atom, a nitrogen atom and a sulfur atom. The content of the polymerizable unsaturated monomer containing the monofunctional polymerizable unsaturated monomer containing a portion having one kind and containing the monofunctional polymerizable unsaturated monomer is 48 to 99 masses. % Of the composition. More preferably, it is a composition containing 15% by mass or more, more preferably 25 to 60% by mass of the monofunctional polymerizable unsaturated monomer.
The monofunctional polymerizable unsaturated monomer is preferably a monofunctional polymerizable unsaturated monomer selected from the following (a), (b) and (c).
(A) a polymerizable unsaturated monomer (b) having an aliphatic cyclic moiety containing a moiety having an ethylenically unsaturated bond and a hetero atom (preferably an oxygen atom, a nitrogen atom and a sulfur atom) in one molecule; ) A polymerizable unsaturated monomer having a site having an ethylenically unsaturated bond in one molecule and a -C (= O)-bond and an NR bond (R is a hydrogen atom or a methyl group) (c) in one molecule A polymerizable unsaturated monomer having a portion having an ethylenically unsaturated bond and an alicyclic portion having 6 to 12 carbon atoms

  The monofunctional polymerizable unsaturated monomer used in the present invention is preferably a polymerizable unsaturated monomer represented by any one of the following general formulas (I) to (VIII).

（一般式（Ｉ）中、Ｒ¹¹は水素原子またはメチル基を表し、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵は、それぞれ、水素原子、メチル基、エチル基、ブロピル基、ブチル基、メトキシ基、エトキシ基を表す。ｎ１は１または２、ｍ１は、０、１、２のいずれかを表す。Ｚ¹¹は、メチレン基、酸素原子、−ＮＨ−基を表し、２つのＺ¹¹は互いに異なっていてもよい。Ｗ¹¹は−Ｃ（＝Ｏ）−または−ＳＯ₂−を表す。Ｒ¹²とＲ¹³およびＲ¹⁴とＲ¹⁵は、それぞれ、互いに結合して環を形成してもよい。）
ここで、Ｒ¹¹は水素原子が好ましい。Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵は、それぞれ、水素原子、メチル基が好ましく、水素原子がより好ましい。ｍ１は、０または１が好ましい。Ｚ¹¹は、少なくとも一方が酸素原子であることが好ましい。Ｗ¹¹は−Ｃ（＝Ｏ）−が好ましい。
ｎ１が２以上のとき、Ｒ¹⁴、Ｒ¹⁵は、それぞれ、同一であってもよいし、異なっていてもよい。 Formula (I)

(In the general formula (I), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, respectively. Group represents an ethoxy group, n1 represents 1 or 2, m1 represents any of 0, 1, and 2. Z ¹¹ represents a methylene group, an oxygen atom, and an —NH— group, and two Z ¹¹ represent each other W ¹¹ represents —C (═O) — or —SO ₂ —, R ¹² and R ^13, and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. .)
Here, R ¹¹ is preferably a hydrogen atom. R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are each preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. m1 is preferably 0 or 1. At least one of Z ¹¹ is preferably an oxygen atom. W ¹¹ is preferably —C (═O) —.
When n1 is 2 or more, R ¹⁴ and R ¹⁵ may be the same or different.

Specific examples of the compound represented by the general formula (I) include the following formulas (I-1) to (I-19).

（一般式（ＩＩ）中、Ｒ²¹は水素原子またはメチル基を表し、Ｒ²²、Ｒ²³、Ｒ²⁴およびＲ²⁵は、それぞれ、水素原子、メチル基、エチル基、ブロピル基、ブチル基、ハロゲン原子、メトキシ基、エトキシ基を表す。Ｒ²²とＲ²³およびＲ²⁴とＲ²⁵は、それぞれ、互いに結合して環を形成してもよい。ｎ２は１、２、３のいずれかであり、ｍ２は、０、１、２のいずれかを表す。Ｙ²¹はメチレン基または酸素原子を表す。）
Ｒ²¹は水素原子が好ましい。Ｒ²²、Ｒ²³、Ｒ²⁴およびＲ²⁵は、それぞれ、水素原子、メチル基、エチル基、プロピル基、ブチル基が好ましく、水素原子、メチル基、エチル基がより好ましい。ｎ２は１または２が好ましい。ｍ２は、０または１が好ましい。 Formula (II)

(In the general formula (II), R ²¹ represents a hydrogen atom or a methyl group, and R ²² , R ²³ , R ²⁴ and R ²⁵ represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, respectively. Each of R ²² and R ²³ and R ²⁴ and R ²⁵ may be bonded to each other to form a ring, n2 is any one of 1, 2, and 3; m2 represents any of 0, 1, and 2. Y ²¹ represents a methylene group or an oxygen atom.)
R ²¹ is preferably a hydrogen atom. R ²² , R ²³ , R ²⁴ and R ²⁵ are each preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group, more preferably a hydrogen atom, a methyl group or an ethyl group. n2 is preferably 1 or 2. m2 is preferably 0 or 1.

Specific examples of the compound represented by the general formula (II) include the following formulas (II-1) to (II-9).

（一般式（ＩＩＩ）中、Ｒ³²、Ｒ³³、Ｒ³⁴およびＲ³⁵は、それぞれ、水素原子、メチル基、エチル基、ブロピル基、ブチル基、ハロゲン原子、メトキシ基、エトキシ基を表す。ｎ３は１、２、３のいずれかであり、ｍ３は、０、１、２のいずれかを表す。Ｘ³¹は−Ｃ（＝Ｏ）−、メチレン基、エチレン基を表し、２つのＸ³¹は互いに異なっていてもよい。Ｙ³²は、メチレン基または酸素原子を表す。）
Ｒ³²、Ｒ³³、Ｒ³⁴およびＲ³⁵は、それぞれ、水素原子、メチル基、エチル基、プロピル基が好ましく、水素原子がより好ましい。ｎ３は１または２が好ましい。 Formula (III)

(In the general formula (III), R ³² , R ³³ , R ³⁴ and R ³⁵ represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group and an ethoxy group, respectively. Is any one of 1, 2, and 3, and m3 represents either 0, 1, or 2. X ³¹ represents —C (═O) —, a methylene group, or an ethylene group, and two X ³¹ represent Y ³² represents a methylene group or an oxygen atom.
R ³² , R ³³ , R ³⁴ and R ³⁵ are each preferably a hydrogen atom, a methyl group, an ethyl group or a propyl group, more preferably a hydrogen atom. n3 is preferably 1 or 2.

Specific examples of the compound represented by the general formula (III) include the following formulas (III-1) to (III-11).

（一般式（ＩＶ）中、Ｒ⁴¹は水素原子またはメチル基を表す。Ｒ⁴²およびＲ⁴³は、それぞれ、水素原子、メチル基、エチル基、ブロピル基、ブチル基、ハロゲン原子、メトキシ基、エトキシ基を表す。Ｗ⁴¹は、単結合、結合無し、または−Ｃ（＝Ｏ）−を表す。ｎ４は２、３、４のいずれかを表す。Ｘ⁴²は−Ｃ（＝Ｏ）−、−Ｃ＝Ｃ−、−Ｃ＝Ｎ−、またはメチレン基を表し、それぞれのＸ⁴²は同一でも異なっていてもよい。Ｍ⁴¹は炭素数が１〜４の炭化水素連結基、酸素原子または窒素原子を表し、それぞれのＭ⁴¹は同一でも異なっていてもよい。）
Ｒ⁴¹は水素原子が好ましい。Ｒ⁴²およびＲ⁴³は、それぞれ、水素原子、メチル基、エチル基が好ましく、水素原子がより好ましい。Ｍ⁴¹はメチレン基、エチレン基、プロピレン基、ブチレン基のいずれかであることが好ましい。 Formula (IV)

(In the general formula (IV), R ⁴¹ represents a hydrogen atom or a methyl group. R ⁴² and R ⁴³ represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group, and an ethoxy group, respectively. W ⁴¹ represents a single bond, no bond, or —C (═O) —, n4 represents 2, 3, or 4. X ⁴² represents —C (═O) —, — C = C-, -C = N-, or a methylene group, and each X ⁴² may be the same or different, M ⁴¹ is a hydrocarbon linking group having 1 to 4 carbon atoms, an oxygen atom or a nitrogen atom And each M ⁴¹ may be the same or different.)
R ⁴¹ is preferably a hydrogen atom. R ⁴² and R ⁴³ are each preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom. M ⁴¹ is preferably any one of a methylene group, an ethylene group, a propylene group, and a butylene group.

Specific examples of the compound represented by the general formula (IV) include the following formulas (IV-1) to (IV-13).

（一般式（Ｖ）中、Ｒ⁵¹は水素原子またはメチル基を表す。Ｚ⁵²は酸素原子、−ＣＨ＝Ｎ−またはメチレン基を表す。Ｗ⁵²はメチレン基または酸素原子を表す。Ｙ⁵²は単結合またはーＣ（Ｃ＝Ｏ）―を表す。Ｙ⁵³は単結合またはーＣ（Ｃ＝Ｏ）―を表す。Ｒ⁵⁴およびＲ⁵⁵は、それぞれ、水素原子、メチル基、エチル基、ブロピル基、ブチル基、ハロゲン原子、メトキシ基、エトキシ基を表し、Ｒ⁵⁴とＲ⁵⁵は互いに結合して環を形成してもよい。Ｘ⁵¹は単結合もしくは結合なしでよい。ｍ５は０、１、２のいずれかである。Ｗ⁵²、Ｚ⁵²、Ｒ⁵⁴、Ｒ⁵⁵のうち少なくとも一つは酸素原子または窒素原子を含む。）
ここで、Ｘ⁵¹が結合なしの場合とは、後述する一般式（Ｖ）の例示化合物の（Ｖ−７）、（Ｖ−８）のような結合形態をいう。
Ｒ⁵¹は水素原子が好ましい。Ｒ⁵⁴およびＲ⁵⁵は、それぞれ、水素原子、メチル基、エチル基が好ましく、水素原子、メチル基がより好ましい。ｍ５は１または２が好ましい。 General formula (V)

(In the general formula (V), R ⁵¹ represents a hydrogen atom or a methyl group. Z ⁵² represents an oxygen atom, —CH═N— or a methylene group. W ⁵² represents a methylene group or an oxygen atom. Y ⁵² represents Represents a single bond or —C (C═O) —, Y ⁵³ represents a single bond or —C (C═O) —, and R ⁵⁴ and R ⁵⁵ represent a hydrogen atom, a methyl group, an ethyl group, or a propyl, respectively. Represents a group, butyl group, halogen atom, methoxy group or ethoxy group, R ⁵⁴ and R ⁵⁵ may be bonded to each other to form a ring, X ⁵¹ may be a single bond or no bond, m5 is 0, 1 Or at least one of W ⁵² , Z ⁵² , R ⁵⁴ , and R ⁵⁵ contains an oxygen atom or a nitrogen atom.)
Here, the case where X ⁵¹ is not bonded refers to a bonded form such as (V-7) and (V-8) of an exemplary compound of the general formula (V) described later.
R ⁵¹ is preferably a hydrogen atom. R ⁵⁴ and R ⁵⁵ are each preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group. m5 is preferably 1 or 2.

Specific examples of the compound represented by the general formula (V) include the following formulas (V-1) to (V-8).

（一般式（ＶＩ）中、Ｒ⁶¹は水素原子またはメチル基、Ｒ⁶²およびＲ⁶³は、それぞれ、水素原子、メチル基、エチル基、ヒドロキシエチル基、プロピル基、（ＣＨ₃）₂Ｎ−（ＣＨ₂）_m6−（ｍ６は１、２または３）、ＣＨ₃ＣＯ−（ＣＲ⁶⁴Ｒ⁶⁵）_p6−（Ｒ⁶⁴およびＲ⁶⁵は、それぞれ、水素原子またはメチル基を表し、ｐ６は１、２または３のいずれかである。）、（ＣＨ₃）₂−Ｎ−（ＣＨ₂）_p6−（ｐ６は１、２または３のいずれかである。）。但し、該一般式（ＶＩ）中の−ＮＲ⁶²（Ｒ⁶³）の部分が、−Ｎ＝Ｃ＝Ｏ基であってもよい。またＲ⁶²およびＲ⁶³は同時に水素原子になることはない。またＸ⁶は−ＣＯ−、−ＣＯＣＨ₂−、−ＣＯＣＨ₂ＣＨ₂−、−ＣＯＣＨ₂ＣＨ₂ＣＨ₂−、−ＣＯＯＣＨ₂ＣＨ₂−のいずれかである。）
一般式(ＶＩＩ) Formula (VI)

(In the general formula (VI), R ⁶¹ is a hydrogen atom or a methyl group, R ⁶² and R ⁶³ are a hydrogen atom, a methyl group, an ethyl group, a hydroxyethyl group, a propyl group, (CH ₃ ) ₂ N— ( CH ₂ ) _m6 — (m6 is 1, 2 or 3), CH ₃ CO— (CR ⁶⁴ R ⁶⁵ ) _p6 — (R ⁶⁴ and R ⁶⁵ each represents a hydrogen atom or a methyl group, and p6 is 1, 2; Or ( ₃ )), (CH ₃ ) ₂ —N— (CH ₂ ) _p6 — (p6 is 1, 2 or 3), provided that in general formula (VI) The moiety of —NR ⁶² (R ⁶³ ) may be a —N═C═O group, R ⁶² and R ⁶³ do not simultaneously become a hydrogen atom, and X ⁶ represents —CO— or —COCH. _{2 -, - COCH 2 CH 2} -, - COCH 2 CH 2 CH 2 -, - COOCH 2 CH 2 - is either )
Formula (VII)

Specific examples of the compound represented by the general formula (VI) include the following formulas (VI-1) to (VI-10).

（一般式(ＶＩＩ)中、Ｒ⁷¹およびＲ⁷²は、それぞれ、水素原子またはメチル基であり、Ｒ⁷³は水素原子、メチル基またはエチル基を表す。） Formula (VII)

(In general formula (VII), R ⁷¹ and R ⁷² are each a hydrogen atom or a methyl group, and R ⁷³ represents a hydrogen atom, a methyl group, or an ethyl group.)

Specific examples of the compound represented by the general formula (VII) include the following formulas (VII-1) to (VII-3).

（一般式（ＶＩＩＩ）中、Ｒ⁸¹は水素原子、メチル基またはヒドロキシメチル基を表す。Ｒ⁸²、Ｒ⁸³、Ｒ⁸⁴、Ｒ⁸⁵は、それぞれ、水素原子、水酸基、メチル基、エチル基、ヒドロキシメチル基、ヒドロキシエチル基、プロピル基およびブチル基を表し、Ｒ⁸²、Ｒ⁸³、Ｒ⁸⁴およびＲ⁸⁵の少なくとも２つが互いに結合して環を形成してもよい。Ｗ⁸¹はメチレン基、−ＮＨ−、−Ｎ（ＣＨ₃）−、−Ｎ（Ｃ₂Ｈ₅）−である。Ｗ⁸²は単結合または、−Ｃ（＝Ｏ）−を表す。Ｗ⁸²が単結合の場合、Ｒ⁸²、Ｒ⁸³、Ｒ⁸⁴およびＲ⁸⁴は、いずれも、水素原子でない。ｎ７は０から８の整数を表す。）。
Ｒ⁸¹は水素原子が好ましい。
一般式（ＶＩＩＩ）で表される化合物の具体例としては、下記式(ＶＩＩＩ−１)〜(ＶＩＩＩ−１４)を挙げることができる。 General formula (VIII)

(In the general formula (VIII), R ⁸¹ represents a hydrogen atom, a methyl group or a hydroxymethyl group. R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ are a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, a hydroxy group, respectively. Represents a methyl group, a hydroxyethyl group, a propyl group and a butyl group, and at least two of R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ may be bonded to each other to form a ring, W ⁸¹ represents a methylene group, —NH _{-, - N (CH 3)} -, - N (C 2 H 5) - .W 82 is a single bond or, -C (= O) - when .W ⁸² representing a single bond, R ^82, R ⁸³ , R ⁸⁴ and R ⁸⁴ are not hydrogen atoms, and n7 represents an integer of 0 to 8.
R ⁸¹ is preferably a hydrogen atom.
Specific examples of the compound represented by the general formula (VIII) include the following formulas (VIII-1) to (VIII-14).

Second polymerizable unsaturated monomer In the present invention, a polymerizable unsaturated monomer other than the polymerizable unsaturated monomer may be included. For example, the polymerizable unsaturated monomer containing the site | part which has an ethylenically unsaturated bond, and a silicone atom and / or a phosphorus atom is mentioned. Such a second polymerizable unsaturated monomer may be a monofunctional polymerizable unsaturated monomer or a polyfunctional polymerizable unsaturated monomer. Such a polymerizable unsaturated monomer is preferably contained in an amount of 0.1% by mass or more in the polymerizable unsaturated monomer.

As the second polymerizable unsaturated monomer, for example, the following (IX-1) to (IX-23) can be employed.

 The composition of the present invention further comprises a polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group (monofunctional polymerizable unsaturated monomer) for the purpose of improving film hardness, flexibility and the like. Body) may be used in combination. 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, aliphatic epoxy (meth) acrylate, benzyl (meth) acrylate , Butanediol mono (meth) acrylate, 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, isomyristyl (meth) acrylate, lauryl (meth) acrylate, methoxydi Propylene 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, nonylphenoxypolypropylene 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 Acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, tert-butyl (meth) acrylate, tribromophenyl (meth) acrylate, EO-modified tribromophenyl (meth) acrylate, Tridodecyl (meth) acrylate, p-isopropenylphenol, styrene, α-methylstyrene, acrylonitrile, vinylcarbazole, isocyanate methyl (meth) acrylate, isocyanate ethyl (meth) acrylate, isocyanate n-propyl (meth) acrylate, isocyanate isopropyl ( (Meth) acrylate, isocyanate n-butyl (meth) acrylate, isocyanate isobutyl (meth) acrylate, isocyanate sec-butyl Isocyanate alkyl (meth) acrylates such as (meth) acrylate and isocyanate tert-butyl (meth) acrylate; (meth) acryloylmethyl isocyanate, (meth) acryloylethyl isocyanate, (meth) acryloyl n-propyl isocyanate, (meth) acryloylisopropyl isocyanate And (meth) acryloyl n-butyl isocyanate, (meth) acryloyl isobutyl isocyanate, (meth) acryloyl sec-butyl isocyanate, (meth) acryloyl tert-butyl isocyanate, and the like.

  As another polymerizable unsaturated monomer used in the present invention, a polyfunctional polymerizable unsaturated monomer having two or more ethylenically unsaturated bond-containing groups is preferably used.

 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, dimethylol dicyclopentane di (meta ) 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, allyloxy polyethylene glycol acrylate, 1,9-nonanediol di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) Acrylate, modified screw Enol 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) Di) (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, tricyclodecane dimethanol (di) 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, divinylethyleneurine Examples thereof include silicon and divinylpropylene urea.

  Among these, 1,9-nonanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate and the like are preferably used in the present invention.

  Examples of the polyfunctional polymerizable unsaturated monomer having 3 or more ethylenically unsaturated bond-containing groups include ECH-modified glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meta) ) Acrylate, pentaerythritol triacrylate, EO modified phosphoric acid triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylol Propane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) Chryrate, dipentaerythritol hydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) Examples include acrylate, pentaerythritol ethoxytetra (meth) acrylate, and pentaerythritol tetra (meth) acrylate.

  Among these, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like are preferably used in the present invention.

  When using a compound having two or more photopolymerizable functions in one molecule, a large amount of photopolymerizable functional groups are introduced into the composition as described above, so that the crosslink density of the composition becomes very large. The effect of improving various physical properties after curing is high. Among the various physical properties after curing, heat resistance and durability (abrasion resistance, chemical resistance, water resistance) are improved by increasing the crosslink density, and even when exposed to high heat, friction or solvent, Deformation, disappearance, and damage are less likely to occur.

  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 higher than that of the polyfunctional polymerizable unsaturated monomer may be blended within a range that achieves the object of the present invention. it can. Polyfunctional oligomers having photo-radical polymerizability include various acrylate oligomers such as polyester acrylate, polyurethane acrylate, polyether acrylate, polyepoxy acrylate, oligomers having a bulky structure such as phosphazene skeleton, adamantane skeleton, cardo skeleton, norbornene skeleton, or Examples thereof include polymers.

 As the polymerizable unsaturated 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 Glycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Glycidyl ethers; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; aliphatic long-chain dibasic acids Diglycidyl esters of aliphatic higher alcohols; monoglycidyl ethers of higher aliphatic alcohols; monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol or alkylene oxide to these; glycidyl esters of higher fatty acids, etc. can do.

  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, 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 ( Product)). 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, 213, 1992, Ed. By Alfred Hasfner, The chemistry of cyclic compounds-Small Ring Heterocycles part 3 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 the polymerizable unsaturated 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, triethylene glycol divinyl ether, 1,2- Propanediol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, Trimethylolethane trivinyl ether, hexanediol divinyl ether, tetraethyleneglycol Rudivinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene vinyl ether, triethylene glycol Methylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether, pentaerythritol triethylene vinyl ether, pentaerythritol tetraethylene vinyl ether, 1,1,1-tris [4- (2 Vinyloxy ethoxy) phenyl] ethane, bisphenol A divinyloxyethyl carboxyethyl ether.

  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.

 As the polymerizable unsaturated monomer used in the present invention, a styrene derivative can also be employed. Examples of the styrene derivative include p-methoxystyrene, p-methoxy-β-methylstyrene, p-hydroxystyrene, and the like.

 Other examples of the styrene derivative 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 vinyl naphthalene 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 with fluorine atoms such as (meth) acrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, etc. Can do.

 As the polymerizable unsaturated 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.

Next, the preferable blend form of the polymerizable unsaturated monomer in the composition of the present invention will be described. The composition of the present invention contains a polymerizable unsaturated monomer containing a site having at least one of oxygen, nitrogen, or sulfur as an essential component, and further contains a polyfunctional polymerizable unsaturated monomer. It is preferable that
A monofunctional polymerizable unsaturated monomer is usually used as a reactive diluent and is effective in reducing the viscosity of the composition of the present invention. % Or more is added. Preferably, it is added in the range of 20 to 80% by mass, more preferably 25 to 70% by mass, and particularly preferably 30 to 60% by mass.
By setting the ratio of the monofunctional polymerizable unsaturated monomer selected from the above (a), (b) and (c) to 80% by mass or less, a cured film machine obtained by curing the composition of the present invention. The strength, etching resistance, and heat resistance tend to be better, and when used as a mold material for optical nanoimprint, it is preferable that the mold can be prevented from swelling and deteriorating. On the other hand, since the above-mentioned monofunctional polymerizable unsaturated monomer is better as a reactive diluent, it is preferable to add 15% by mass or more of the total polymerizable unsaturated monomer.
The monomer having two unsaturated bond-containing groups (bifunctional polymerizable unsaturated monomer) is preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 80% by mass or less of the total polymerizable unsaturated monomer. Preferably, it is added in a range of 70% by mass or less. The ratio of the monofunctional and bifunctional polymerizable unsaturated monomer is preferably 1 to 95% by mass, more preferably 3 to 95% by mass, and particularly preferably 5 to 90% by mass of the total polymerizable unsaturated monomer. It is added in the range of mass%. The ratio of the polyfunctional polymerizable unsaturated monomer having 3 or more unsaturated bond-containing groups is preferably 80% by mass or less, more preferably 70% by mass or less, and particularly preferably the total polymerizable unsaturated monomer. Is added in a range of 60% by mass or less. Since the viscosity of a composition can be lowered | hung by making the ratio of the polymerizable unsaturated monomer which has 3 or more of polymerizable unsaturated bond containing groups into 80 mass% or less, it is preferable.

  In particular, in the composition of the present invention, the polymerizable unsaturated monomer component is 15 to 80% by mass of the monofunctional polymerizable unsaturated monomer, and 0 to 60% by mass of the bifunctional polymerizable unsaturated monomer. It is preferably composed of 1 to 60% by mass of a polyfunctional polymerizable unsaturated monomer that is at least functional, and 20 to 70% by mass of a monofunctional polymerizable unsaturated monomer. More preferably, it is composed of a monomer in an amount of 0 to 50% by mass and a trifunctional or higher polyfunctional polymerizable unsaturated monomer of 2 to 50% by mass.

 In particular, in the composition of the present invention, it is preferable to blend a polymerizable unsaturated monomer containing a site having at least one ethylenically unsaturated bond and a silicone atom and / or a phosphorus atom. The polymerizable unsaturated monomer containing at least one ethylenically unsaturated bond and a silicone atom and / or a phosphorus atom usually improves the releasability from the mold and the adhesion to the substrate. For the purpose, 0.1% by mass in the total polymerizable unsaturated monomer is added. Preferably it is 0.2-10 mass%, More preferably, it is 0.3-7 mass%, Most preferably, it adds in 0.5-5 mass%. As for the number of the site | parts (number of functional groups) which have an ethylenically unsaturated bond, 1-3 are preferable.

  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.

  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 is not necessarily contained. There is no need. 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 that is generally used in a curable composition for optical nanoimprint lithography and a photoresist, and dissolves and uniformly disperses the compound used in the present invention. Any material can be used as long as it 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.

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. A preferred photopolymerization initiator and / or photoacid generator addition amount for the curable composition for photo nanoimprint lithography is not reported. That is, in a system containing dyes and / or pigments, these may act as radical trapping agents, affecting the photopolymerizability and sensitivity. Considering this point, the amount of 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 Phonyl) propan-1-one, N-1414 Adeka optomer (registered trademark) N-1414 (carbazole phenone) available from Asahi Denka Co., Adeka optomer (registered trademark) N-1717 (acridine), 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.

  Furthermore, in addition to the photopolymerization initiator, a photosensitizer can be added to the composition of the present invention to adjust the wavelength in the UV region. Typical sensitizers that can be used in the present invention include those disclosed in Krivello [JVCrivello, Adv. In Polymer Sci, 62, 1 (1984)], specifically, pyrene. Perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like.

  The content ratio of the photosensitizer in the composition of the present invention is preferably 15% by mass or less, more preferably 8% by mass or less, and particularly preferably 5% by mass or less in the composition. Although the minimum of a photosensitizer content rate is not specifically limited, In order to express an effect, the minimum of a photosensitizer content rate is about 0.1 mass%.

  For the purpose of promoting the photocuring reaction, a photoacid generator that initiates photopolymerization by receiving energy rays such as ultraviolet rays may be added to the composition of the present invention.

 Examples of the photoacid generator include thiobililium salts, iron / allene complexes, aluminum complexes / photolytic silicon compound-based initiators described in US Pat. No. 4,139,655, and halides that generate hydrogen halide. , O-nitrobenzyl ester compounds, imide sulfonate compounds, bissulfonyldiazomethane compounds, and oxime sulfonate compounds.

  As a photoacid generator that can be used in the present invention, for example, a chemical amplification type photoresist or a compound used for photocationic polymerization can be widely employed (imaging organic materials, edited by Organic Electronics Materials Research Group, Bunshin Publishing (1993), see pages 187-192). These compounds are the same as the photoacid generators described in THE CHEMICAL SOCIETY OF JAPAN Voi.71 No.11 (1998) and organic materials for imaging (Organic Electronics Materials Research Group, Bunshin Publishing (1993)). Can be easily synthesized by a known method.

  Examples of commercially available photoacid generators include IRGACURE261, IRGACURE OXE01, IRGACURE CGI-1397 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.) and the like. The above photoacid generators can be used singly or in combination of two or more.

 Moreover, the said acid generator can be used in combination as the said photoinitiator. In this case, the photoacid generator is preferably used in the range of 0.05 to 3.0% by mass, and the photopolymerization initiator and the photoacid generator are preferably used in the range of 0.5 to 15.0% by mass. .

  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. Therefore, the mold has to be frequently cleaned, and the curable composition for optical nanoimprint lithography is deformed in the mold, resulting in deterioration of the transfer pattern accuracy. . Those that do not generate gas are preferable from the viewpoints that the mold is not easily contaminated, the frequency of cleaning the mold is reduced, and the curable composition for optical nanoimprint lithography is not easily deformed in the mold, so that the transfer pattern accuracy is not easily deteriorated. .

Surfactant The composition of the present invention contains 0.001 to 5% by mass of at least one of a fluorine-based surfactant, a silicone-based surfactant, and a fluorine / silicone-based surfactant. The surfactant ratio in the composition is preferably 0.002 to 4% by mass, particularly preferably 0.005 to 3% by mass.
If the fluorine-based surfactant, silicone-based surfactant and fluorine-silicone-based surfactant are less than 0.001 in the composition, the effect of coating uniformity is insufficient, while if exceeding 5% by mass, This is not preferable because it deteriorates the mold transfer characteristics. The fluorine-based surfactant, silicone-based surfactant and fluorine-silicone-based surfactant used in the present invention may be used alone or in combination of two or more. In the present invention, it is preferable to include both a fluorine-based surfactant and a silicone-based surfactant, or a fluorine / silicone-based surfactant.
In particular, it is most preferable to contain a fluorine / silicone 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 semiconductor devices, a glass square substrate for manufacturing liquid crystal devices, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, and tantalum. Striations and scale-like patterns that occur during coating on the substrate, such as alloy films, silicon nitride films, amorphous silicone films, various films such as tin oxide-doped indium oxide (ITO) films and tin oxide films ( 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. In particular, in the composition of the present invention, the coating uniformity can be greatly improved by adding the above-mentioned surfactant, and in coating using a spin coater or slit scan coater, good coating suitability can be obtained regardless of the substrate size. can get.

Examples of the nonionic fluorosurfactant used in the present invention include trade names Fluorard 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 name Megafuk 171, 172, 173, 178K, 178A (all manufactured by Dainippon Ink & Chemicals, Inc.). Examples of nonionic silicon-based surfactants include the trade name SI-10 series (manufactured by Takemoto Yushi Co., Ltd.), MegaFac Paintad 31 (manufactured by Dainippon Ink & Chemicals), 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.).

  In addition to the above, other nonionic surfactants may be used in combination with the composition of the present invention for the purpose of improving the flexibility of the curable composition for optical nanoimprint lithography. Examples of commercially available nonionic surfactants include polyion such as D-3110, D-3120, D-3412, D-3440, D-3510, D-3605 of Pionein series manufactured by Takemoto Yushi Co., Ltd. Oxyethylene alkylamine, polyoxyethylene alkyl such as D-1305, D-1315, D-1405, D-1420, D-1504, D-1508, D-1518 of Pionein series manufactured by Takemoto Yushi Co., Ltd. Ether, polyoxyethylene monofatty acid esters such as D-2112-A, D-2112-C, and D-2123-C of the Pionein series manufactured by Takemoto Yushi Co., Ltd., Pionein manufactured by Takemoto Yushi Co., Ltd. Series D-2405-A, D-2410-D, D-2110-D and other polyoxyethylene difatty acid esters, Takemoto Yushi Pioxynin series D-406, D-410, D-414, D-418 and other polyoxyethylene alkylphenyl ethers manufactured by Nissin Chemical Industry Co., Ltd. Surfinol series 104S, 420, 440 And polyoxyethylenetetramethyldecynediol diether such as 465,485. Moreover, the reactive surfactant which has a polymerizable unsaturated group can also be used together with the surfactant used by this invention. For example, allyloxy polyethylene glycol monomethacrylate (Nippon Yushi Co., Ltd. trade name: Blenmer PKE series), nonylphenoxy polyethylene glycol monomethacrylate (Nippon Yushi Co., Ltd. trade name: Blenmer PNE series), nonylphenoxy polypropylene glycol monometa. Acrylate (Nippon Yushi Co., Ltd. trade name: Blenmer PNP series), Nonylphenoxy poly (ethylene glycol-propylene glycol) monomethacrylate (Nippon Yushi Co., Ltd. trade name: Blenmer PNEP-600), Aqualon RN-10, RN- 20, RN-30, RN-50, RN-2025, HS-05, HS-10, HS-20 (Daiichi Kogyo Seiyaku Co., Ltd.). The addition amount of the other nonionic surfactant is preferably 0.001 to 5% by mass, and more preferably 0.005 to 3% by mass.

Inorganic oxide fine particles The composition of the present invention contains inorganic oxide fine particles.
The inorganic oxide fine particles useful in the composition of the present invention improve the heat resistance, tackiness, hardness, etc. of the photocurable resin composition, and improve the mechanical strength such as scratch resistance, abrasion resistance, mechanical properties, etc. The type, particle size, and form are not particularly limited as long as the resulting composition becomes transparent. In addition, the addition of inorganic oxide fine particles is also effective for improving deterioration of substrate adhesion accompanying curing shrinkage. Examples of inorganic oxide fine particles include silica (particularly colloidal silica), alumina, titanium oxide, tin oxide, foreign element-doped tin oxide (ATO, etc.), indium oxide, foreign element-doped indium oxide (ITO, etc.), cadmium oxide. , Antimony oxide, zinc oxide, cerium oxide, zirconium oxide and the like. These may be used alone or in combination of two or more. Such inorganic oxide fine particles can be used in either powder form or solvent-dispersed sol. In the case of a solvent dispersion sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. Esters such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone . Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred. When the solvent-dispersed sol is blended with the composition of the present invention, the solvent is also blended at the same time. At that time, the blending is performed so that the content of the organic solvent is 3% by mass or less in the total composition. It is preferable. As described above, 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 in 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 particularly preferably not contained. Therefore, it is particularly preferable to add particles dispersed in powder or the reactive monomer (diluent) of the present invention rather than adding a solvent-dispersed sol. Various surfactants, dispersants and amines may be added to improve the dispersibility of the particles.

 The shape of the inorganic oxide fine particles used in the present invention is not particularly defined, but may be spherical, hollow, porous, rod-like, plate-like, fibrous, or indefinite, preferably spherical.

 The particle size of the inorganic oxide fine particles is usually preferably 200 nm or less from the viewpoint of the transparency of the resulting photocurable resin composition layer. More preferably, it is 100 nm or less, More preferably, it is 50 nm or less. Moreover, the addition amount of inorganic oxide microparticles | fine-particles contains in the range of 0.1-50 mass% with respect to the composition of this invention. Preferably, it is contained in the range of 1 to 40% by mass, more preferably 5 to 30% by mass. When the addition amount of the inorganic oxide fine particles is less than 0.1% by mass, the effect of improving the mechanical strength such as scratch resistance, abrasion resistance and mechanical properties may not be recognized, and the addition amount is 50. When it exceeds mass%, the liquid viscosity of a photocurable resin composition may become high, and storage stability and transparency may fall.

 As a commercial item of the inorganic oxide fine particles used in the present invention, for example, as an aqueous dispersion of alumina, manufactured by Nissan Chemical Industries, Ltd., trade names: Alumina sol-100, -200, -520; aqueous dispersion of titanium oxide As a product, manufactured by Ishihara Sangyo Co., Ltd., trade name: TTO-W5; As an aqueous dispersion of zinc antimonate powder, manufactured by Nissan Chemical Industries, Ltd., trade name: Celnax; alumina, titanium oxide, tin oxide , Indium oxide, zinc oxide and other powders and solvent dispersions are manufactured by CI Kasei Co., Ltd., trade name: Nanotech; titanium oxide, tin oxide composite oxide water dispersions are manufactured by Nissan Chemical Industries, Ltd. Product name: HIT-15W1; Water dispersion sol of antimony-doped tin oxide manufactured by Ishihara Sangyo Co., Ltd. Product name: SN-100D; ITO powder manufactured by Mitsubishi Materials Corporation; oxidation As a water dispersion of lithium, manufactured by Taki Chemical Co., Ltd., trade name: Nidral, and as a water dispersion of tin oxide, manufactured by Ishihara Sangyo Co., Ltd., trade names: SN-38F, SN-88F; Examples of the water-dispersed product include Sumitomo Osaka Cement Co., Ltd., trade name: FFT-150W, Nissan Chemical Industries, trade name: HZ-307W6;

 Among the inorganic oxide fine particles used in the present invention, from the viewpoint of easy availability, price, transparency of the resulting photocurable resin composition layer and expression of mechanical properties (omitted), for example, Nalcoag 1034A as colloidal silica. (Trade name of US Nalco Chemical Company), manufactured by Nissan Chemical Industries, Ltd. Trade name: methanol silica sol, IPA-ST, MEK-ST, MIBK-ST, NBA-ST, XBA-ST, DMAC-ST, EAC- ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, manufactured by Fuso Chemical Industry Co., Ltd., trade name: PL -1-MA, PL-1-TOL, PL-1-IPA, PL-1-MEK, PL-1-PGME, PL-2L-MA, PL-2L-IPA, etc. Can be mentioned. As powdered silica, manufactured by Nippon Aerosil Co., Ltd., trade names: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, manufactured by Asahi Glass Co., Ltd., trade names: Sildex H31, H32, H51, H52 , H121, H122, manufactured by Nippon Silica Industry Co., Ltd., trade names: E220A, E220, manufactured by Fuji Silysia Co., Ltd., trade name: SYLYSIA470, manufactured by Nippon Sheet Glass Co., Ltd., trade name: SG Flakes, etc. Can do. If the colloidal silica dispersed in commercially available water or organic solvent is used as it is in the composition of the present invention, water or organic solvent is also blended as it is, so when using a commercially available colloidal silica dispersion as it is, as a silica component A blending amount of 5% by mass or less is preferable.

As the silica used in the present invention, it is preferable to use colloidal silica whose surface is treated with a compound having a functional group. The functional group to be introduced by the treatment or modification of the surface of the silica preferably has a radical polymerizable functional group or a diphotosensitive group (for example, an azonium base, an azido group, a cinnamoyl group, or a cinnamylidene group). The introduction of a functional group is particularly preferred.
For example, the surface-treated colloidal silica fine particles used in the present invention can be obtained by subjecting a monomer or hydrolyzate of a radical polymerizable silane compound to a hydrolytic condensation reaction in the presence thereof. By surface-treating silica in this way, compatibility with other components can be improved, and the storage stability of the composition can be dramatically improved. Furthermore, since the mechanical strength such as scratch resistance, abrasion resistance, and mechanical properties of the obtained composition is improved, it is preferable.

 The radical polymerizable silane compound used for the surface treatment of the silane is a silane compound having at least one radical polymerizable group in the molecule, and a compound having a photopolymerizable functional group by irradiation with active energy rays such as ultraviolet rays. A bond is formed between the silica particles and contributes to the development of the surface hardness and abrasion resistance after curing of the composition of the present invention, and the surface of the silica particles is hydrophobized to contribute to the development of adhesion.

 Examples of the radical polymerizable group in the silane compound include radical polymerizable groups such as a (meth) acryl group, an allyl group, a vinyl group, and a styryl group. From the viewpoint of photocuring reactivity, a (meth) acryl group is particularly preferable. Is preferred.

 The silane compound having a (meth) acryl group is represented by the following formula (1), for example.

CH ₂ = C (R ² ) COO (CH ₂ ) _p SiR ³ _n (OR ¹ ) _3-n (1)
(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms in total, R ² represents a hydrogen atom or a methyl group, R ³ represents an ether bond, an ester bond, an epoxy bond, a mercapto bond, or This represents a hydrocarbon residue having 1 to 10 carbon atoms in total which may have an amino bond, n is an integer of 0 to 2, and p is an integer of 1 to 6.)
When a plurality of R ¹ and / or R ³ are included in the formula, these R ¹ and / or R ³ may be the same or different from each other.
R ¹ is preferably a methyl group or an ethyl group. R ³ is preferably a methyl group.
Specifically, β- (meth) acryloyloxyethylmethyldimethoxysilane, β- (meth) acryloyloxyethylmethyldiethoxysilane, β- (meth) acryloyloxyethyldimethylmethoxysilane, β- (meth) acryloyloxyethyl Dimethylethoxysilane, β- (meth) acryloyloxyethyltrimethoxysilane, β- (meth) acryloyloxyethyltriethoxysilane, γ- (meth) acryloyloxypropyldimethylmethoxysilane, γ- (meth) acryloyloxypropyldimethylethoxy Silane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- Meth) acryloyloxy propyl triethoxysilane, and the like.

The silane compound having an allyl group is represented by the following structural formula (2), for example.
CH ₂ = CHCH ₂ R ² SiR ³ _n (OR ¹ ) _3-n (2)
(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms in total, and R ² and R ³ each have an ether bond, an ester bond, an epoxy bond, a mercapto bond, or an amino bond. Represents a hydrocarbon residue having 1 to 10 carbon atoms in total, and n is an integer of 0 to 2.)
When a plurality of R ¹ and / or R ³ are included in the formula, these R ¹ and / or R ³ may be the same or different from each other.
Specific examples include allyltrimethoxysilane, allyltriethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, γ-allylaminopropyltrimethoxysilane, γ-allylaminopropyltriethoxysilane, and the like.

 The silane compound having a vinyl group is represented by, for example, the following formula (3).

CH ₂ = CHSiR ² _n (OR ¹ ) _3-n (3)
(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms in total, and R ² represents a total carbon which may have an ether bond, an ester bond, an epoxy bond, a mercapto bond, or an amino bond. Represents a hydrocarbon residue of formula 1 to 10, and n is an integer of 0 to 2.)
When a plurality of R ¹ and / or R ² are included in the formula, these R ¹ and / or R ² may be the same or different from each other.
Specific examples include vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

 The silane compound having a styryl group is represented by, for example, the following formula (4).

(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms in total, R ² represents a hydrogen atom or a methyl group, R ³ represents an ether bond, an ester bond, an epoxy bond, a mercapto bond, or A hydrocarbon residue having 1 to 10 carbon atoms which may have an amino bond, and n is an integer of 0 to 2)
When a plurality of R ¹ and / or R ³ are included in the formula, these R ¹ and / or R ³ may be the same or different from each other.
Specifically, for example, p-vinylphenylmethyldimethoxysilane, p-vinylphenylmethyldiethoxysilane, p-vinylphenyltrimethoxysilane, p-vinylphenyltriethoxysilane, o-vinylphenyltrimethoxysilane, m- Examples thereof include vinylphenyltrimethoxysilane.

 In addition to the above silane compounds, epoxysilane was allowed to act on the reaction product of a hydroxyl group-containing polyfunctional (meth) acrylate and an acid anhydride as described in JP-A-5-247373. ) Acrylic group-containing silane compound, (meth) acrylic group-containing silane in which polyfunctional (meth) acrylate is Michael-added to aminosilane as described in JP-A-3-93372, JP-A-3-207765, etc. Compounds, (meth) acrylic group-containing silane compounds obtained by reacting a hydroxyl group-containing (meth) acrylate and an isocyanate silane as described in JP-A-5-287215 and JP-A-6-1000079, etc. Mercaptosilane, diisocyanate compound, hydroxyl group as described in JP-A-287308 A (meth) acrylic group-containing silane compound reacted with a (meth) acrylate, a mercaptosilane and a polyfunctional (meth) acrylate compound as described in JP-A No. 11-157014 and the like are added by Michael (meta) ) Acrylic group-containing silane compounds and the like can also be used as the radical polymerizable silane compound of the present invention.

 These silane compounds may be used alone or in combination of two or more.

 Further, the surface-treated silica used in the present invention may be treated with a non-radically polymerizable silane compound (a silane compound having no radical polymerizable group in the molecule). Although non-radically polymerizable silane compounds are involved in the surface modification of silica, they do not cause a bond between the compound having a photopolymerizable functional group and silica, so that they are flexible in the photocurable resin composition after curing. It is performed for the purpose of imparting the properties and contributing to the expression of weather resistance and adhesion to the substrate. Moreover, since it does not involve a binding reaction, it contributes to the expression of long-term storage stability of the photocurable resin composition.

 The non-radically polymerizable silane compound is represented, for example, by the following formula (5).

SiR ² _a R ³ _b (OR ¹ ) _c (5)
(In the above formula, R ¹ represents a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms in total, and R ² and R ³ each have an ether bond, an ester bond, an epoxy bond, a mercapto bond, or an amino bond. Represents a hydrocarbon residue having 1 to 10 carbon atoms in total, a and b are each an integer of 0 to 3, and c is an integer of 1 to 4 that satisfies 4-ab. is there.)
When c is 2 or more, each R ¹ may be the same or different.
Specifically, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltrimethoxysilane, Ethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, methylethyldiethoxysilane, methylphenyldimethoxysilane, trimethylethoxysilane, methoxyethyltriethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane N-nonyltrimethoxysilane, n-decyltrimethoxysilane, n-undecyltrimethoxysilane, tridecyltrimethoxysilane, Ladecyltrimethoxysilane, pentadecyltrimethoxysilane, hexadecyltrimethoxysilane, heptadecyltrimethoxysilane, octadecyltrimethoxysilane, nonadecyltrimethoxysilane, eicodecyltrimethoxysilane, acetoxyethyltriethoxysilane, diethoxyethyl Dimethoxysilane, tetraacetoxysilane, methyltriacetoxysilane, tetrakis (2-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxy Silane, .gamma.-aminopropyltrimethoxysilane, .gamma. isocyanate propyl trimethoxysilane and the like. These silane compounds may be used alone or in combination of two or more.

The radical polymerizable silane compound and the non-radically polymerizable silane compound have a silica solid content of 1 mol part (the amount of particles having the number of grams equal to the formula weight of the particles is 1 mol. Therefore, colloidal silica (SiO ₂ = 28 + 16 × 2 = 60) is preferably used in a proportion of 0.0001 to 3 mole parts per 60 moles of solid content). More preferably, it is used in the composition of the present invention at a ratio of 0.01 to 2 mol. When the total amount of the silane compound is 3 mol parts or less, the mechanical strength of the composition of the present invention tends to be improved, and when it is 0.0001 mol parts or more, the effect of the silane treatment is improved. It tends to be played more easily.

 Moreover, you may use together with a radically polymerizable silane compound and a non-radically polymerizable silane compound, It is preferable that the use molar ratio exists in the range of 1: 99-99: 1, 2: 98-98: 2. A range is more preferable, a range of 5:95 to 95: 5 is further preferable, and a range of 10:90 to 80:20 is most preferable.

 Next, an example of the hydrolytic condensation reaction of the radical polymerizable silane compound silica will be described. First, a dispersion solution in which silica is dispersed in an appropriate dispersion medium such as alcohol and a silane compound are mixed. Subsequently, a hydrolysis catalyst such as 0.5 to 6 mol of water or 0.00001 to 0.1 N aqueous hydrochloric acid is added to 1 mol of the silane compound, and it is generated by hydrolysis while stirring under heating. Remove alcohol out of the system. Further, the water generated in the condensation reaction following the hydrolysis reaction is similarly removed outside the system under heating, and the condensation reaction is completed.

 Silica can be added not only before the hydrolysis / condensation reaction of the silane compound but also during or after the hydrolysis / condensation reaction. This reaction can be carried out under normal pressure or under reduced pressure / pressure. Furthermore, when stirring under heating during the hydrolysis / condensation reaction, the dispersion medium of silica can be replaced with another dispersion medium by azeotropic distillation.

 In the above reaction, an aqueous solution of an inorganic acid or an organic acid can be used as a hydrolysis catalyst. As the inorganic acid, for example, hydrohalic acid such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and the like are used. Examples of the organic acid include formic acid, acetic acid, oxalic acid, (meth) acrylic acid, and the like.

 Further, it is preferable to use a solvent in order to perform the hydrolysis / condensation reaction gently and uniformly. As this solvent, a silica dispersion medium may be used as it is, or a necessary amount of a new solvent may be added. As a newly added solvent, water; alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); ethers such as dioxane and tetrahydrofuran (THF) be able to.

Antioxidant Furthermore, the composition of the present invention may contain a known antioxidant. 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). In particular, in the present invention, the addition of an antioxidant has an advantage that the cured film can be prevented from being colored or the decrease in film thickness due to decomposition can be reduced. 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, saccharides, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like. Among these, hindered phenol antioxidants and thioether antioxidants are particularly preferable from the viewpoint of coloring of the cured film and reduction of the film thickness.

  As commercially available products of antioxidants, Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Geigy Co., Ltd.), Antigene P, 3C, FR, Sumilyzer S, Sumilyzer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), ADK STAB AO70, AO80, AO503 (made by ADEKA Co., Ltd.), etc. are mentioned, These may be used independently and may be mixed and used. It is preferable to mix | blend antioxidant in the ratio of 0.01-10 mass% with respect to the whole quantity of the composition of this invention, and it is further more preferable to mix | blend in the ratio of 0.2-5 mass%.

Other components In addition to the above components, the composition of the present invention may include a mold release agent, a silane coupling agent, a polymerization inhibitor, an ultraviolet absorber, a light stabilizer, an antiaging agent, a plasticizer, and an adhesion promoter. , Thermal polymerization initiators, colorants, 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. Silicone mold release agent is a mold release agent having an organopolysiloxane structure as a basic structure, and includes, for example, unmodified or modified silicone oil, polysiloxane containing trimethylsiloxysilicic acid, 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 to the surface and has excellent peelability, 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 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 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 deposited 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 or less, the problem of surface roughness of the coating film due to repelling at the time of coating the composition hardly occurs, and the substrate itself and the adjacent layer in the product, for example, It is preferable in that it hardly inhibits the adhesion of the vapor-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.

  The composition of the present invention may contain a polymerization inhibitor in order to improve storage stability and the like. Examples of the polymerization inhibitor include phenols such as hydroquinone, tert-butylhydroquinone, catechol, and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines; coppers and the like. The polymerization inhibitor is preferably blended arbitrarily in a proportion of 0.001 to 10% by mass with respect to the total amount of the composition of the present invention.

  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).

You may add an antistatic agent to the composition of this invention as needed.
The antistatic agent may be any of anionic, cationic, nonionic, and amphoteric. Specifically, Electro Stripper A (manufactured by Kao Corporation), Elenon No. 19 (Daiichi Kogyo Seiyaku Co., Ltd.) and other alkyl phosphate anionic surfactants, Amorgen K (Daiichi Kogyo Seiyaku Co., Ltd.) betaine amphoteric surfactants, Nissan Nonion L (Nippon Yushi) Polyoxyethylene fatty acid ester-based nonionic surfactants such as Emulgen 106, 120, 147, 420, 220, 905, 910 (manufactured by Kao Corporation) and Nissan Nonion E Polyoxyethylene alkyl ether nonionic surfactants (manufactured by NOF Corporation), polyoxyethylene alkylphenol ethers, polyhydric alcohol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines And other nonionic surfactants. These may be used individually by 1 type and may use 2 or more types together.

  Next, the formation method of the pattern (especially fine concavo-convex pattern) using the composition of this invention is demonstrated. In the present invention, the composition of the present invention can be applied and cured to form a pattern. Specifically, a pattern forming layer comprising at least the composition of the present invention is applied on a substrate or a support, and dried as necessary to form a layer (pattern forming layer) comprising the composition of the present invention. Then, a pattern receptor is prepared, a mold is pressed against the pattern forming layer surface of the pattern receptor, a process of transferring the mold pattern is performed, and the fine uneven pattern forming layer is exposed and cured. The optical imprint lithography according to the pattern forming method of the present invention can be laminated and multiple patterned, and can be used in combination with ordinary thermal imprint.

  As an application of the composition of the present invention, the composition of the present invention is applied on a substrate or a support, and a layer comprising the composition is exposed, cured, and dried (baked) as necessary. Permanent films such as overcoat layers and insulating films can also be produced.

  Hereinafter, a pattern forming method and a pattern transfer method using the composition of the present invention will be described.

  The composition of the present invention is a generally well-known coating method 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 coating 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 production substrates such as silicone, silicon 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).

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 optical imprint lithography applied to the present invention, a curable composition for optical nanoimprint lithography is applied onto a substrate, a light-transmitting mold is pressed, light is irradiated from the back of the mold, and curing for optical nanoimprint lithography is performed. The adhesive composition is cured. Alternatively, the curable composition for optical nanoimprint lithography 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 curable composition for optical nanoimprint lithography.
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 peelability between the curable composition for optical nanoimprint lithography and the mold. Those having been treated with a silane coupling agent such as a silicone type or a fluorine type, for example, commercially available mold release agents such as those manufactured by Daikin Industries, Optool DSX, Sumitomo 3M, Novec EGC-1720 and the like can also be suitably used.

  When performing photoimprint lithography using the present invention, it is usually preferred that the mold pressure be 10 atmospheres or less. By setting the mold pressure to 10 atm or less, 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, which is preferable. The pressure of the mold is preferably selected in a region where the mold transfer uniformity can be ensured within a range in which the remaining film of the curable composition for photo-nanoimprint lithography 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 optical nanoimprint lithography 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 to increase the reactivity. As a pre-stage of light irradiation, if it is in a vacuum state, it is effective in preventing bubble contamination, suppressing the decrease in reactivity due to oxygen contamination, and improving the adhesion between the mold and the curable composition for optical nanoimprint lithography. Light irradiation may be performed. In the present invention, the preferable degree of vacuum is 10 ⁻¹ Pa to normal pressure.

  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. Mixing and dissolution of the curable composition for optical nanoimprint lithography 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 the filtration may be polyethylene resin, polypropylene resin, fluorine resin, nylon resin, etc., but are not particularly limited.

The case where the composition of the present invention is applied to an etching resist will be described. The etching step can be performed by a method appropriately selected from known etching methods, and is performed to remove the underlying portion not covered with the resist pattern, thereby obtaining a thin film pattern. Either a treatment with an etching solution (wet etching) or a treatment in which a reactive gas is activated by plasma discharge under reduced pressure (dry etching) is performed.
The etching process may be a batch system in which an appropriate number of sheets are processed together, or a single wafer process in which each sheet is processed.

As etching solutions for performing the wet etching, many etching solutions have been developed and used, typically ferric chloride / hydrochloric acid, hydrochloric acid / nitric acid, hydrobromic acid, and the like. For Cr, mixed solution of cerium ammonium nitrate or cerium nitrate / hydrogen peroxide solution, for Ti, diluted hydrofluoric acid, hydrofluoric acid / nitric acid solution, for Ta, mixed solution of ammonium solution and hydrogen peroxide solution For Mo, hydrogen peroxide solution, a mixture of ammonia water and hydrogen peroxide solution, a mixture solution of phosphoric acid and nitric acid, and MoW and Al, a mixture solution of phosphoric acid and nitric acid, a mixture solution of hydrofluoric acid and nitric acid, phosphoric acid Nitric acid / acetic acid mixed solution For ITO, diluted aqua regia, ferric chloride solution, hydrogen iodide water, SiNx and SiO ₂ are buffered hydrofluoric acid, hydrofluoric acid / ammonium fluoride mixed solution, Si, poly Si Is a mixture of hydrofluoric acid, nitric acid and acetic acid, W is a mixture of ammonia water and hydrogen peroxide, PSG is a mixture of nitric acid and hydrofluoric acid, and BSG is a mixture of hydrofluoric acid and ammonium fluoride. used.
Wet etching may be either a shower method or a dip method, but the etching rate, in-plane uniformity, and wiring width accuracy largely depend on the processing temperature, so conditions are optimal according to the substrate type, application, and line width. It is necessary to make it. Further, when performing the wet etching, it is desirable to perform post-baking in order to prevent undercut due to the penetration of the etching solution. Usually, these post-baking is performed at about 90 ° C. to 140 ° C., but is not necessarily limited thereto.

The dry etching basically uses a parallel plate type dry etching apparatus having a pair of electrodes arranged in parallel in a vacuum apparatus and setting a substrate on one of the electrodes. Reactive ion etching (RIE) mode in which ions are mainly involved and radicals are mainly involved depending on whether the high-frequency power source for generating plasma is connected to the electrode on the side where the substrate is installed or to the opposite electrode The plasma etching (PE) mode is classified.
As an etchant gas used in the dry etching, an etchant gas suitable for each film type is used. Carbon tetrafluoride (chlorine) + oxygen, carbon tetrafluoride (sulfur hexafluoride) + hydrogen chloride (chlorine) for a-Si / n ⁺ and s-Si, carbon tetrafluoride for a-SiNx + oxygen, carbon tetrafluoride for a-SiO _x + oxygen trifluoride carbon + oxygen, is for Ta carbon tetrafluoride (sulfur hexafluoride) + oxygen tetrafluoride is for MoTa / MoW Carbon + oxygen, chlorine + oxygen for Cr, boron trichloride + chlorine, hydrogen bromide, hydrogen bromide + chlorine, hydrogen iodide and the like for Al. In the dry etching process, the resist structure may be greatly altered by ion bombardment or heat, which also affects the peelability.

  A method for removing the resist used for pattern transfer to the lower substrate after etching will be described. Peeling can be removed with a liquid (wet peeling), or oxidized by plasma discharge of oxygen gas under reduced pressure and removed in a gaseous state (dry peeling / ashing), or oxidized with ozone and UV light. The resist can be removed by several stripping methods such as removing it in a gaseous state (dry stripping / UV ashing). As the stripping solution, an aqueous solution system such as an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and ozone-dissolved water and an organic solvent system such as a mixture of an amine and dimethyl sulfoxide or N-methylpyrrolidone are generally known. As an example of the latter, a monoethanolamine / dimethyl sulfoxide mixture (mass mixing ratio = 7/3) is well known.

 The resist stripping speed is greatly influenced by temperature, liquid amount, time, pressure, etc., and can be optimized depending on the substrate type and application. In the present invention, it is preferable to immerse the substrate (from several minutes to several tens of minutes) in the temperature range of room temperature to 100 ° C., and rinse with water such as butyl acetate and then rinse with water. From the viewpoint of improving the rinsing properties, particle removability, and corrosion resistance of the stripping solution itself, only water rinsing may be used. A preferable example is a pure water shower for washing and an air knife drying for drying. When the amorphous silicone is exposed on the substrate, an oxide film is formed in the presence of water and air. Therefore, it is preferable to block air. Moreover, you may apply the method of using together ashing (ashing) and peeling by a chemical | medical solution. Examples of ashing include plasma ashing, downflow ashing, ashing using ozone, and UV / ozone ashing. For example, when an Al substrate is processed by dry etching, a chlorine-based gas is generally used, but aluminum chloride, which is a product of chlorine and Al, may corrode Al. In order to prevent these, a stripping solution containing a preservative may be used.

  There is no restriction | limiting in particular as other processes other than the said etching process, peeling process, rinse process, and water washing, It can mention selecting from the process in well-known pattern formation suitably. For example, a hardening process process etc. are mentioned. These may be used alone or in combination of two or more. There is no restriction | limiting in particular as a hardening process, Although it can select suitably according to the objective, For example, a whole surface heat processing, a whole surface exposure process, etc. are mentioned suitably.

 Examples of the method for the entire surface heat treatment include a method for heating the formed pattern. By heating the entire surface, the film strength on the surface of the pattern is increased. As heating temperature in whole surface heating, 80-200 degreeC is preferable and 90-180 degreeC is more preferable. When the heating temperature is 80 ° C. or higher, the film strength due to the heat treatment tends to be further improved. By setting the heating temperature to 200 ° C. or lower, the components in the curable composition for optical nanoimprint lithography are decomposed, resulting in film quality. The tendency to weaken and become brittle can be suppressed more effectively. There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned. Moreover, when using a hot plate, in order to heat uniformly, it is desirable to carry out by lifting the substrate on which the pattern is formed from the plate.

 Examples of the entire surface exposure processing method include a method of exposing the entire surface of the formed pattern. The entire surface exposure accelerates the curing in the composition forming the photosensitive layer and the surface of the pattern is cured, so that the etching resistance can be increased. There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

  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.

Polymerizable unsaturated monomer <monofunctional monomer>
R-1: Compound (I-2) gamma-butyrolactone acrylate (GBLA: manufactured by ENF)
R-2: Compound (I-3) α-acryloyloxy-β, β-dimethyl-γ-butyrolactone (reagent manufactured by Aldrich)
R-3: Compound (I-4) mevalonic lactone (meth) acrylate (synthetic product: synthesized according to Japanese Patent Application Laid-Open No. 2004-2243)
R-4: Compound (II-3) 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane (Biscoat MEDOL10: manufactured by Osaka Organic Industry Co., Ltd.)
R-5: Compound (II-5) 4-acryloyloxymethyl-2cyclohexyl-1,3-dioxolane (Biscoat HDOL10, manufactured by Osaka Organic Chemical Industry)
R-6: Compound (II-7) (3-Methyl-3-oxetanyl) methyl acrylate (Biscoat OXE10, manufactured by Osaka Organic Chemical Industry)
R-7: Compound (III-2) N-vinylsuccinimide (synthetic product) synthesized according to DokladyAkademii Nauk Respubliki Uzbekistan (1), 39-49 (1993) R-8: Compound (III-6) N-piperidinoethyl acrylate ( Synthetic product) According to Journal fuer Praktische Chemie (Leipzig), 7, 308-10. (1959) Synthesis R-9: Compound (III-7) 2-Propenoic acid 2-methyl-oxiranylmethyl ester (synthetic product) Gaofenzi Synthesis R-10 according to Xuebao (1), 109-14, (1993): Compound (III-8) N-morpholinoethyl acrylate (synthetic product) Synthesis R according to American Chemical Society, 71, 3164-5, (1949) -11: Compound (IV-1) N-vinyl-2-pyrrolidone (Aronix M-150: manufactured by Toa Gosei Co., Ltd.)
R-12: Compound (IV-2) N-vinylcaprolactone (reagent manufactured by Aldrich)
R-13: Compound (IV-3) N-vinylsuccinimide (synthetic product) Synthesis according to Kunststoffe Plastics, 4, 257-64, (1957) R-14: Compound (IV-5) 1-vinylimidazole (manufactured by Aldrich) reagent)
R-15: Compound (IV-8) N-acryloylmorpholine (ACMO: manufactured by Kojin Co., Ltd.)
R-16: Compound (V-1) 4-vinyl-1-cyclohexene 1,2-epoxide (Celoxide 2000 manufactured by Daicel Chemical Industries)
R-17: Compound (V-2) 2-vinyl-2-oxazoline (VOZO: manufactured by Kojin Co., Ltd.)
R-18: Compound (V-6) 4-vinyl 1,3-dioxolan-2-one (reagent manufactured by Aldrich)
R-19: Compound (VI-1) Isobornyl acrylate (Aronix M-156: manufactured by Toa Gosei Co., Ltd.)
R-20: Compound (VI-10) 2-methacryloyloxyethyl isocyanate (Cainz MOI: manufactured by Showa Denko KK)
R-21: Compound (VII-2) N-hydroxyethylacrylamide (HEAA: manufactured by Kojin Co., Ltd.)
R-22: Compound (VII-1) N-vinylformamide (Beam Set 770: manufactured by Arakawa Chemical Industries)
R-23: Compound (IX-2) Acrylic acid 3- (trimethoxysilyl) propyl ester (Reagent manufactured by Tokyo Chemical Industry)
R-24: Compound (IX-20) 2-methacryloxyethyl acid phosphate (Light Ester P-1M: manufactured by Kyoeisha Chemical Co., Ltd.)
R-25: Ethoxydiethylene glycol acrylate (Light acrylate EC-A: manufactured by Kyoeisha Chemical Co., Ltd.)
R-26: benzyl acrylate (Biscoat # 160: manufactured by Osaka Organic Chemical Co., Ltd.)
R-27: Phenoxyethyl acrylate (Light acrylate PO-A: manufactured by Kyoeisha Yushi Co., Ltd.)
R-28: Epoxy acrylate (Evekril 3701: manufactured by Daicel UCB)
R-29: α-methylstyrene (reagent obtained from Tokyo Chemical Industry Co., Ltd.)
R-30: Compound (IX-20) 2-Methacryloxyethyl acid phosphate (Light Ester P-1M: manufactured by Kyoeisha Chemical Co., Ltd.)

<Bifunctional monomer>
S-01: Compound (IX-23) ethylene oxide-modified phosphate dimethacrylate (Kayamer PM-21: manufactured by Nippon Kayaku Co., Ltd.)
S-02: Hydroxypivalic acid neopentyl glycol diacrylate (Kalayad MANDA: manufactured by Nippon Kayaku Co., Ltd.)
S-03: Polyethylene glycol diacrylate (New Frontier PE-300: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
S-04: Tripropylene glycol diacrylate (Karayad TPGDA: manufactured by Nippon Kayaku Co., Ltd.)
S-05: Ethylene oxide modified neopentyl glycol diacrylate (Photomer 4160: manufactured by San Nopco)
S-06: 1,6-hexanediol diacrylate (Frontier HDDA: manufactured by Daiichi Kogyo Seiyaku)
S-07: Ethylene oxide modified bisphenol A diacrylate (SR-602: manufactured by Kayaku Sartomer)
S-08: Ethylene oxide modified bisphenol A diacrylate (Aronix M-211B: manufactured by Toagosei Co., Ltd.)
S-09: Tricyclodecane dimethanol acrylate (Karayad R684: manufactured by Nippon Kayaku Co., Ltd.)
S-10: Ethylene glycol dimethacrylate (light ester EG: manufactured by Kyoeisha Chemical Co., Ltd.)

<Trifunctional or higher monomer and oligomer>
S-11: Ethylene oxide modified trimethylolpropane triacrylate (SR-454: manufactured by Kayaku Sartomer)
S-12: Propylene oxide-modified trimethylolpropane triacrylate (New Frontier TMP-3P: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
S-13: Pentaerythritol ethoxytetraacrylate (Ebercryl 40: manufactured by Daicel UCB)
S-14: Dipentaerythritol hexaacrylate (Karayad DPHA: manufactured by Nippon Kayaku Co., Ltd.)
S-15: Trimethylolpropane triacrylate (Aronix M-309: manufactured by Toa Gosei Co., Ltd.)
S-16: Aqualon RN-20: Daiichi Kogyo Seiyaku Co., Ltd.

The abbreviations of the photopolymerization initiator and photoacid generator used in Examples and Comparative Examples of the present invention are as follows.
<Photopolymerization initiator>
P-1: 2,4,6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (Lucirin TPO-L: manufactured by BASF)
P-2: 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651: Ciba Specialty Chemicals)
P-3: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173: manufactured by Ciba Specialty Chemicals)
P-4: Mixture of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 4265: manufactured by Ciba Specialty Chemicals)
P-5: Mixture of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2,2-dimethoxy-1,2-diphenylethan-1-one (Irgacure 1300: Ciba Specialty)・ Made by Chemicals
P-6: 1- [4-Benzoylphenylsulfanyl] phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one (ESACUR1001M: manufactured by Nippon Siebel Hegner)
P-7: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- "(Irgacure-907: manufactured by Ciba Specialty Chemicals)
P-8: Hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals: Irgacure-184)

Abbreviations for the surfactants and additives used in the examples and comparative examples of the present invention are as follows.
<Surfactant>
W-1: Fluorosurfactant (manufactured by Tochem Products: Fluorosurfactant)
W-2: Silicone-based surfactant (Dainippon Ink & Chemicals, Inc .: Megafuck Paintad 31)
W-3: Fluorine / silicone surfactant (manufactured by Dainippon Ink & Chemicals, Inc .: Megafuk R-08)
W-4: Fluorine / silicone surfactant (Dainippon Ink Chemical Industries, Ltd .: Megafuak XRB-4)
W-5: Fluorosurfactant (Dainippon Ink Chemical Co., Ltd .: F-173)
W-6: Fluorine-based surfactant (manufactured by Sumitomo 3M: FC-430)

CS-1: colloidal silica (manufactured by Nissan Chemical Industries, Ltd .: MIBK-ST, 30% methyl isobutyl ketone solution)
CS-2: Tin oxide aqueous dispersion (Ishihara Sangyo Co., Ltd .: SN-38F) substituted with propylene carbonate solvent, 30% solution)
CS-3: Surface-treated silica synthesized in Synthesis Example 1 CS-4: Surface-treated silica synthesized in Synthesis Example 2 CS-5: Surface-treated silica synthesized in Synthesis Example 3 CS-6: In Synthesis Example 4 Surface-treated silica CS-7 synthesized: surface-treated silica CS-8 synthesized in Synthesis Example 5: surface-treated silica CS-9 synthesized in Synthesis Example 6: surface-treated silica CS- synthesized in Synthesis Example 7 10: Surface-treated silica synthesized in Synthesis Example 8

<Additives>
A-1: 2-chlorothioxanthone A-2: 9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
A-3: Silane coupling agent (vinyltriethoxysilane) (manufactured by Shin-Etsu Silicone)
A-4: Silicone oil (Nihon Unicar Co., Ltd .: L-7001)
A-5: 2-dimethylaminoethyl benzoate A-6: benzophenone A-7: ethyl 4-dimethylaminobenzoate A-8: modified dimethylpolysiloxane (manufactured by Big Chemie Japan Co., Ltd .: BYK-307)
A-9: Red 225 (Sudan III)
A-10: Polyether-modified dimethyl silicone oil (manufactured by Big Chemy Japan: BYK302)

<Evaluation of curable composition for optical nanoimprint lithography>
About each of the composition obtained by Examples 1-27 and Comparative Examples 1-13, it measured and evaluated in accordance with the following evaluation method.
Tables 1 and 4 show the blending ratios (Examples and Comparative Examples) of the polymerizable unsaturated monomers used in the compositions.
Tables 2 and 5 show the compounding ratios (Examples and Comparative Examples) of various components of the composition.
Tables 3 and 6 show the evaluation results (Examples and Comparative Examples) of the compositions, respectively.

<Viscosity measurement>
The viscosity was measured at 25 ± 0.2 ° C. using a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd.
The rotational speed during the 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 less than 30 mPa · s for 10 mPa · s, and 60 mPa · s for 30 mPa · s to 60 mPa · s. Less than 10 rpm, 60 mPa · s or more and less than 120 mPa · s was 5 rpm, and 120 mPa · s or more was 1 rpm or 0.5 rpm, respectively.

<Measurement of photocuring speed (photocurability)>
Photocurability is measured using a high-pressure mercury lamp as a light source, and the change in monomer absorption at 810 cm ⁻¹ is measured using a Fourier transform infrared spectrometer (FT-IR) to determine the curing reaction rate (monomer consumption rate). Made in real time. A represents a case where the curing reaction rate is 0.2 / second or more, and B represents a case where the curing reaction rate is less than 0.2 / second.

<Adhesion>
Adhesiveness is determined by visual observation whether the photocured resist pattern photocured on the tape side is attached when the adhesive tape is applied to the surface of the photocured resist pattern and peeled off. It was evaluated as follows.
A: No pattern adherence on the tape side B: Very thin pattern adherence to the tape side, but C: Adherence of pattern clearly recognized on the tape side

<Peelability>
The peelability was evaluated by observing with an optical microscope whether or not an uncured product remained in the mold when the mold was peeled off after photocuring.
A: No residue B: There is a partial residue C: There is a residue on the entire surface

<Observation of residual film properties and pattern shape>
The shape of the transferred pattern and the residue of the transferred pattern were observed with a scanning electron microscope, and the remaining film property and the pattern shape were evaluated as follows.
(Residual film properties)
A: No residue is observed B: A little residue is observed C: Many residues are observed (pattern shape)
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 20%). C: The pattern pattern of the mold is clearly different from the original pattern, or the film thickness of the pattern is 20% or more different from the original pattern.

<Spin coating suitability>
Applicability (I)
The composition of the present invention was spin-coated on a 4-inch 0.7 mm thick glass substrate on which an aluminum (Al) film having a thickness of 4000 angstroms was formed, and then the glass substrate. Was allowed to stand for 1 minute, surface observation was performed, and evaluation was performed as follows.
A: No repelling and coating streaks (striation) observed B: Some coating streaks observed C: Repelling or coating streaks were observed strongly

<Slit application suitability>
Applicability (II)
Using the composition of the present invention, a slit coater resist coating apparatus (a head coater system manufactured by Hirata Kiko Co., Ltd.) for coating a large substrate was used to form a 4-inch 0.3 mm aluminum (Al) film having a thickness of 4000 angstroms. The coating was applied on a 7 mm thick glass substrate (550 mm × 650 mm) to form a resist film having a thickness of 3.0 μm, and the presence or absence of streaky irregularities appearing vertically and horizontally was observed and evaluated as follows.
A: Streaky unevenness was not observed B: Streaky unevenness was observed to be weak C: Streaky unevenness was observed strongly or repellency was observed on the resist film

<Etching property>
The composition of the present invention is formed in a pattern on the aluminum (Al) formed on the glass substrate, and after curing, the aluminum thin film is etched with a phosphoric nitrate etchant, and a 10 μm line / space is visually and microscopically observed. It was evaluated as follows.
A: An aluminum line having a line width of 10 ± 2.0 μm was obtained. B: Variation in line width of the line became a line exceeding ± 2.0 μm. C: A defective portion of the line was partially present. Lines were partially connected D: Deficient part was present on the entire surface, or lines were connected

<Comprehensive evaluation>
Comprehensive evaluation was performed according to the following criteria. Withstands practical use above B rank.
A: B rank is within 1 item.
B: B rank is 2 items.
C: B rank is 3 or more items, or C rank is 1 item.
D: When the D rank is one item.

Synthesis Example 1: Surface treatment of colloidal silica; Synthesis of CS-3 Isopropanol 120 g, Nalcoag 1034A (manufactured by Nalco Chemical Co., 35% colloidal silica aqueous dispersion) 60.6 g, γ-methacryloxypropyltrimethoxysilane 5.8 g The mixture was heated to 80 ° C. and refluxed for 3 hours, and then the solvent was distilled off by about half under reduced pressure. Further, 140 g of butoxyethanol was added to this solution, the solvent was distilled off, and the surface was treated with a silane compound. An ethoxybutanol 30% by mass solution (CS-3) of silica was obtained.

Synthesis Example 2: Surface treatment of colloidal silica; synthesis of CS-4 A mixture of 50 parts of tert-butanol, 16.6 g of Nalcoag 1034A and 1.4 g of γ-methacryloxypropyltrimethoxysilane was heated to reflux for 5 minutes. Thereafter, about half of the solvent was distilled off under reduced pressure, 140 g of butoxyethanol was further added to this solution, the solvent was distilled off under reduced pressure, and a 30% by mass solution of ethoxybutanol in silica whose surface was treated with a silane compound ( CS-4) was obtained.

Synthesis Example 3: Surface treatment of colloidal silica; synthesis of CS-5 In a flask equipped with a stirrer, a condenser and a thermometer, IPA-ST (isopropanol-dispersed colloidal silica sol, manufactured by Nissan Chemical Industries, Ltd., silica particle size 15 nm, silica Solid content 30% by mass) 63.0 g, 0.0012 part of MEHQ as a polymerization inhibitor and 50 g of dilute hydrochloric acid aqueous solution as a hydrolysis catalyst were added, and the temperature of the hot water bath was raised to 80 ° C. while stirring. As soon as the refluxing started, 11.7 g of γ-acryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM503, molecular weight 290), trimethylmethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name LS-) 510, molecular weight 104) 1.6 g of a mixed solution was added dropwise over about 30 minutes, and after completion of the addition, the silica was dispersed in isopropanol and the surface was treated with a silane compound by heating and stirring for about 2 hours. Of 30% by mass (CS-5) was obtained.

Synthesis Example 4: Surface treatment of colloidal silica; synthesis of CS-6 0.6 g of trimethylmethoxysilane (manufactured by Toray Dow Corning Co., Ltd.) was added to 20.0 g of methanol-dispersed colloidal silica having a solid content of 20.0% by mass. The mixture was heated and stirred at 60 ° C. for 3 hours. Thereafter, 14.0 g of methoxypropanol was added, and the mixture was concentrated at a temperature of 80 ° C. to obtain dispersed colloidal silica (CS-6) having a solid content of 30.0% by mass.

Synthesis Example 5: Surface treatment of colloidal silica; synthesis of CS-7 PL-1-IPA (isopropanol-dispersed colloidal silica, manufactured by Fuso Chemical Industry Co., Ltd., silica solid content 12.5% by weight) to 300 g of isopropanol and 15 g of acetic acid , 9.20 g of γ-acryloyloxypropyltrimethoxysilane and 8.20 g of n-hexyltrimethoxysilane were added and heated to reflux. Thereafter, isopropanol was distilled off to obtain surface-treated silica (CS-7) dispersed at a solid content of 12% by mass.

Synthesis Example 6: Surface treatment of colloidal silica; synthesis of CS-8 MEK-ST (methyl ethyl ketone-dispersed colloidal silica, manufactured by Nissan Chemical Industries, Ltd., silica solid content 30% by weight) 30 g of methyl ethyl ketone 200 g and dilute hydrochloric acid aqueous solution 2.0 g, 2.5 g of γ-methacryloyloxypropyltrimethoxysilane was added and heated to reflux to obtain surface-treated silica (CS-8).

Synthesis Example 7 Surface Treatment of Colloidal Silica; Synthesis of CS-9 In 300 g of methanol, 100 g of methanol-dispersed colloidal silica having a silica solid content of 20 wt%, formic acid 5.0 g, and γ-acryloyloxypropyltrimethoxysilane 1.00 g And 2.60 g of n-decyltrimethoxysilane were added and stirred at room temperature for 24 hours. Thereafter, 80 g of methyl isobutyl ketone was added while distilling off methanol by heating to 80 ° C., to obtain methyl isobutyl ketone-dispersed surface-treated silica (CS-9).

Synthesis Example 8 Surface Treatment of Colloidal Silica; Synthesis of CS-10 1.0 g of 1% acetic acid aqueous solution and 8.35 g of γ-acryloyloxypropyltrimethoxysilane were added to 91.3 g of IPA-ST, and the mixture was heated to reflux for 3 hours. Thereafter, 1.47 g of hexamethyldisilazane was added and the mixture was further heated under reflux for 1 hour to obtain surface-treated silica (CS-10).

Example 1
As a polymerizable unsaturated monomer, gamma-butyrolactone acrylate monomer (R-01) 19.096 g, tripropylene glycol diacrylate monomer (S-04) 66.84 g, ethylene oxide modified trimethylolpropane triacrylate single 9.548 g of monomer (S-11), 2,4,6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (Lucirin TPO-L manufactured by BASF) (P-1) 2.50 g as a photopolymerization initiator, interface As activators, EFTOP EF-122A (fluorine surfactant, W-1) 0.02 g, colloidal silica (manufactured by Nissan Chemical Industries, Ltd .: MIBK-ST, 30% methyl isobutyl ketone solution) 6.67 g are precisely weighed. The mixture was stirred at room temperature until methyl ethyl ketone was less than 2% by mass to obtain a uniform solution. The composition ratio of the polymerizable unsaturated monomer used here is shown in Table 1, and the solid content ratio of the composition is shown in Table 2.
This prepared composition was spin-coated on a 4-inch 0.7 mm-thick glass substrate on which an aluminum (Al) film having a thickness of 4000 angstroms was formed so as to have a thickness of 5.0 μm. The spin-coated coated base film is set in a nanoimprint apparatus using an ORC high pressure mercury lamp (lamp power: 2000 mW / cm ² ) as a light source. / 100 mJ / cm ² from the back surface of a mold having a space pattern and a groove depth of 5.0 μm made of polydimethylsiloxane (made by Toray Dow Corning, SILPOT184 cured at 80 ° C. for 60 minutes) After exposure, the mold was released to obtain a resist pattern. Subsequently, the aluminum (Al) portion not covered with the resist was removed with a phosphoric nitrate etchant to form an aluminum (Al) electrode pattern. Further, the resist was stripped by dipping at 80 ° C. for 3 minutes using a mixed stripping solution of monoethanolamine / dimethyl sulfoxide. The results are shown in Table 3. From the results of Table 3, the composition of the present invention was satisfactory in all of adhesion, peelability, residual film property, pattern shape, coatability (spin coatability, slit coatability), and etchability. .

Example 2
As a polymerizable unsaturated monomer, 38.11 g of α-acryloyloxy-β, β-dimethyl-γ-butyrolactone monomer (R-2), neopentyl glycol diacrylate monomer of hydroxypivalate (S-2) 47.74 g, 9.547 g of propylene oxide-modified trimethylolpropane triacrylate (S-12), 2,4,6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (Lucirin TPO-L manufactured by BASF) as a photopolymerization initiator (P-1) 2.5 g, as a surfactant, Daifuku Ink Chemical Co., Ltd. MegaFuck R-08 (fluorine / silicone surfactant) (W-3), and surface-treated colloidal silica 30% by mass Weigh precisely 6.67 g of the solution and stir at room temperature until methyl ethyl ketone is less than 2% by mass. It was a liquid. The composition was exposed and patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 3. From the results shown in Table 3, the composition of the present invention is generally satisfactory in terms of adhesion, peelability, residual film properties, pattern shape, coatability (spin coatability, slit coatability), and etchability. It was recognized that

Examples 3 to 27
In the same manner as in Example 1, polymerizable unsaturated monomers were mixed in the proportions shown in Table 1, and the compositions described in Table 2 were prepared. The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 4. Any of the compositions of Examples 3 to 27 can be generally satisfied with respect to photocurability, adhesion, peelability, remaining film properties, pattern shape, coatability (spin coatability, slit coatability), and etchability. It was a thing.

Comparative Example 1
In the same manner as in Example 1 of the present invention, the composition described in Example 4 of the UV curable coating for optical disk protective film disclosed in JP-A-7-70472 is represented as a polymerizable unsaturated monomer. 4 were mixed at the ratio shown in Table 4 to prepare the compositions shown in Table 5. The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 6.
As shown in Table 6, the composition of Comparative Example 1 was not totally satisfactory.

Comparative Example 2
The composition described in the examples of the optical disc overcoat composition disclosed in JP-A-4-149280 is the same as in Example 1 of the present invention, and the polymerizable unsaturated monomers are shown in Table 5. The composition was prepared by mixing at a ratio. The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 6.
As shown in Table 6, the composition of Comparative Example 2 was not totally satisfactory.

Comparative Example 3
The composition described in Example 1 of the protective coating composition disclosed in JP-A-7-62043 is the same as Example 1 of the present invention, and the polymerizable unsaturated monomer is shown in Table 5. Mixing at a ratio, the composition was adjusted. This prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 6.
As shown in Table 6, the composition of Comparative Example 3 was not totally satisfactory.

Comparative Example 4
In the protective coat composition disclosed in JP-A-2001-93192, the composition described in Comparative Example 2 was treated in the same manner as in Example 1 of the present invention. The composition was prepared by mixing at the ratio shown. The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 6.
As shown in Table 6, the composition of Comparative Example 4 was not totally satisfactory.

Comparative Example 5
The composition described in Example 2 of the ultraviolet ray and electron beam curable composition disclosed in JP-A-2001-270973 is treated in the same manner as in Example 1 of the present invention by using a polymerizable unsaturated monomer. The composition was prepared by mixing at a ratio shown in Table 5. The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 6.
As shown in Table 6, the composition of Comparative Example 5 was inferior in terms of residual film property, pattern shape, coatability (I), and etching property, and was not satisfactory in total.

Comparative Example 6
The composition described in Example 1 of the protective coating composition disclosed in Japanese Patent Application Laid-Open No. 7-53895 is similar to Example 1 of the present invention, and the polymerizable unsaturated monomer is shown in Table 5. The composition was prepared by mixing at a ratio. The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 6.
As shown in Table 6, the composition of Comparative Example 6 was not totally satisfactory.

Comparative Example 7
The composition described in Example 1 of the painting composition disclosed in JP-A No. 2003-165930 is the same as Example 1 of the present invention, and the polymerizable unsaturated monomers are shown in Table 5. Mixing at a ratio, the composition was adjusted. The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 6.
As shown in Table 6, the composition of Comparative Example 7 was inferior in adhesiveness, residual film property, pattern shape, and etching property, and was not completely satisfactory.

Comparative Example 8
The composition containing NVP (N-vinyl pyrrolidone) described on page 157 of “Beginner's Book 38 First Nanoimprint Technology” published in 2005 by the Industrial Research Committee was patterned in the same manner as in Example 1 of this application, and the characteristics of the composition were examined. It was. The results are shown in Table 6.
As shown in Table 6, the composition of Comparative Example 8 was inferior in applicability and etching properties, and was not completely satisfactory.

Comparative Example 9
The composition (viscosity of 35 cP) described in Example 5 of the resin composition for hard coat disclosed in JP-A-2006-63244 was treated in the same manner as in Example 1 of the present invention, and the polymerizable unsaturated monomer. The body was mixed in the ratio shown in Table 5 to prepare a composition. The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 6.
As shown in Table 6, in addition to being inferior in applicability, it was not entirely satisfactory.

Comparative Example 10
Proc. SPIE Int. Soc. Opt. Eng., Vol. In the same manner as in Example 1, polymerizable unsaturated monomers were mixed at a ratio shown in Table 5 to prepare a composition. Since the specific chemical name of the (meth) acrylic monomer is not described in this document, a commercially available monomer was arbitrarily selected to prepare a composition. The monofunctional monomer was an acrylic monomer, the bifunctional monomer was a (meth) acrylic monomer, and the trifunctional monomer was an acrylic monomer. As a photopolymerization initiator, 1.25% of a compound (DAROCURE4265) disclosed in the document was blended. Since the surfactant is not blended in this document, it was not blended. As shown in Table 6, the composition of Comparative Example 10 was inferior in terms of peelability and coatability (II), and was not completely satisfactory.

Comparative Example 11
Proc. SPIE Int. Soc. Opt. Eng., Vol. In the same manner as in Example 1, polymerizable unsaturated monomers were mixed at a ratio shown in Table 5 to prepare a composition. Since the specific chemical name of the (meth) acrylic monomer is not described in this document, a commercially available monomer was arbitrarily selected to prepare a composition. The monofunctional monomer was an acrylic monomer, the bifunctional monomer was a methacrylic monomer, and the trifunctional monomer was an acrylic monomer. As a photopolymerization initiator, 1.25% of a compound (DAROCURE4265) disclosed in the document was blended. Since the surfactant is not blended in this document, it was not blended. As shown in Table 6, the composition of Comparative Example 11 was inferior in terms of peelability and coatability (II), and was not completely satisfactory.

Comparative Example 12
The monofunctional polymerizable unsaturated monomer of the present invention (a monofunctional polymerizable unsaturated monomer having a site having an ethylenically unsaturated bond in the molecule and at least one of oxygen, nitrogen, or sulfur atoms) The monofunctional monomer of Example 9 was replaced by using α-methylstyrene (reagent) as a different monofunctional polymerizable unsaturated monomer, and the polymerizable unsaturated monomer was used in the same manner as in Example 1 of the present invention. The body was mixed in the ratio shown in Table 5 to prepare a composition. However, in Comparative Example 12, inorganic oxide particles were not added. The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 6. As shown in Table 6, the composition of Comparative Example 12 was inferior in terms of photocurability, remaining film property, and pattern shape, and was not satisfactory from the overall viewpoint.

Comparative Example 13
Surface-treated silica (CS-3) was blended with the composition used in Comparative Example 12, and the composition was prepared in the same manner as in Example 1 of the present invention. The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 6.
As shown in Table 6, the composition of Comparative Example 13 was not totally satisfactory.

<Evaluation of Photocurable Composition-II>
The composition of the present invention was evaluated as a permanent film (protective film).

<Residual film ratio>
The photocurable composition of the present invention is spin-coated on a glass substrate to a thickness of 4 μm, set in a nanoimprint apparatus using a high-pressure mercury lamp as a light source, and exposed from the back surface of the mold under conditions of 500 mJ / cm ^2. After the exposure, the mold was released and heated in an oven at 230 ° C. for 150 minutes. The film thickness of the pattern part of the photocurable resin before and after heating was measured with a profiler P11 manufactured by Tenkor, and the remaining film ratio after heating was determined. The results are shown in Table 7.
A: Remaining film ratio exceeding 90% B: Remaining film ratio 85-90%
C: Remaining film ratio less than 85

<Transmissivity>
The photocurable composition of the present invention is spin-coated on a glass substrate so as to have a film thickness of 4 μm, set in a nanoimprint apparatus using a high-pressure mercury lamp as a light source, and irradiated with ultraviolet rays from the back surface of the mold at 500 mJ / cm ^2. Exposed to form a cured film. After exposure, the mold was released and heated in an oven at 230 ° C. for 150 minutes. The light transmittance (T /%) at a wavelength of 550 nm was measured for the light transmittance of the patterned portion of the photocurable resin after heating using a spectrophotometer, and the transmittance after heating was determined. The obtained light transmittance was judged according to the following criteria. The results are shown in Table 7.
A: The light transmittance is 90% or more.
B: Light transmittance is a value of 85 to less than 90%.
C: Light transmittance is less than 85.

<Abrasion resistance test>
After the photocurable composition was spin-coated on a silicon wafer, a cured film having a thickness of 5 μm was formed by irradiating with ultraviolet rays so that the exposure amount was 300 mJ / cm ² using a high-pressure mercury lamp. The cured film was placed on a Gakushin-type wear tester, and was reciprocated 10 times on steel wool with a load of 200 g. The state of abrasion was judged with the naked eye according to the following criteria. The results are shown in Table 7.
A: No scratches B: 1-3 scratches C: 4-10 scratches D: 10 or more scratches

<Solvent resistance>
The photocurable composition of the present invention is spin-coated on a glass substrate to a thickness of 4 μm, set in a nanoimprint apparatus using a high-pressure mercury lamp as a light source, and exposed from the back surface of the mold under conditions of 500 mJ / cm ^2. After the exposure, the mold was released and heated in an oven at 230 ° C. for 150 minutes. After heating, it was immersed in each solution of N-methylpyrrolidone (NMP), 5% sodium hydroxide, and 5% hydrochloric acid for 30 minutes, and the change in film thickness before and after immersion was determined. The results are shown in Table 7.
A: Almost no change in film thickness is observed (less than 1%)
B: Some change in film thickness is observed (less than 1 to 5%)
C: Change in film thickness is slightly observed (5% or more)

<Comprehensive evaluation>
Comprehensive evaluation was performed according to the following criteria. Withstands practical use above B rank. The results are shown in Table 7.
A: B rank is within 2 items.
B: B rank is 3 items.
C: When the B rank is 4 items or more, or the C rank is also 1 item.
D: When the C rank is two or more items or the D rank is one item.

Example 36
The amount of the antioxidant (manufactured by ADEKA, Adeka Stub AO503) was 2 masses in the composition without changing the monomer, photopolymerization initiator, surfactant, type of inorganic oxide particles and blending ratio used in Example 3. %, And the composition was prepared in the same manner as in Example 1. The prepared composition was spin-coated on a glass substrate to a thickness of 4 μm, and the spin-coated base film was applied to a nanoimprint apparatus using a high-pressure mercury lamp (lamp power 2000 mW / cm ² ) manufactured by ORC as a light source. Set, mold pressure is 10 kN / cm ² , vacuum degree during exposure is 0.2 Torr, polydimethylsiloxane having a 5 mm square pattern (SILPOT 184 manufactured by Toray Dow Corning Co., Ltd. cured at 80 ° C. for 60 minutes) The film was exposed under the condition of 500 mJ / cm ² from the back surface of the mold, and after the exposure, the mold was released, and the remaining film rate, transmittance, and scratch resistance of the pattern portion of the photocurable resin before and after heating were measured. Thereafter, the solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 36 was excellent in residual film rate, transmittance, scratch resistance and solvent resistance, and was excellent in properties as a permanent film.

Example 37
The amount of the antioxidant (manufactured by ADEKA, Adeka Stub AO503) was 2 masses in the composition without changing the monomer, photopolymerization initiator, surfactant, type of inorganic oxide particles, and blending ratio used in Example 7. %, And the composition was prepared in the same manner as in Example 1. The prepared composition was spin-coated on a glass substrate to a thickness of 4 μm, and the spin-coated base film was applied to a nanoimprint apparatus using a high-pressure mercury lamp (lamp power 2000 mW / cm ² ) manufactured by ORC as a light source. Set, mold pressure is 10 kN / cm 2, vacuum degree during exposure is 0.2 Torr, polydimethylsiloxane having 5 mm square pattern (SILPOT 184 manufactured by Toray Dow Corning Co., Ltd. cured at 80 ° C. for 60 minutes) It exposed on the conditions of 500 mJ / cm < ² > from the back surface of the mold used as a material, the mold was released after exposure, and the residual film rate, the transmittance | permeability, and scratch resistance of the pattern part of the photocurable resin before and behind a heating were measured. Thereafter, the solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 37 was excellent in residual film rate, transmittance, scratch resistance and solvent resistance, and was excellent in properties as a permanent film.

Example 38
Without changing the monomer, photopolymerization initiator, surfactant, inorganic oxide particle type and blend ratio used in Example 15, an antioxidant (Sumitomo Chemical Industries, Sumilizer GA80) was added to the composition. 2.0% by mass was added and the composition was prepared in the same manner as in Example 1. The prepared composition was spin-coated on a glass substrate to a thickness of 4 μm, and the spin-coated base film was applied to a nanoimprint apparatus using a high-pressure mercury lamp (lamp power 2000 mW / cm ² ) manufactured by ORC as a light source. Set, mold pressure is 10 kN / cm 2, vacuum degree during exposure is 0.2 Torr, polydimethylsiloxane having a 5 mm square pattern (SILPOT 184 manufactured by Toray Dow Corning Co., Ltd. cured at 80 ° C. for 60 minutes) It exposed on the conditions of 500 mJ / cm < ² > from the back surface of the mold used as a material, the mold was released after exposure, and the residual film rate, the transmittance | permeability, and scratch resistance of the pattern part of the photocurable resin before and behind a heating were measured. Thereafter, the solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 38 was excellent in residual film rate, transmittance, scratch resistance and solvent resistance, and was excellent in properties as a permanent film.

Example 39
The monomer, photopolymerization initiator, surfactant, type of inorganic oxide particles, and blending ratio used in Example 17 were not changed, and an antioxidant (Sumilyzer GA80 manufactured by Sumitomo Chemical Co., Ltd.) 2 was added to the composition. 0.0% by mass was added and the composition was prepared in the same manner as in Example 1. The prepared composition was spin-coated on a glass substrate to a thickness of 4 μm, and the spin-coated base film was applied to a nanoimprint apparatus using a high-pressure mercury lamp (lamp power 2000 mW / cm ² ) manufactured by ORC as a light source. Set, mold pressure is 10 kN / cm ² , vacuum degree during exposure is 0.2 Torr, polydimethylsiloxane having a 5 mm square pattern (Toray Dow Corning, SILPT 184 cured at 80 ° C. for 60 minutes) ) Was exposed from the back surface of the mold made of material under the condition of 500 mJ / cm ² , and after the exposure, the mold was released, and the remaining film rate, transmittance, and scratch resistance of the pattern part of the photocurable resin before and after heating were measured. . Thereafter, the solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 39 was excellent in residual film rate, transmittance, scratch resistance, solvent resistance, and excellent properties as a permanent film.

Example 40
The monomers, photopolymerization initiators, surfactants, inorganic oxide particles, types of sensitizers used in Example 19 and the blending ratio were not changed, and an antioxidant (Sumitomo Chemical Co., Ltd., A composition was prepared in the same manner as in Example 1 by adding 2.0% by mass of Sumilizer GA80 and 0.5% by mass of ADEKA (Adeka Stub AO503). The prepared composition was spin-coated on a glass substrate to a thickness of 4 μm, and the spin-coated base film was applied to a nanoimprint apparatus using a high-pressure mercury lamp (lamp power 2000 mW / cm ² ) manufactured by ORC as a light source. Set, mold pressure is 10 kN / cm ² , vacuum degree during exposure is 0.2 Torr, polydimethylsiloxane having a 5 mm square pattern (SILPOT 184 manufactured by Toray Dow Corning Co., Ltd. cured at 80 ° C. for 60 minutes) The film was exposed under the condition of 500 mJ / cm ² from the back surface of the mold, and after the exposure, the mold was released, and the remaining film rate, transmittance, and scratch resistance of the pattern portion of the photocurable resin before and after heating were measured. Thereafter, the solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 40 was excellent in residual film rate, transmittance, scratch resistance, solvent resistance, and excellent properties as a permanent film.

Example 41
The monomers, photopolymerization initiators, surfactants, inorganic oxide particles, types of sensitizers used in Example 22, and the ratio of the sensitizers were not changed, and the antioxidants (Sumitomo Chemical Industries, The composition was adjusted in the same manner as in Example 1 by adding 2.0% by mass of Sumilizer GA80). The prepared composition was spin-coated on a glass substrate to a thickness of 4 μm, and the spin-coated base film was applied to a nanoimprint apparatus using a high-pressure mercury lamp (lamp power 2000 mW / cm ² ) manufactured by ORC as a light source. Set, mold pressure is 10 kN / cm ² , vacuum degree during exposure is 0.2 Torr, polydimethylsiloxane having a 5 mm square pattern (Toray Dow Corning, SILPT 184 cured at 80 ° C. for 60 minutes) ) Was exposed from the back surface of the mold made of material under the condition of 500 mJ / cm ² , and after the exposure, the mold was released, and the remaining film rate, transmittance, and scratch resistance of the pattern part of the photocurable resin before and after heating were measured. . Thereafter, the solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 41 was excellent in residual film rate, transmittance, scratch resistance and solvent resistance, and was excellent in properties as a permanent film.

Example 42
As a polymerizable unsaturated monomer, 28 g of benzyl acrylate monomer (R-26), 22.0 g of neopentyl glycol diacrylate monomer (KAYARAD NPGDA; manufactured by Nippon Kayaku), trimethylolpropane triacrylate monomer (S-15) 1.9 g, as a photopolymerization initiator, 2,4,6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (BASF, Lucirin TPO-L) (P-1) 3.0 g, surfactant EFTOP EF-122A (fluorine surfactant, W-1) 0.05 g, antioxidant (Sumitomo Chemical Industries, Sumilizer GA80) 2.0 g, surface-treated colloidal silica 30 mass% solution 83. 3 g was precisely weighed and stirred at room temperature until methyl ethyl ketone was less than 2% by mass to obtain a uniform solution. The prepared composition was spin-coated on a glass substrate to a thickness of 4 μm, and the spin-coated base film was applied to a nanoimprint apparatus using a high-pressure mercury lamp (lamp power 2000 mW / cm ² ) manufactured by ORC as a light source. Set, mold pressure is 10 kN / cm ² , vacuum degree during exposure is 0.2 Torr, polydimethylsiloxane having a 5 mm square pattern (SILPOT 184 manufactured by Toray Dow Corning Co., Ltd. cured at 80 ° C. for 60 minutes) The film was exposed under the condition of 500 mJ / cm ² from the back surface of the mold, and after the exposure, the mold was released, and the remaining film rate, transmittance, and scratch resistance of the pattern portion of the photocurable resin before and after heating were measured. Thereafter, the solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 42 was excellent in residual film rate, transmittance, scratch resistance, solvent resistance, and excellent properties as a permanent film.

Example 43
The monomer, photopolymerization initiator, surfactant, type of inorganic oxide particles, and blending ratio used in Example 29 were not changed, and 2 masses of an antioxidant (manufactured by ADEKA, Adeka Stub AO503) was contained in the composition. %, And the composition was prepared in the same manner as in Example 1. The prepared composition was spin-coated on a glass substrate so as to have a film thickness of 4 μm, and the spin-coated base film was applied to a nanoimprint apparatus using a high-pressure mercury lamp (lamp power 2000 mW / cm ² ) manufactured by ORC as a light source. The mold pressure is 10 kN / cm ² , the degree of vacuum during exposure is 0.2 Torr, and a polydimethylsiloxane having a 5 mm square pattern (SILPOT 184 manufactured by Toray Dow Corning Co., Ltd. cured at 80 ° C. for 60 minutes) The film was exposed from the back surface of the mold made of the material under conditions of 500 mJ / cm ² , and after the exposure, the mold was released, and the remaining film rate, transmittance, and scratch resistance of the pattern portion of the photocurable resin before and after heating were measured. Thereafter, the solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 43 was excellent in residual film rate, transmittance, scratch resistance, solvent resistance, and excellent properties as a permanent film.

Example 44
The monomer, photopolymerization initiator, surfactant, type of inorganic oxide particles, and blending ratio used in Example 31 were not changed, and 2 masses of antioxidant (manufactured by ADEKA, ADK STAB AO503) was contained in the composition. %, And the composition was prepared in the same manner as in Example 1. The prepared composition was spin-coated on a glass substrate so as to have a film thickness of 4 μm, and the spin-coated base film was applied to a nanoimprint apparatus using a high-pressure mercury lamp (lamp power 2000 mW / cm ² ) manufactured by ORC as a light source. The mold pressure is 10 kN / cm ² , the degree of vacuum during exposure is 0.2 Torr, and a polydimethylsiloxane having a 5 mm square pattern (SILPOT 184 manufactured by Toray Dow Corning Co., Ltd. cured at 80 ° C. for 60 minutes) The film was exposed under the condition of 500 mJ / cm <2> from the back surface of the mold, and after the exposure, the mold was released, and the remaining film rate, transmittance, and scratch resistance of the pattern portion of the photocurable resin before and after heating were measured. Thereafter, the solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 44 was excellent in residual film rate, transmittance, scratch resistance, solvent resistance, and excellent properties as a permanent film.

Example 45
The monomer, photopolymerization initiator, surfactant, type of inorganic oxide particles, and mixing ratio used in Example 36 were not changed, and 2 mass of an antioxidant (manufactured by ADEKA, Adeka Stub AO503) was contained in the composition. %, And the composition was prepared in the same manner as in Example 1. The prepared composition was spin-coated on a glass substrate to a thickness of 4 μm, and the spin-coated base film was applied to a nanoimprint apparatus using a high-pressure mercury lamp (lamp power 2000 mW / cm ² ) manufactured by ORC as a light source. Set, mold pressure is 10 kN / cm 2, vacuum degree during exposure is 0.2 Torr, polydimethylsiloxane having 5 mm square pattern (SILPOT 184 manufactured by Toray Dow Corning Co., Ltd. cured at 80 ° C. for 60 minutes) It exposed on the conditions of 500 mJ / cm < ² > from the back surface of the mold used as a material, the mold was released after exposure, and the residual film rate, the transmittance | permeability, and scratch resistance of the pattern part of the photocurable resin before and behind a heating were measured. Thereafter, the solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 45 was excellent in residual film rate, transmittance, scratch resistance, solvent resistance, and excellent properties as a permanent film.

Comparative Example 14
The prepared composition used in Comparative Example 1 was patterned in the same manner as in Example 36, and the characteristics of the composition were examined. The results are shown in Table 7. The antioxidant added to Example 36 was not added. The composition of Comparative Example 14 tended to be somewhat inferior in the remaining film rate, permeability, and solvent resistance (NMP), and was inferior overall.

Comparative Example 15
The prepared composition used in Comparative Example 2 was patterned in the same manner as in Example 36, and the characteristics of the composition were examined. The results are shown in Table 7. The composition of Comparative Example 12 had a tendency to be somewhat inferior in the remaining film ratio and solvent resistance (NMP), inferior in permeability, and inferior overall.

Comparative Example 16
The prepared composition used in Comparative Example 3 was patterned in the same manner as in Example 36, and the characteristics of the composition were examined. The results are shown in Table 7. The composition of Comparative Example 12 was inferior in the remaining film rate and transmittance, in the tendency to be somewhat inferior in solvent resistance (NMP, HCl), and was inferior overall.

Comparative Example 17
The prepared composition used in Comparative Example 4 was patterned in the same manner as in Example 36, and the characteristics of the composition were examined. The results are shown in Table 5. The composition of Comparative Example 13 had a tendency to be somewhat inferior in the remaining film rate, transmittance, and solvent resistance (NMP, HCl), inferior in permeability, and inferior overall.

Comparative Example 18
The prepared composition used in Comparative Example 9 was patterned in the same manner as in Example 36, and the characteristics of the composition were examined. The results are shown in Table 7. The composition of Comparative Example 18 had a tendency to be somewhat inferior in the remaining film rate, transmittance, and solvent resistance (NaOH), inferior in permeability, and inferior overall.

Examples 1-45
When the viscosity of the photocurable composition of this invention of Examples 1-45 was measured, all were the range of 3-18 mPa * s.

Comparative Examples 1-7, 9, 12, 13
When the viscosities of the photocurable compositions of Comparative Examples 1 to 7, 9, 12, and 13 were measured, all were 20 mPa or more.

Comparative Examples 8, 10, and 11
When the viscosities of the photocurable compositions of Comparative Examples 8, 10, and 11 were measured, all were in the range of 5 to 15 mPa.

 The composition of the present invention includes a semiconductor integrated circuit, a flat screen, a micro electro mechanical system (MEMS), a sensor element, an optical disk, a magnetic recording medium such as a high density memory disk, an optical component such as a diffraction grating relief hologram, a nanodevice, Optical devices, optical films and polarizing elements for flat panel display production, thin film transistors for liquid crystal displays, organic transistors, color filters, overcoat layers, pillar materials, rib materials for liquid crystal alignment, microlens arrays, immunoassay chips, It can be used as an optical nanoimprint resist composition for forming a fine pattern when producing a DNA separation chip, microreactor, nanobiodevice, optical waveguide, optical filter, photonic liquid crystal, and the like.

Claims (12)

35 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 15% by mass of a photopolymerization initiator, at least one of a fluorine-based surfactant, a silicone-based surfactant and a fluorine / silicone-based surfactant. A curable composition for optical nanoimprint lithography, comprising 001 to 5% by mass and 0.1 to 50% by mass of inorganic oxide fine particles. The composition according to claim 1, wherein the polymerizable unsaturated monomer has a site having an ethylenically unsaturated bond in the molecule and a site having at least one of an oxygen atom, a nitrogen atom and a sulfur atom. And a monofunctional polymerizable unsaturated monomer containing at least 15% by mass in the composition and 48 to 99% by mass of the polymerizable unsaturated monomer. Sex composition. The composition according to claim 2, comprising at least one compound selected from the following (a), (b) and (c) as a monofunctional polymerizable unsaturated monomer.
(A) a polymerizable unsaturated monomer having a portion having an ethylenically unsaturated bond in one molecule and an aliphatic cyclic portion containing a hetero atom (b) a portion having an ethylenically unsaturated bond in one molecule; A polymerizable unsaturated monomer having a —C (═O) — bond and an NR bond (R is a hydrogen atom or a methyl group) (c) a site having an ethylenically unsaturated bond in one molecule and 6 carbon atoms Polyunsaturated unsaturated monomer having 12 alicyclic moieties The composition according to claim 3, wherein the heteroatom of the monofunctional polymerizable unsaturated monomer (a) is any one or more of an oxygen atom, a nitrogen atom and a sulfur atom. The composition according to any one of claims 2 to 4, wherein the monofunctional polymerizable unsaturated monomer is at least one selected from the following general formulas (I) to (VIII).
Formula (I)

(In the general formula (I), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, respectively. Group represents an ethoxy group, n1 represents 1 or 2, m1 represents any of 0, 1, and 2. Z ¹¹ represents a methylene group, an oxygen atom, and an —NH— group, and two Z ¹¹ represent each other W ¹¹ represents —C (═O) — or —SO ₂ —, R ¹² and R ^13, and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. .)
Formula (II)

(In the general formula (II), R ²¹ represents a hydrogen atom or a methyl group, and R ²² , R ²³ , R ²⁴ and R ²⁵ represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, respectively. Each of R ²² and R ²³ and R ²⁴ and R ²⁵ may be bonded to each other to form a ring, n2 is any one of 1, 2, and 3; m2 represents any of 0, 1, and 2. Y ²¹ represents a methylene group or an oxygen atom.)
Formula (III)

(In the general formula (III), R ³² , R ³³ , R ³⁴ and R ³⁵ represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group and an ethoxy group, respectively. Is any one of 1, 2, and 3, and m3 represents either 0, 1, or 2. X ³¹ represents —C (═O) —, a methylene group, or an ethylene group, and two X ³¹ represent Y ³² represents a methylene group or an oxygen atom.
Formula (IV)

(In the general formula (IV), R ⁴¹ represents a hydrogen atom or a methyl group. R ⁴² and R ⁴³ represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group, and an ethoxy group, respectively. W ⁴¹ represents a single bond, no bond, or —C (═O) —, n4 represents 2, 3, or 4. X ⁴² represents —C (═O) —, — C = C-, -C = N-, or a methylene group, and each X ⁴² may be the same or different, M ⁴¹ is a hydrocarbon linking group having 1 to 4 carbon atoms, an oxygen atom or a nitrogen atom And each M ⁴¹ may be the same or different.)
General formula (V)

(In the general formula (V), R ⁵¹ represents a hydrogen atom or a methyl group. Z ⁵² represents an oxygen atom, —CH═N— or a methylene group. W ⁵² represents a methylene group or an oxygen atom. Y ⁵² represents Represents a single bond or —C (C═O) —, Y ⁵³ represents a single bond or —C (C═O) —, and R ⁵⁴ and R ⁵⁵ represent a hydrogen atom, a methyl group, an ethyl group, or a propyl, respectively. A group, a butyl group, a halogen atom, a methoxy group or an ethoxy group, R ⁵⁴ and R ⁵⁵ may be bonded to each other to form a ring, X ⁵¹ may be a single bond or no bond, m5 is 0, 1 Or at least one of W ⁵² , Z ⁵² , R ⁵⁴ , and R ⁵⁵ contains an oxygen atom or a nitrogen atom.)
Formula (VI)

(In the general formula (VI), R ⁶¹ is a hydrogen atom or a methyl group, R ⁶² and R ⁶³ are a hydrogen atom, a methyl group, an ethyl group, a hydroxyethyl group, a propyl group, (CH ₃ ) ₂ N— ( CH ₂ ) _m6 — (m6 is 1, 2 or 3), CH ₃ CO— (CR ⁶⁴ R ⁶⁵ ) _p6 — (R ⁶⁴ and R ⁶⁵ each represents a hydrogen atom or a methyl group, and p6 is 1, 2; Or ( ₃ )), (CH ₃ ) ₂ —N— (CH ₂ ) _p6 — (p6 is 1, 2 or 3), provided that in general formula (VI) The moiety of —NR ⁶² (R ⁶³ ) may be a —N═C═O group, R ⁶² and R ⁶³ do not simultaneously become a hydrogen atom, and X ⁶ represents —CO— or —COCH. _{2 -, - COCH 2 CH 2} -, - COCH 2 CH 2 CH 2 -, - COOCH 2 CH 2 - is either )
Formula (VII)

(In general formula (VII), R ⁷¹ and R ⁷² are each a hydrogen atom or a methyl group, and R ⁷³ represents a hydrogen atom, a methyl group, or an ethyl group.)
General formula (VIII)

(In the general formula (VIII), R ⁸¹ represents a hydrogen atom, a methyl group or a hydroxymethyl group. R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ are a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, a hydroxy group, respectively. Represents a methyl group, a hydroxyethyl group, a propyl group and a butyl group, and at least two of R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ may be bonded to each other to form a ring, W ⁸¹ represents a methylene group, —NH _{-, - N (CH 3)} -, - N (C 2 H 5) - .W 82 is a single bond or, -C (= O) - when .W ⁸² representing a single bond, R ^82, R ⁸³ , R ⁸⁴ and R ⁸⁴ are not hydrogen atoms, and n7 represents an integer of 0 to 8. The composition according to any one of claims 1 to 5, further comprising a site having at least one ethylenically unsaturated bond, and a second polymerization containing a silicone atom and / or a phosphorus atom. The composition of any one of Claims 1-5 which contains 0.1 mass% or more of a polymerizable unsaturated monomer in the said polymerizable unsaturated monomer. The composition according to any one of claims 1 to 6, wherein the inorganic oxide fine particles are colloidal silica. The composition according to claim 7, wherein the colloidal silica is a surface-treated colloidal silica. The composition according to claim 8, wherein the colloidal silica is colloidal silica surface-treated with a compound having a reactive (meth) acrylate group. The composition according to any one of claims 1 to 9, comprising an antioxidant. It is a composition of any one of Claims 1-10, Comprising: The composition of any one of Claims 1-10 whose viscosity in 25 degreeC is 25 mPa * s or less. From the step of applying the composition according to any one of claims 1 to 11, pressurizing the light-transmitting mold to the resist layer on the substrate, and deforming the applied composition, from the back of the mold or the back of the substrate A pattern forming method including a step of irradiating light, curing a coating film, forming a resist pattern that fits into a desired pattern, and a step of detaching a light-transmitting mold from the coating film.