JP2010067935A - Curable composition for nanoimprint, cured article and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition for nanoimprint, which can provide a cured article excelling in permeability. <P>SOLUTION: The curable composition for nanoimprint contains (A) a monomer having two or more curable functional groups different in reactivity in the same molecule, (C) antioxidant, and (D) a mold release agent. The (D) mold release agent is a silicone-based mold release agent. The composition contains 0.001-10 mass% of the (D) mold release agent. At least one of the curable functional groups is α,β-unsaturated ester group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

  The nanoimprint method has been developed by developing embossing technology, which is well-known in optical disc production, and mechanically pressing a mold master (generally called a mold, stamper, or template) with a concavo-convex pattern onto a resist. This is a technology that precisely deforms and transfers fine patterns. Once the mold is made, it is economical because nanostructures and other microstructures can be easily and repeatedly molded, and it is economical, and since it is a nano-processing technology with less harmful waste and emissions, it has recently been applied to various fields. Is expected.

  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 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. For example, Patent Document 1 and Patent Document 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 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 instead of conventional lithography, the production of transistors in liquid crystal displays, and the like. 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 is dramatically increased to 256 mega, 1 giga, and 4 giga, the pattern formation time is remarkably increased correspondingly, and there is a concern that the throughput is extremely 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, 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 in the field of semiconductor microlithography. On the other hand, active studies are underway to apply nanoimprint to semiconductor integrated circuit production, such as fine mold production technology, mold durability, mold production cost, mold release from resin, imprint uniformity and alignment accuracy, and inspection technology. Began to turn.

Next, an application example of nanoimprint to a flat display such as a liquid crystal display (LCD) or a plasma display (PDP) will be described.
With the trend toward larger and higher definition LCD substrates and PDP substrates, optical nanoimprints have recently attracted attention as inexpensive lithography that replaces conventional photolithography methods used in the manufacture of thin film transistors (TFTs) and electrode plates. Therefore, it has become necessary to develop a photo-curable resist that replaces the etching photoresist used in the conventional photolithography method.
Further, as a structural member such as an LCD, application of optical nanoimprinting to a transparent protective film material described in Patent Document 5 and Patent Document 6 or a spacer described in Patent Document 6 has begun to be 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 the flat display panel or the like. The permanent film used on the TFT substrate will be specifically described. In the case of a liquid crystal panel, a thin film transistor is formed on a glass substrate, and a transparent protective film layer (permanent film) is formed thereon to protect the thin film transistor. Further, ITO (indium tin oxide), which is a transparent electrode, is provided by sputtering in order to drive the liquid crystal with voltage. In the protective film, a contact hole is formed by photolithography before ITO sputtering so that the thin film transistor and ITO can be electrically connected, and further cured by post-baking to ensure heat resistance. As a material, a positive resist or the like is often used.
Next, the transparent permanent film for color filters will be described. In general, in a liquid crystal display, a black matrix using a chromium oxide or a carbon black-containing resist is formed on a glass substrate, and then R, G, and B color filter layers are formed on the front surface. A photocurable resin or the like is applied onto the color filter, the electrode lead-out portion or the like is removed by photolithography, and a protective film (permanent film) is formed by heat treatment by post-baking. The permanent film for a color filter can reduce the level difference between the color filter layers, and can improve the resistance to high-temperature treatment during the sputtering film formation of ITO, which is a transparent electrode.
Conventionally, as a transparent permanent film for a color filter, a transparent permanent film is formed using a photocurable resin or a thermosetting resin such as siloxane polymer, silicone polyimide, epoxy resin, acrylic resin (Patent Document 7, Patent) Reference 8).
In the formation of a permanent film provided on a thin film transistor or a color filter, the uniformity of the coating film, substrate adhesion, high light transmittance after heat treatment at least 200 ° C., planarization characteristics, solvent resistance, Characteristics such as scratch resistance are required.

In addition, 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 generally a pattern having a size of about 10 μm to 20 μm by photolithography after applying the photocurable composition after forming the color filter on the color filter substrate or after forming the protective film for the color filter. And then heat-cured by post-baking.
The spacer is required to have performance such as high mechanical characteristics against external pressure, hardness, developability, pattern accuracy, and adhesion.

  However, a transparent protective film used in the nanoimprint method or a preferable composition of a photocurable composition for forming a spacer has never 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 related to optical nanoimprint will be described in more detail. In optical nanoimprinting, a liquid curable composition for optical nanoimprinting is dropped onto a substrate such as a silicon wafer, quartz, glass, film or other material such as a ceramic material, a metal, or a polymer, and approximately several tens nm to several μm. The film is applied with a film thickness of approximately several tens of nanometers to several tens of micrometers, and a mold having fine irregularities is pressed and pressurized, and the composition is cured by irradiation with light in the pressurized state, and then the coating film In general, the mold is released from the mold to obtain a transferred pattern. Therefore, in the case of optical nanoimprint, at least one of the substrate or the mold needs to be transparent for the convenience of performing 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.
In particular, irradiating light from the mold side is effective in constructing a structure using the optical nano-imprint method on a color filter used for an LCD having a light-blocking substrate. .
The optical nanoimprint method is (1) no heating / cooling process is required and high throughput is expected compared to the thermal nanoimprint method, and (2) imprinting at a low pressure is possible because a liquid composition is used. 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, in order to apply a thermal and / or optical nanoimprint method and imprint micrometer or nanometer size patterns 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.

The mold used in the optical nanoimprint can be manufactured from various materials such as metal, semiconductor, ceramic, 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.
Regarding the optical nanoimprint method, the releasability of the mold and the curable composition for optical nanoimprinting is important. The mold and the surface treatment of the mold, specifically, hydrogenated silsesquioxane or fluorinated ethylene propylene copolymer mold. Attempts have been made so far to solve the adhesion problem using slag.

  Here, the photocurable resin used for optical nanoimprint 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 radically polymerizable vinyl group or (meth) acryl group 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 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 characteristics 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 to be applied to such optical nanoimprint applications, Non-Patent Document 6 discloses a photocurable material having a viscosity of about 60 mPa · s (25 ° C.) and is well known. 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.

  Examples of photocurable resins that have been applied to optical nanoimprints 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 nanoimprinting 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.

  Patent Document 27 discloses a photocurable composition for nano-imprint using a (meth) acrylate monomer containing a cyclic structure in order to impart dry etching properties.

  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 photo-cationic polymerizable composition containing an epoxy compound and a photoacid generator is applied to nanoimprint and thermal stability and mold releasability are examined 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 nanoimprinting 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 curable composition for optical nanoimprinting containing a monofunctional acrylic monomer, a silicone-containing monofunctional monomer, and a photopolymerization initiator is formed on a silicon substrate, and optical nanoimprinting is performed using a surface-treated mold. It is disclosed that defects after molding are reduced.

In Non-Patent Document 11, a curable composition for optical nanoimprinting containing a silicone monomer, a trifunctional acrylic monomer, and a photopolymerization initiator is formed on a silicon substrate, and high resolution and coating uniformity are achieved by SiO ₂ mold. An excellent composition 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 are disclosed, they are preferable as a composition. No guidance is provided regarding material design such as type, optimal monomer type, monomer combination, optimal monomer or resist viscosity, preferred resist solution properties, and improved resist coatability. Therefore, a preferable composition for widely applying the composition to optical nanoimprint 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 inorganic / organic hybrid materials composed of a mixture of silica sol treated with a photofunctional crosslinking material, (meth) acrylic monomer, and photopolymerization initiator, and their application to optical nanoimprints is reported. ing. 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 have low viscosity, but both of them are photocured to form a pattern, and the transmittance of the cured film is low when subsequently heat-treated, that is, It is colored and the hardness is insufficient. In particular, a composition that is practically usable as a permanent film is not known.

Patent Document 24 discloses a composition for hard coat containing 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 peelability from the mold and the substrate coating property were insufficient, and the application to the optical nanoimprint was difficult. Furthermore, after photocuring, the transmittance when heat-treated is low, that is, it is colored and cannot be used as a permanent film.
Further, Patent Document 27 reports an etching resist composition using a (meth) acrylate having a cyclic structure, but these compositions have low transmittance when heat-treated after photocuring, That is, it is colored and cannot be used as a permanent film, and the hardness and solvent resistance of the cured film are insufficient, so that it cannot be put into practical use.

As a means of increasing the hardness and mechanical strength of the cured film, it can be achieved by using a polyfunctional monomer that gives a high crosslink density. However, such a polyfunctional monomer is a high viscosity compound, and under a low viscosity constraint. It was difficult to obtain satisfactory cured film properties. Furthermore, the polyfunctional monomer is rapidly polymerized at the time of light irradiation, and there is a problem that a residue remains when a resin mold is used.
Patent Document 25 has been reported as a curable composition for inkjet using a monomer having a photopolymerization site and a thermal reaction site in the same molecule. However, in this invention, the viscosity of the composition is high and optical nanoimprint is used as it is. It cannot be applied. Also, the cured film is highly colored, and there is a problem in terms of permeability when used as a spacer protective film for a liquid crystal color filter, and no improvement method has been disclosed.

Patent Document 26 reports a curable composition of an acrylate monomer having a vinyl ether group in the same molecule. Although the present invention has a low viscosity and can be applied to optical nanoimprinting, the hardness of the cured film is insufficient, and an improvement method thereof is not disclosed.
Thus, the actual situation is that no resist composition that can be practically used as a permanent film and that can be applied with the photo-nanoimprint method has been proposed.

The main technical issues as a permanent film are pattern accuracy, adhesion, permeability 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 nanoimprinting as a permanent film for optical nanoimprinting, as with conventional resists using acrylic resins,
It is important to provide (1) coating film uniformity, (2) permeability 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 points (4) and (5) as a curable composition for optical nanoimprinting, which makes it difficult to design the composition. The degree becomes even higher.
(4) Ensure fluidity of the resist to the recess of the mold, and it is necessary to reduce the viscosity without using a solvent or a small amount of solvent. (5) After photocuring, it can be easily peeled off from the mold and transferred to the mold. Although various materials have been disclosed for curable compositions for optical nanoimprints for nanoimprints, compositions that have been known for use in inkjet compositions and protective films for magneto-optical disks have been disclosed. Curable composition for photo-nanoimprint used as an etching resist or an etching resist, although there are common parts with curable composition for photo-nanoimprint used for permanent film, high-temperature heat treatment, mechanical strength viewpoint The photo-curing resin applied for inkjet, magneto-optical disk protective film, and etching resist applications. When applied as a resist for a permanent film as it is, it is difficult to obtain one that can withstand practicality in terms of permeability, mechanical strength, solvent resistance, and the like. In particular, a material having high permeability is required.

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 International Publication WO2004 / 099272 Pamphlet JP 2005-255854 A JP 2007-186570 A

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  The present invention has been accomplished in view of the above circumstances, and an object thereof is to provide a curable composition for nanoimprints that is excellent in photocurability and excellent in transparency. Furthermore, it aims at providing the curable composition for nanoimprints suitable for permanent films, such as a flat panel display. In particular, an object is to provide a composition excellent in all of permeability, peelability, and pattern accuracy after heat curing.

As a result of intensive studies on the above-mentioned Patent Document 25 (International Publication WO 2004/099272 pamphlet), a single monomer having two or more curable functional groups having different reactivity in the same molecule, for example, a photopolymerization site and a thermal reaction site. In the case of using a body, it has a viscosity having nanoimprint suitability and gives satisfactory cured film properties. Further, since it is in a semi-cured state at the time of photopolymerization, an inexpensive resin mold can be used. It was found that the effect that almost no residue remains was obtained. Based on this knowledge, it has been found that the above-mentioned problems can be solved by the following means.
(1) Curing for nanoimprinting comprising (A) a monomer having at least two types of curable functional groups having different reactivity in the same molecule, (C) an antioxidant, and (D) a release agent. Sex composition.
(2) The curable composition for nanoimprints according to (1), wherein the (D) release agent is a silicone-based release agent.
(3) The curable composition for nanoimprints according to (1), wherein (D) the release agent is a modified silicone oil.
(4) The curable composition for nanoimprints according to any one of (1) to (3), wherein the (D) release agent is contained in the composition at a ratio of 0.001 to 10 mass%.
(5) The curable composition for nanoimprints according to any one of (1) to (4), wherein at least one of the curable functional groups is an α, β-unsaturated ester group.
(6) The curable composition for nanoimprints according to any one of (1) to (5), wherein the viscosity of the composition is in the range of 3 to 18 mPa · s.
(7) The curable composition for nanoimprints according to any one of (1) to (6), wherein the monomer is represented by the following general formula (1).

（一般式（１）中、Ｒ¹は水素原子、または、ヒドロキシメチル基を表し、Ｘは有機基を表す。ｍは１〜３の整数を表し、ｎは１〜４の整数を表す。Ｙは、炭素−炭素不飽和結合を有する硬化性官能基、炭素−窒素不飽和結合を有する硬化性官能基、酸素原子を含む環状基を有する硬化性官能基または下記一般式（２）で表される基を表す。）

(In General Formula (1), R ¹ represents a hydrogen atom or a hydroxymethyl group, X represents an organic group, m represents an integer of 1 to 3, and n represents an integer of 1 to 4. Y Is represented by a curable functional group having a carbon-carbon unsaturated bond, a curable functional group having a carbon-nitrogen unsaturated bond, a curable functional group having a cyclic group containing an oxygen atom, or the following general formula (2): Represents a group.

（Ｒ²はそれぞれアルキル基またはアリール基を表す。）
硬化性組成物。
（８）上記単量体（Ａ）以外の重合性単量体、および光重合開始剤を含む、（１）〜（７）のいずれか１項に記載のナノインプリント用硬化性組成物。
（９）分子量が１０００を超える化合物を含まない（１）〜（８）のいずれか１項に記載のナノインプリント用硬化性組成物。
（１０）前記組成物の表面張力が１８〜３０ｍＮ／ｍの範囲にある、（１）〜（９）のいずれか１項に記載のナノインプリント用硬化性組成物。
（１１）光照射および加熱を行うことにより硬化することを特徴とする、（１）〜（１０）のいずれか１項に記載のナノインプリント用硬化性組成物。
（１２）さらに、界面活性剤を含む、（１）〜（１１）のいずれか１項に記載のナノインプリント用硬化性組成物。
（１３）（１）〜（１２）のいずれか１項に記載のナノインプリント用硬化性組成物を硬化させた硬化物。
（１４）（１）〜（１２）のいずれか１項に記載のナノインプリント用硬化性組成物を、光照射および加熱を複数回行うことにより硬化させることを含む、硬化物の製造方法。
（１５）（１３）に記載の硬化物を用いた液晶表示装置用部材。
（１６）（１）〜（１２）のいずれか１項に記載の組成物を、光照射および加熱を複数回行うことにより硬化させることを含む、液晶表示装置用部材の製造方法。

(R ² represents an alkyl group or an aryl group, respectively.)
Curable composition.
(8) The curable composition for nanoimprints according to any one of (1) to (7), comprising a polymerizable monomer other than the monomer (A) and a photopolymerization initiator.
(9) The curable composition for nanoimprints according to any one of (1) to (8), which does not contain a compound having a molecular weight of more than 1000.
(10) The curable composition for nanoimprints according to any one of (1) to (9), wherein the surface tension of the composition is in the range of 18 to 30 mN / m.
(11) The curable composition for nanoimprints according to any one of (1) to (10), which is cured by light irradiation and heating.
(12) The curable composition for nanoimprints according to any one of (1) to (11), further comprising a surfactant.
(13) A cured product obtained by curing the curable composition for nanoimprints according to any one of (1) to (12).
(14) A method for producing a cured product, comprising curing the curable composition for nanoimprints according to any one of (1) to (12) by performing light irradiation and heating a plurality of times.
(15) A member for a liquid crystal display device using the cured product according to (13).
(16) A method for producing a member for a liquid crystal display device, comprising curing the composition according to any one of (1) to (12) by performing light irradiation and heating a plurality of times.

  By this invention, it became possible to provide the curable composition for nanoimprint from which the hardened | cured material excellent in the transmittance | permeability is obtained.

  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, and it goes without saying that the nanoimprint is not limited to a nano-order.

 The curable composition for optical nanoimprint of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) has high permeability before curing, and is excellent in the ability to form a fine uneven pattern. , It can be excellent in coating suitability and other processing suitability. Moreover, after hardening, it is excellent in hardness, and also it can be set as the film property which was comprehensively excellent in other points. Therefore, the composition of the present invention can be widely used for optical nanoimprint.

That is, the composition of the present invention can have the following characteristics when used for optical nanoimprint.
(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) Since it is excellent in coating uniformity, it is suitable for the field of coating / microfabrication on large substrates.
(4) 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. .

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

  The viscosity of the composition of the present invention will be described. The viscosity in the present invention means a viscosity at 25 ° C. unless otherwise specified. The composition of the present invention has a viscosity at 25 ° C. of preferably 3 to 18 mPa · s, more preferably 5 to 15 mPa · s, and further preferably 7 to 12 mPa · s. 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 18 mPa · s or less, even when a mold having a fine concavo-convex pattern is adhered to the composition, the composition 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 (A) a monomer having two or more curable functional groups having different reactivity in the same molecule, (C) an antioxidant, and (D) a release agent. . Furthermore, in the present invention, (B) a surfactant may be included. Moreover, (A) monomer may be only one type and may be two or more types. The composition of the present invention preferably contains the monomer (A) in the range of 10 to 99% by mass, more preferably 20 to 80% by mass of the composition. Furthermore, the composition of the present invention may contain other polymerizable monomers, photopolymerization initiators, and the like. Hereinafter, these contents will be described in detail.

First, a compound having two or more kinds of curable functional groups having different reactivity contained in the same molecule in the composition of the present invention will be described (hereinafter sometimes referred to as “monomer in the present invention”). Here, two types of curable functional groups having different reactivity can be distinguished as follows, for example. As a first example, polymerization (reaction) proceeds during light irradiation, but the functional groups have different reactivity. Examples of such a curable functional group include an acrylate group, an N-vinyl group, and a (meth) acryloylamide group. As a second example, there are a group in which polymerization (reaction) proceeds upon irradiation with light and a group in which polymerization (reaction) proceeds by heating. Specific examples of groups that do not react when irradiated with light include vinyl ether groups, allyl ether groups, allyl ester groups, cyclohexenyl groups, cyclopentenyl groups, dicyclopentenyl groups, styryl groups, methacryloyloxy groups, vinyl silane groups, and maleimide groups. Can be mentioned. A methacryloyloxy group, a styryl group, and a vinyl ter group are usually radically polymerized. However, since polymerization at the time of light irradiation is performed at around room temperature, these polymerizable groups do not react and polymerize by heating.
The monomer in the present invention is preferably a monomer in which at least one of the curable functional groups is an α, β-unsaturated ester group, and is a monomer represented by the general formula (1). More preferably.

（一般式（１）中、Ｒ¹は水素原子、または、ヒドロキシメチル基を表し、Ｘは有機基を表す。ｍは１〜３の整数を表し、ｎは１〜４の整数を表す。Ｙは、炭素−炭素不飽和結合を有する硬化性官能基、炭素−窒素不飽和結合を有する硬化性官能基、酸素原子を含む環状基を有する硬化性官能基または下記一般式（２）で表される基を表す。）

(In General Formula (1), R ¹ represents a hydrogen atom or a hydroxymethyl group, X represents an organic group, m represents an integer of 1 to 3, and n represents an integer of 1 to 4. Y Is represented by a curable functional group having a carbon-carbon unsaturated bond, a curable functional group having a carbon-nitrogen unsaturated bond, a curable functional group having a cyclic group containing an oxygen atom, or the following general formula (2): Represents a group.

（Ｒ²はそれぞれアルキル基またはアリール基を表す。）

(R ² represents an alkyl group or an aryl group, respectively.)

The organic group represented by X represents a 2-7 valent organic group, and is preferably a 3-6 valent organic group. Either aliphatic or aromatic may be used, and the total carbon number thereof is preferably 2 to 20, and more preferably 3 to 9. By setting the total number of carbon atoms in the range of 3 to 9, the functional group density is increased, the crosslink density of the cured film can be improved, and the low molecular weight can be designed, so the viscosity of the composition of the present invention is more preferable. It can be a range. Further, the organic group may be blocked by an oxygen atom, a sulfur atom, an ester group, or a urethane group. Specific examples include an alkyl chain having 3 to 9 carbon atoms, a propanetriol skeleton, a pentaerythritol skeleton, an aliphatic cyclic skeleton represented by a cyclohexane ring, a cyclopentane ring, a benzene skeleton, and the like.
The curable functional group having a carbon-carbon unsaturated bond represented by Y may be either a double bond or a triple bond, and may have a substituent on the unsaturated bond, either a chain or a ring. It may be. The total carbon number is preferably 2-18.
Y includes vinyl ether group, allyl ether group, allyl ester group, cyclohexenyl group, cyclopentenyl group, dicyclopenitenyl group, styryl group, methacryloyloxy group, methacryloylamide group, acrylamide group, vinylsilane group, N-vinyl complex. Examples thereof include a cyclic group and a maleimide group, and an allyl ether group, a cyclohexenyl group and a dicyclopentenyl group are preferable, and an allyl ether group and an allyl ester group are more preferable.

  Examples of the curable functional group having a carbon-nitrogen unsaturated bond represented by Y include an isocyanate group and a nitrile group.

  Examples of the curable functional group containing a cyclic group containing an oxygen atom represented by Y include an oxirane ring, an oxetane ring, and an ethylene carbonate group. More preferred are an oxirane ring and an oxetane ring.

m is preferably 1 to 3, more preferably 1 or 2, and n is preferably 1 to 4, more preferably 1 to 3. When m is 2 or more, the plurality of R ¹ may be the same or different from each other. When n is 2 or more, the plurality of Y may be the same or different.

The alkyl group represented by R ² is preferably an alkyl group having 1 to 8 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a benzyl group. As the aryl group, an aryl group having 6 to 12 carbon atoms is preferable. Examples of such an aryl group include a phenyl group, a p-tolyl group, and a p-chlorophenyl group.

  In the present invention, it is particularly preferable that at least one of Y is an allyl ether group or an allyl ester group, and the sum of n and m is 3 to 6, and at least one of Y is an allyl ether group or an allyl ester. It is more preferable that the sum of n and m is 3 to 6, and X is an organic group having 3 to 9 carbon atoms in total. By adopting such a monomer, the crosslink density of the cured film can be improved, the mechanical properties and solvent resistance of the cured film can be improved, and the viscosity of the composition is set within a preferred range. The pattern accuracy can be improved.

 The compound represented by the general formula (1) is also preferably a compound represented by any one or more of the following general formulas (3) to (5).

（一般式（３）〜（５）中、Ｒ³はそれぞれ水素原子またはメチル基を表し、Ｒ⁴はそれぞれメチル基またはエチル基を表す。）

(In general formulas (3) to (5), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a methyl group or an ethyl group, respectively.)

  Here, although the preferable example of the monomer in this invention is shown, it cannot be overemphasized that this invention is not what is limited to these.

Other polymerizable monomers The composition of the present invention may further contain other polymerizable monomers for the purpose of improving the composition viscosity, film hardness, flexibility and the like. A polymerizable unsaturated monomer having one saturated bond-containing group (monofunctional polymerizable unsaturated monomer) is preferably 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, benzyl (meth) acrylate, butanediol mono (meth) acrylate Rate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, ethylene oxide modified (hereinafter referred to as “EO”) cresol (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) ) Acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclohentanyl (meth) acrylate, dicyclo Pentanyloxyethyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate Methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, Nonylphenoxy polypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, epichlorohydrin (hereinafter referred to as “ECH”) modified phenoxy acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol ( (Meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene Glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, tert-butyl (meta ) Acrylate, tribromophenyl (meth) acrylate, EO-modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate, p-isopropenylphenol, styrene, α-methylstyrene, acrylonitrile, vinylcarbazole, urethane (meth) acrylate Is exemplified.

Furthermore, it is also preferable to use a polyfunctional polymerizable unsaturated monomer having two or more ethylenically unsaturated bond-containing groups as another polymerizable monomer.
Examples of the bifunctional polymerizable unsaturated monomer having two ethylenically unsaturated bond-containing groups that can be preferably used in the present invention include diethylene glycol monoethyl ether (meth) acrylate, 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, dimethylol tricyclodecane di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, EO Modified tripropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate, dipropylene glycol di (meth) acrylate, divinyl ethyl And urea (divinylpropylene urea) and urethane (meth) acrylate.

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

 As urethane (meth) acrylate mentioned above, mono (meth) acrylate and polyfunctional acrylate can be used. Specific compounds include U-2PPA, UA-4100, UA-5201, U-4H, U-4HA, U-6HA and U-15HA manufactured by Shin-Nakamura Chemical Co., Ltd.

  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 other polyfunctional polymerizable monomer is blended within a range to achieve the object of the present invention. Can do. Examples of the polyfunctional oligomer having photo-radical polymerizability include various acrylate oligomers such as polyester acrylate, polyurethane acrylate, polyether acrylate, and polyepoxy acrylate.

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

  Examples of the epoxy compound that can be preferably used include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S. Diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin tri 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.

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

  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 other polymerizable monomer used in the present invention, a vinyl ether compound may be used in combination.
The vinyl ether compound may be appropriately selected. For example, 2-ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, diethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, 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.

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

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

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

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

  The other polymerizable monomer is preferably contained in the composition in the range of 10 to 90% by mass, and more preferably in the range of 20 to 80% by mass.

Next, a preferable blend form of the monomer and other polymerizable monomer in the present invention (hereinafter, these may be collectively referred to as “polymerizable unsaturated monomer”) will be described. The composition of the present invention has two or more kinds of curable functional groups having different reactivities in the same molecule, and at least one of the curable functional groups is an α, β-unsaturated ester group. It is preferable that the body is an essential component and contains other polymerizable monomers.
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.
Since the 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.

The composition of the present invention preferably has a surface tension in the range of 18 to 30 mN / m, and more preferably in the range of 20 to 28 mN / m. By setting it as such a range, the effect of improving surface smoothness is acquired.
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 other monofunctional and / or bifunctional monomers as described above as reactive diluents, the organic solvent for dissolving the components of the composition of the present invention is It is not always necessary to contain. In addition, if an organic solvent is not included, a baking process for the purpose of volatilization of the solvent is not necessary, so that there is a great merit that it is effective for simplifying the process. Therefore, in the composition of the present invention, the content of the organic solvent is preferably 3% by mass or less, more preferably 2% by mass or less, and it is particularly preferable not to contain it. As described above, the composition of the present invention does not necessarily contain an organic solvent. However, in the case of dissolving a compound that does not dissolve in the reactive diluent as the composition of the present invention, or when finely adjusting the viscosity. Any of these may be added. The organic solvent that can be preferably used in the composition of the present invention is a solvent generally used in curable compositions for optical nanoimprints and photoresists, which dissolves and uniformly disperses the compound used in the present invention. There is no particular limitation 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.

  In the composition of this invention, it is preferable not to contain the compound whose molecular weight exceeds 1000. By setting it as such a composition, the viscosity rise of a composition can be suppressed. The molecular weight referred to here is calculated from the molecular formula of a compound having a fixed structure, and in the case of a complex of a compound having a plurality of structures such as a polymer compound, the molecular weight measured by GPC method (polystyrene conversion). .

(B) Photopolymerization initiator The composition of the present invention preferably contains a photopolymerization initiator. 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. Until now, 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, but for nanoimprinting. A preferred photopolymerization initiator and / or photoacid generator addition amount for the curable composition for photo-nanoimprints 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. In consideration of this point, the amount of the photopolymerization initiator added is optimized in these applications. On the other hand, in the composition of the present invention, the dye and / or pigment is not an essential component, and the optimum range of the photopolymerization initiator is different from that in the field of an ink jet composition or a liquid crystal display color filter composition. There is.

  As the photopolymerization initiator used in the present invention, one that has activity with respect to the wavelength of the light source to be used is blended, and one that generates appropriate active species is used.

  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® 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-trimethylbenzoylethoxyphenylphosphine oxide), ESACURE 1001M (1- [4-benzoylphenylsulfanyl] phenyl] -2-methyl-2- (4-methyl), available from ESACUR Nippon Siebel Hegner Phenyls Honyl) propan-1-one, N-1414 Adeka optomer (registered trademark) N-1414 (carbazole phenone system), Adeka optomer (registered trademark) N-1717 (acridine system) available from Asahi Denka Co., Ltd. Adekaoptomer (registered trademark) N-1606 (triazine type), TFE-triazine (2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1 manufactured by Sanwa Chemical Co., Ltd.) , 3,5-triazine), TME-triazine (2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5, manufactured by Sanwa Chemical Co., Ltd.) -Triazine), MP-triazine (2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine) manufactured by Sanwa Chemical, Midori Chemical TAZ-113 (2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), TAZ-108 (2- (3 , 4-dimethoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine), benzophenone, 4,4'-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzoyl-4'- Methyl diphenyl sulfide, 4-phenylbenzophenone, ethyl Michler's ketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, thioxa Nton ammonium salt, benzoin, 4,4'-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetophenone, diethoxyacetophenone and dibenzosuberone , Methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoyl biphenyl, 4-benzoyl diphenyl ether, 1,4-benzoylbenzene, benzyl, 10-butyl-2-chloroacridone, [4- (methylphenylthio) Phenyl] phenylmethane), 2-ethylanthraquinone, 2,2-bis (2-chlorophenyl) 4,5,4 ′, 5′-tetrakis (3,4,5-trimethoxyphenyl) 1,2′-biimidazole, 2,2-bis (o-chlorophenyl) 4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, tris (4-dimethylaminophenyl) methane, ethyl -4- (dimethylamino) benzoate, 2- (dimethylamino) ethyl benzoate, butoxyethyl-4- (dimethylamino) benzoate, and the like.

  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.

(C) Antioxidant Furthermore, the composition of the present invention contains a known antioxidant. The content of the antioxidant used in the present invention is preferably 10% by mass or less, more preferably 0.01 to 10% by mass, and further preferably 0.2 to 5% by mass in the entire composition. It is. When using 2 or more types of antioxidant, the total amount becomes the said range.
The antioxidant suppresses fading caused by heat or light irradiation and fading caused by various oxidizing gases such as ozone, active oxygen, NO _x , SO _x (X is an integer). 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 film thickness reduction 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, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like.
In the present invention, from the viewpoint of improving the permeability of the cured film and reducing the film thickness, hindered phenol-based antioxidants, hindered amine-based antioxidants, and thioether-based antioxidants are particularly preferable, hindered phenol-based antioxidants and A hindered amine antioxidant is more preferable.

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

(D) Release agent For the purpose of further improving releasability, a release agent is 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 release agents, solid waxes such as polyethylene wax, amide wax, and Teflon powder (Teflon: registered trademark), fluorine-based compounds, and phosphate-based compounds. Can also be used. Moreover, these mold release agents can be adhered to the mold.
The release agent used in the present invention is preferably a silicone release agent, and more preferably a modified silicone oil release agent.

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

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

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

  Examples of commercially available modified silicone oils include TSF4421, XF42-334, XF42-B3629, XF42-A3161, manufactured by GE Toshiba Silicone, BY16-846, SF8416, SH203, SH230, SF8419, manufactured by Toray Dow Corning. SF8422, Shin-Etsu Chemical KF-410, KF-412, KF-413, KF-414, KF-415, KF-351A, KF-4003, KF-4701, KF-4917, KF-7235B, X-22 -2000, X-22-3710, X-22-7322, X-22-1877, X-22-2516, PAM-E and the like.

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

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

Other components In addition to the above-described components, the composition of the present invention includes a surfactant, a silane coupling agent, a polymerization inhibitor, an ultraviolet absorber, a light stabilizer, an anti-aging agent, a plasticizer, and adhesion promotion. An agent, a thermal polymerization initiator, a colorant, elastomer particles, a photoacid growth agent, a photobase generator, a basic compound, a flow regulator, an antifoaming agent, a dispersant, and the like may be added.

Surfactant The composition of the present invention may contain a surfactant. The surfactant used in the present invention contains, for example, 0.001 to 5% by mass, preferably 0.002 to 4% by mass, and more preferably 0.005 to 3% by mass in the entire composition. It is. When using 2 or more types of surfactant, the total amount becomes the said range. If the surfactant is less than 0.001 in the composition, the effect of coating uniformity is insufficient. On the other hand, if it exceeds 5% by mass, the mold transfer characteristics are deteriorated, which is not preferable.
The surfactant preferably contains at least one of a fluorine-based surfactant, a silicone-based surfactant, and a fluorine / silicone-based surfactant. Both the fluorine-based surfactant and the silicone-based surfactant or fluorine -More preferably, a silicone-based surfactant is included, and most preferably, a fluorine-silicone-based surfactant is included.
Here, the fluorine / silicone surfactant refers to one having both requirements of a fluorine surfactant and a silicone surfactant.
By using such a surfactant, the composition of the present invention can be applied to a silicon wafer for manufacturing a semiconductor device, a glass square substrate for manufacturing a liquid crystal device, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, and tantalum. Striations and scale-like patterns (such as alloy films, silicon nitride films, amorphous silicon films, tin oxide-doped indium oxide (ITO) films, tin oxide films, etc.) The purpose is to solve the problem of poor coating such as uneven drying of the resist film), and the fluidity of the composition into the cavity of the mold recess is improved, the peelability between the mold and the resist is improved, and between the resist and the substrate It becomes possible to improve the adhesion and to lower the viscosity of the composition. 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 Florard FC-430 and FC-431 (Sumitomo 3M), trade names Surflon “S-382” (Asahi Glass Co., Ltd.), EFTOP “ EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 "(manufactured by Tochem Products), trade names PF-636, PF-6320, PF-656, PF-6520 ( All are OMNOVA), brand names FT250, FT251, DFX18 (all manufactured by Neos Co., Ltd.), brand names Unidyne DS-401, DS-403, DS-451 (all manufactured by Daikin Industries, Ltd.) ), Trade name Megafuk 171, 172, 173, 178K, 178A (all manufactured by Dainippon Ink & Chemicals, Inc.). Examples of nonionic silicon 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 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. 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 nanoimprints.

  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).

  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. Here, the composition of the present invention is usually cured by light irradiation or heat, preferably by light irradiation and heat. Specifically, a pattern forming layer comprising at least the composition of the present invention is applied on a substrate or a support, and dried as necessary to form a layer (pattern forming layer) comprising the composition of the present invention. 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 cured by light irradiation and heating. Usually, light irradiation and heating are performed a plurality of times. 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.

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

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 , Polyester film, polycarbonate film, polymer film such as polyimide film, TFT array substrate, PDP electrode plate, glass and transparent plastic substrate, conductive substrate such as ITO and metal, insulating substrate, silicone, silicone nitride, poly There are no particular restrictions on semiconductor fabrication substrates such as silicone, silicone oxide, and amorphous silicone. The shape of the substrate may be a plate shape or a roll shape.

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

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

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

Next, the molding material that can be used in the present invention will be described. In the optical nanoimprint 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 the optical imprint lithography applied to the present invention, a curable composition for optical nanoimprint is applied on a substrate, a light transmissive mold is pressed, light is irradiated from the back of the mold, and the curable composition for optical nanoimprint is applied. The object is cured. Moreover, the curable composition for optical nanoimprint can be apply | coated on a transparent substrate, a mold can be pressed, light can be irradiated from the back surface of a mold, and the curable composition for optical nanoimprint can also be hardened.
The light irradiation may be performed in a state where the mold is attached, or may be performed after the mold is peeled off, but in the present invention, it is preferably performed in a state where the mold is adhered.

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

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

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

  When performing photoimprint lithography using the present invention, it is usually preferred that the mold pressure be 10 atmospheres or less. It is preferable to set the mold pressure to 10 atm or less because the mold and the substrate are less likely to be deformed and the pattern accuracy tends to be improved, and because the pressure is low, the apparatus can be reduced. The mold pressure is preferably selected in a region where the mold transfer uniformity can be ensured within a range in which the remaining film of the curable composition for photo-nanoimprinting 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 and the tackiness of the cured film.
In the photoimprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually room temperature, but the light irradiation may be performed while heating in order to increase the reactivity. As a pre-stage of light irradiation, if it is kept in a vacuum state, it is effective in preventing bubble mixing, suppressing the decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the curable composition for optical nanoimprinting. It may be irradiated. 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 is usually performed in the range of 0 ° C to 100 ° C. Filtration may be performed in multiple stages or repeated many times. Moreover, the filtered liquid can be refiltered. Materials used for filtration can be polyethylene resin, polypropylene resin, fluorine resin, nylon resin, etc., but are not particularly limited.

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

  The composition of the present invention can also be applied as an etching resist for semiconductor integrated circuits, recording materials, flat panel displays and the like.

  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.

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

<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 or more and less than 5 mPa · s, 50 rpm for 5 mPa · s or more and less than 10 mPa · s, 20 rpm for 30 mPa · s or more for 10 mPa · s or more, and 60 mPa · s for 30 mPa · s or more. 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.

<Observation of pattern accuracy>
Each composition consisting of a monomer, a photopolymerization initiator, an antioxidant and a release agent shown in the following table was prepared and spin-coated on a glass substrate so as to have a film thickness of 3.0 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. / 240 mJ / cm ² from the surface of a mold having a space pattern and having a groove depth of 4.0 μm and 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. The obtained resist pattern was completely cured by heating in an oven at 230 ° C. for 30 minutes.
The pattern shape after the transfer was observed with a scanning electron microscope or an optical microscope, and the pattern shape was evaluated as follows.
A: Almost the same as the pattern of the original plate that is the basis of the pattern shape of the mold. B: There is a portion that is partially different from the pattern shape of the original plate that is the basis of the pattern shape of the mold (the range of the original pattern is less than 10%). C: There is a part (a range of 10% or more and less than 20% of the pattern of the original plate) that is partly different from the original pattern shape of the mold pattern shape. D: Clearly different from the original pattern of the mold pattern shape. Or the film thickness of the pattern differs from the original pattern by 20% or more.

<Evaluation of peelability>
Using the same sample used for pattern accuracy observation, observe whether the composition component is attached to the mold used for pattern formation with a scanning electron microscope or optical microscope, and evaluate the peelability as follows: did.
A: Adhesion of the curable composition to the mold was not recognized at all.
B: Slight adhesion of the curable composition was observed on the mold.
C: Adhesion of the curable composition of the mold was clearly recognized.

<Evaluation of hardness>
Each composition was spin-coated on a glass substrate so that the film thickness was in the range of 3 to 10 μm, the mold was not pressure-bonded, and was exposed at an exposure amount of 240 mJ / cm ² in a nitrogen atmosphere. The film cured by heating for 30 minutes was measured for dynamic hardness using a micro hardness tester manufactured by Shimadzu Corporation. The measurement conditions were a triangular pyramid indenter, a load of 1 mN, and a holding time of 1 second.
Dynamic hardness A: 32 or more B: 28 or more, less than 32 C: 25 or more, less than 28 D: less than 25

<Evaluation of transmittance>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm, the mold was not pressure-bonded, and was exposed at an exposure amount of 240 mJ / cm ² in a nitrogen atmosphere, and then heated in an oven at 230 ° C. for 270 minutes. The film thus cured was measured for transmittance at 400 nm using UV-2400PC manufactured by Shimadzu Corporation.
Transmittance A: 97% or more B: 95% or more, less than 97% C: 90 or more, less than 95% D: less than 90

<Solvent resistance test>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm, the mold was not pressure-bonded, and was exposed at an exposure amount of 240 mJ / cm ² in a nitrogen atmosphere, and then heated in an oven at 230 ° C. for 30 minutes. The cured film was immersed in an N-methylpyrrolidone solvent at 25 ° C. for 30 minutes, and changes in the cured film before and after immersion were evaluated as follows.
A: Change in film thickness less than 1% B: Change in film thickness 1% or more and less than 2% C: Change in film thickness 2% or more and less than 10% D: Surface roughness occurs

<Monomer having two or more curable functional groups with different reactivity in the same molecule>
Q-5: Compound (M-24) (3-Ethyl-3-oxetanyl) methyl acrylate (Biscoat OXE10: manufactured by Osaka Organic Chemical Industry Co., Ltd.)
Q-6: Compound (M-29) 3-trimethoxysilylpropyl acrylate (KBM-5103: manufactured by Shin-Etsu Chemical Co., Ltd.)
Q-10: Compound (M-34) Acrylic acid-3,5-diallyloxycyclohexyl ester Q-11: Compound (M-38) 3,5-bis (allyloxycarbonyl) phenyl acrylate Q-12: Compound (M -39) 4-allyloxycarbonylphenyl acrylate Q-13: compound (M-40) allyloxycarbonyl-3,5-bis (acryloyloxy) benzene Q-14: compound (M-41) bisacryloyloxymethylpropionic acid Allyl Q-15: Compound (M-42) Bisallyloxycarbonylethyl acrylate Q-16: Compound (M-43) Allyloxycarbonylmethyl acrylate Q-17: Compound (M-44) Allyloxycarbonylethyl acrylate

<Other monofunctional monomers>
R-1: benzyl acrylate (Biscoat # 160: manufactured by Osaka Organic Chemical Co., Ltd.)
R-2: 2-naphthyl acrylate R-3: 1-naphthylmethyl acrylate

<Other bifunctional monomers>
S-01: Neopentyl glycol diacrylate <other trifunctional or higher monomer>
S-10: Trimethylolpropane triacrylate (Aronix M-309: manufactured by Toagosei Co., Ltd.)
S-11: 1,3,5-trisacryloyloxybenzene
<Amount of other trifunctional or more>
S-12: 4-functional urethane acrylate (U-4HA: manufactured by Shin-Nakamura Chemical Co., Ltd.)

<Other polymerizable monomers>
S-23: HOA-MS (2-acryloyloxyethyl succinic acid, manufactured by Kyoeisha Chemical Co., Ltd.)

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

<Surfactant>
W-1: Non-fluorinated surfactant (manufactured by Takemoto Yushi Co., Ltd .: Pionein D6315)
W-2: Fluorosurfactant (manufactured by DIC Corporation: MegaFuck F780F)

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

<Silicone oil>
X-1: X-22-3710 (manufactured by Shin-Etsu Chemical Co., Ltd.)
X-2: X-22-2000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
X-3: KF-410 (manufactured by Shin-Etsu Chemical Co., Ltd.)
X-4: KF-351A (manufactured by Shin-Etsu Chemical Co., Ltd.)
X-5: PAM-E (manufactured by Shin-Etsu Chemical Co., Ltd.)

  The above-mentioned monomers were blended so as to have the composition shown in the above table to prepare the compositions of the examples, and the viscosity, pattern accuracy, peelability, hardness, transmittance, and solvent resistance were measured. The results are shown in the table described later.

Comparative Example 1
The composition described in Example 6 of the inkjet composition disclosed in International Publication No. WO 2004/099272 is performed in the same manner as in this Example, and pattern accuracy, peelability, hardness, transmittance, solvent resistance Measured for sex. The composition and test results of the composition are shown below.

Comparative Example 2
The composition described in Example 1 of the nanoimprinting composition disclosed in Japanese Patent Application Laid-Open No. 2007-84625 is performed in the same manner as in this example, and pattern accuracy, peelability, hardness, transmittance, and solvent resistance are performed. Was measured. The composition and test results of the composition are shown below.

Comparative Example 3
The composition described in Example 3 of the photocurable composition disclosed in Japanese Patent Application Laid-Open No. 2005-255854 was measured in the same manner as in this example, and the pattern accuracy, hardness, transmittance, and solvent resistance were measured. did. The composition and test results of the composition are shown below.

Comparative Example 4
The composition described in Example 2 of the photocurable resin composition disclosed in Japanese Patent Application Laid-Open No. 2007-186570 was performed in the same manner as in this example, and the pattern accuracy, hardness, and transmittance were measured. The composition and test results of the composition are shown below.

Comparative Example 5
The composition described in Example 6 of the photocurable resin composition disclosed in Japanese Patent Application Laid-Open No. 2007-186570 was performed in the same manner as in this example, and the pattern accuracy, hardness, and transmittance were measured. The composition and test results of the composition are shown below.

  None of the above Comparative Examples 1 to 5 contains an antioxidant and a release agent. Moreover, Comparative Example 2 and Comparative Example 4 do not contain two or more kinds of curable functional groups having different reactivity.

  The composition of the present invention was excellent in any of pattern accuracy, peelability, hardness, and transmittance. On the other hand, the compositions of the comparative examples were all inferior in hardness. In Comparative Example 1, the pattern accuracy and transmittance were also inferior.

  According to the present invention, when used as a permanent film, it has become possible to provide a composition that is comprehensively excellent in terms of permeability and mechanical strength, peelability, pattern shape, coatability, and solvent resistance after heat curing. . Further, when used as a permanent film such as a transparent protective film or a spacer, it is possible to provide a composition having excellent residual film properties, light transmission properties, scratch resistance, mechanical properties such as solvent resistance, and the like.

Claims (16)

 (A) A curable composition for nanoimprints containing a monomer having at least two kinds of curable functional groups having different reactivity in the same molecule, (C) an antioxidant, and (D) a release agent. .  The curable composition for nanoimprints according to claim 1, wherein the (D) release agent is a silicone release agent.  The curable composition for nanoimprints according to claim 1, wherein the (D) release agent is a modified silicone oil.  The curable composition for nanoimprints according to any one of claims 1 to 3, wherein the (D) release agent is contained in the composition in a proportion of 0.001 to 10% by mass.   The curable composition for nanoimprints according to any one of claims 1 to 4, wherein at least one of the curable functional groups is an α, β-unsaturated ester group.   It is a curable composition for nanoimprints of any one of Claims 1-5, Comprising: The composition whose viscosity of this composition is the range of 3-18 mPa * s. The curable composition for nanoimprints according to any one of claims 1 to 6, wherein the monomer is represented by the following general formula (1).

(In General Formula (1), R ¹ represents a hydrogen atom or a hydroxymethyl group, X represents an organic group, m represents an integer of 1 to 3, and n represents an integer of 1 to 4. Y Is represented by a curable functional group having a carbon-carbon unsaturated bond, a curable functional group having a carbon-nitrogen unsaturated bond, a curable functional group having a cyclic group containing an oxygen atom, or the following general formula (2): Represents a group.

(R ² represents an alkyl group or an aryl group, respectively.)
Curable composition.  The curable composition for nanoimprints according to any one of claims 1 to 7, comprising a polymerizable monomer other than the monomer (A) and a photopolymerization initiator.  The curable composition for nanoimprints according to any one of claims 1 to 8, which does not contain a compound having a molecular weight exceeding 1000.  The curable composition for nanoimprints according to any one of claims 1 to 9, wherein the surface tension of the composition is in the range of 18 to 30 mN / m.  The curable composition for nanoimprints according to any one of claims 1 to 10, which is cured by light irradiation and heating.   Furthermore, the curable composition for nanoimprints of any one of Claims 1-11 containing surfactant.  Hardened | cured material which hardened the curable composition for nanoimprints of any one of Claims 1-12.  The manufacturing method of hardened | cured material including hardening the curable composition for nanoimprints of any one of Claims 1-12 by performing light irradiation and heating in multiple times.  The member for liquid crystal display devices using the hardened | cured material of Claim 13.  The manufacturing method of the member for liquid crystal display devices including hardening the composition of any one of Claims 1-12 by performing light irradiation and heating in multiple times.