TW200923003A - Curable composition for nanoimprint, cured product and production method thereof - Google Patents

Abstract

This invention is to provide a curable nanoimprint composition offering cured materials of excellent transparency. The curable nanoimprint composition comprises (A) a monomer having at least 2 curable functional groups of different reactivity in a molecule, and (C) an antioxidant.

Description

[Technical Field] The present invention relates to a curable composition for nanoimprint, a cured product, a method for producing the same, and a member for a liquid crystal display device using the cured product, and a method for producing the same. [Prior Art] The embossing technique of the conventional embossing method for optical disc production has been developed, and the original mold (generally called a mold, a stamper, a template) having a concave-convex pattern is pressed against the photoresist to cause mechanical deformation thereof. The technology of precision transfer of fine patterns. Once the mold is produced, it is possible to easily reproduce a fine structure such as a nanostructure, which is economical and has a processing technique that is less harmful to waste. In recent years, applications in various fields have been expected. There are two proposals for nanoimprinting, using thermoplastic resins as materials to be processed (S. Chou et al.: Appl. Phys. Lett., Vol. 67, 3114 (19.9)), and using photon pressure. A hardenable composition is printed (M. Colbun et al.: Pr.c. SPIE, Vol. 3, 67, 379 (1, 999)). The hot type nano embossing presses the mold to a polymer resin heated to a temperature higher than the glass transition temperature, and after cooling, the mold is detached to transfer the resin finely structured on the substrate. Since a variety of resin materials and glass materials can be used, applications in various fields are expected. For example, U.S. Patent No. 5,772,905, and U.S. Patent No. 5,95,2,166, the disclosure of which is incorporated herein by reference. Further, by irradiating light through a transparent mold and photo-hardening the light-hardening composition of the photo-nano imprinting composition, room temperature imprinting is possible. Recently, there have been reports on new developments such as the nano-casting method combining the advantages of the two, and the production of the three-dimensional laminated structure 200923003. With such a nanoimprint method, you can imagine the following applications. First, the molded article itself has functions and can be applied to various elemental components of nanotechnology, and various micro-nano optical components, high-density recording media, optical films, structural members of flat displays, and the like. Secondly, the micron structure and the nanostructure are integrally formed at the same time, or a simple interlayer structure is used to construct a laminate structure, which can be applied to a producer of //TAS or a biochip. Thirdly, it can be used for the fabrication of high-density semiconductor integrated circuits or the manufacture of liquid crystal display transistors by replacing the conventional photolithography with high-precision position matching and high integration. In recent years, the practical development of the nanoimprint method for these applications is becoming increasingly active. First, an application example of the nanoimprint method will be described, and an application example of a high-density semiconductor integrated circuit will be described. In recent years, the miniaturization and integration of semiconductor integrated circuits have progressed, and the pattern transfer technology for microfabrication has been realized, and the precision of the photolithographic apparatus has progressed. However, the photolithography approaching the limit due to the approaching approach to the wavelength of the exposure source. Therefore, in order to further promote miniaturization and high precision, instead of photolithography, one of the charged particle beam devices and the use of an electron beam drawing device have been used. The pattern formation using the electron beam is different from the one in the pattern formation using a light source such as a 1-line or excimer laser, and the method of gradually drawing the mask pattern is adopted, so that the more the pattern is drawn, the exposure (drawing) is performed. The more time consuming, time consuming pattern formation becomes a disadvantage. Therefore, as the degree of integration increases from 256M, 1G to 4G, the pattern formation time is also prolonged in proportion, and there is a significant deterioration in productivity. Therefore, in order to increase the speed of the electron beam drawing device, there is a combination of various types of photomasks including an electron beam which is irradiated with an electron beam to form a complicated shape, and the development of the pattern irradiation method. On the other hand, on the other hand, the electron beam drawing device needs to be enlarged in 200923003, and a mechanism for controlling the position of the mask with higher precision is also necessary, and there is a disadvantage that the cost of the device is increased. On the other hand, there is a proposal to use nanoimprint as a technique for forming a fine pattern at a low cost. For example, U.S. Patent No. 5,772,905 and U.S. Patent No. 5,259,926 disclose the use of a tantalum wafer as a stamper to form a nano-imprint technique of a fine structure of 25 nm or less. Japanese Patent Laid-Open Publication No. 2005-5-27119 discloses a composite composition for nanoimprinting in the field of semiconductor lithography. The micro-mold making technology, mold durability, mold manufacturing cost, mold peelability from resin, imprint uniformity, alignment accuracy, inspection technology, etc., have begun to be active in the use of semiconductor integrated circuit manufacturing. Next, an application example of nanoimprinting for a flat panel display such as a liquid crystal display (LCD) or a plasma display (PDP) will be described. As the LCD substrate and the PDP substrate tend to be larger and more refined, the photolithographic embossing method has been used in recent years as an inexpensive lithography method which replaces the conventional photolithography method for manufacturing a thin film transistor (TFT) or an electrode plate. Received attention. Therefore, it has been necessary to develop a photocurable photoresist which replaces the etching photoresist for the conventional photolithography method. Further, as a structural member such as an LCD, the transparent protective film material described in Japanese Laid-Open Patent Publication No. 2005-1 97699, No. 2005-30 No. 289, or the special opening No. 2 0 0 5 - 3 0 1 2 8 9 As discussed in the bulletin, the discussion of the application of photon imprinting to spacers and the like has also begun. The photoresist used for such a structural member is different from the above-described etching photoresist, and may eventually remain in the display, and may be a permanent photoresist or a permanent film. A permanent film using conventional photolithography is described. The permanent film is different from the touch resist and directly remains on the elements such as the flat display panel. The permanent film on the TFT substrate using 200923003 is specifically described. In the liquid crystal panel, a thin film transistor is formed on the glass substrate, and a transparent protective film layer (permanent film) for protecting the thin film transistor is formed thereon. The liquid crystal transparent electrode ITO (indium tin oxide) is driven by a sputtering voltage. The protective film is such that the thin film transistor can be electrically contacted with the ITO, and the contact hole is formed by photolithography before the ITO sputtering, and is post-baked and hardened to ensure heat resistance. Positive materials are used for materials. Next, a transparent permanent film for a color filter will be described. In a general liquid crystal display, a black matrix using a photoresist containing chromium oxide and carbon black is formed on a glass substrate, followed by formation of R, G, and B color filter layers on the front side. The color filter is coated with a photocurable resin or the like, and the electrode drawing portion or the like is removed by photolithography, and subjected to post-baking heat treatment to form a protective film (permanent film). The permanent film for the color filter can reduce the interlayer drop of the color filter and improve the high-temperature processing resistance of the transparent electrode ITO when it is sputtered. In the case of a permanent color filter for color filters, a color filter is used to form a color filter using a photocurable resin such as a decyl alkoxylate polymer, a polyfluorene ketone polyimide, an epoxy resin or an acryl resin, or a thermosetting resin. A permanent film (Japanese Unexamined Patent Publication No. Hei. No. 2000-3971-3, No. Hei 6-43 643). The formation of a permanent film on a thin film transistor or a color filter has uniformity of coating film, adhesion of the substrate, high light transmittance after heat treatment at least over 200 ° C, and flattening Characteristics of characteristics, solvent resistance, and scratch resistance. The spacer which defines the gap of the element of the liquid crystal display is also a kind of permanent film. In the conventional photolithography, a photocurable composition composed of a resin, a photopolymerizable monomer and an initiator is generally widely used (Specially Opened No. 2004-24024 No. 1) Bulletin). The spacer is generally formed on a color filter substrate to form a color filter 200923003, or after forming a protective film for the color filter, a photocurable material is applied, and a pattern of about 10 to 20/zm is formed by photolithography. And formed by post-baking hardening. The spacer has requirements for high mechanical properties, hardness, and 'pattern accuracy, adhesion, and the like for external pressure. However, the present invention has been used for the transparent protective film of nanoimprint or the preferred composition of the photocurable composition for forming a spacer, and the uniformity of the coating film, due to the enlargement of the substrate, regarding the substrate There are strict requirements for uniformity of coating film thickness in the middle and peripheral portions, or various dimensions such as dimensionality, film thickness, and shape with high resolution. In the field of manufacturing a liquid crystal display element of a glass substrate, a method in which the photoresist coating method is dropped after the center is applied (Electronic Journal 121-123 (2002)). Although the coating method of rotating after the center dripping can obtain good coatability, for example, a large substrate of '1 m square, the amount of light resisted during rotation is quite large, and the substrate is broken and caused by high-speed rotation. To ensure the problem. In the method of rotating after the center is dripped, the coating speed is rotated at the time of rotation and the amount of photoresist applied. If it is to be used in a larger 5th generation substrate, then if there is no general-purpose motor with the necessary acceleration, the motor must be specially made. The problem of increasing costs. The size of the substrate and the device is large, for example, the coating uniformity is ±3%, the bonding time is 60 to 70 seconds/piece, etc., and the required performance in coating is almost impossible to change. Therefore, it is difficult to apply the requirements other than the coating uniformity after the central dripping. correspond. Based on the fact that the ij is applied to the 4th generation substrate, the new coating method of the large substrate from the 5th generation substrate has a proposal of the discharge nozzle type photoresist coating method. The spit-out spray consists of a heating image for the purpose of seeing the central part of the faucet and evenly using the small series of No.8 to evenly dispose of the sticking. The step of the strip is shaped, and the photoresist nozzle type 200923003 is used to make the sputter. A method in which a nozzle and a substrate are relatively moved to apply a photoresist composition to a substrate coated surface, and for example, a discharge port having a plurality of orifices arranged in a row and a slit-shaped discharge port are used, and the photoresist composition can be discharged in a strip shape. A proposal for a method of spouting a nozzle or the like. There is also a proposal for a method of uniformly coating a photoresist composition on a substrate coated surface by a discharge nozzle type, and rotating the substrate to adjust the film thickness. Therefore, in order to replace the photoresist of the conventional photolithography by the nanoimprint composition, it is suitable for the field of manufacture of these liquid crystal display elements, and the uniformity of coating to the substrate becomes important. For the production of a semiconductor integrated circuit, a positive photoresist of a liquid crystal display, a pigment dispersion resist for a color filter, etc., it is known to add a fluorine-based and/or an anthrone-based surfactant to solve the problem of coating properties. Specifically, there is a coating defect such as a ridge pattern or a scaly pattern (the photoresist film is unevenly dried) which is generated when the substrate is coated (Japanese Unexamined Patent Publication No. Hei No. Hei 7-230165, No. 2000-181055, No. 2004-9424) Bulletin No. 1). In order to improve the abrasion resistance and coating property of a protective film such as a disc or a magneto-optical disk, there is a disclosure of a fluorine-free or an fluorenone-based surfactant in a solvent-free photocurable composition (Special opening 2 0 0 4 - 9 4 Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. In order to improve the ink discharge stability of the inkjet composition, a nonionic fluorine-based surfactant is added in the Japanese Patent Publication No. 2005-8759. Japanese Laid-Open Patent Publication No. 2003-160350-A discloses that a paint composition for thick film coating, such as a bristles, a pen, a bar coater, and the like, is processed by a full-phase drawing mold for embossing processing. An example in which the surfactant of the bond is 1% or more, preferably 3% or more, and the water swelling property of the cured film is improved. Thus, a technique of adding a surfactant to a protective film such as a positive-type resist, a pigment dispersion resist for color filter production, or a magneto-optical disk, and improving the applicability is a conventional technique of -10-200923003. As an example of the ink-jet or paint composition, it is known that a surfactant is added to a solvent-free photocurable resin, and a technique of adding a surfactant to improve the properties in each application is also known. JP-A-2007-84625 discloses an example in which a photocurable resin containing a fluorine-containing surfactant is used as an etching resist of a photon imprinting method when a semiconductor integrated circuit is produced. However, there is no known method for improving the substrate coating property of a photocurable nanoimprint resist composition which is not used as a pigment, a dye or an organic solvent for a permanent film. The photon imprinting must improve the fluidity of the composition in the cavity of the mold, and it is necessary to improve the releasability of the mold, the peeling property between the mold and the photoresist, and the adhesion between the photoresist and the substrate. This fluidity, peelability, and adhesion are difficult to achieve. The prior art for photon imprinting is described in more detail. Photon imprinting is generally applied to tantalum wafers, quartz, glass, thin films or other materials, such as ceramic materials, metals or polymers, to have fine irregularities having a pattern size of about several tens of nanometers to several tens of micrometers. The mold is pressed against the pressurization, and after the composition is cured by irradiating light in a pressurized state, the film is released from the mold to obtain a pattern for transferring the pattern. For this reason, at least one of the substrate or the mold is required to be transparent in order to smoothly irradiate the light nano-imprint. Usually, the light is irradiated from the side of the mold, and the mold material is usually made of an inorganic material such as quartz or sapphire which is transparent to UV or a translucent resin. The light is irradiated from the mold side, and it is effective in constructing a structure by a photon imprinting method on a substrate having a light-shielding property (specifically, a color filter for an LCD). The light nano-pressure method has (1) no need for heating/cooling procedures, and can expect high productivity, (2) due to the use of liquid composition, low pressure is -11 - 200923003 Printing, (3) dimensional changes caused by thermal expansion, (4) mold is transparent and easy to align, (5) strong advantages such as three-dimensional crosslinked body can be obtained after hardening. It is especially suitable for semiconductor micromachining applications where alignment accuracy is required, and for microfabrication applications in the field of flat panel displays. Other features of the photon imprinting method are that, compared to the conventional photolithography, the resolution is independent of the wavelength of the light source, and the nanometer-level microfabrication does not require an expensive device such as a stepper or an electron beam drawing device. On the other hand, the photon imprint must have an equal magnification of the mold. Since the mold is in contact with the resin, the durability and cost of the mold need to be considered. In this way, when the pattern of micron or nanometer size is imprinted by a large area by heat and/or photon imprinting, not only the uniformity of the pressing force but also the flatness of the original disc (mold) is required, and the composition is described above. The fluidity in the cavity of the mold and the composition characteristics of the press-out flow also need to be controlled. The mold for photon imprinting can be made of various materials such as metal, semiconductor, ceramic, SOG (SpinOn Glass) or a specific plastic. There is, for example, a proposal for a soft polydimethyl siloxane mold having a desired fine structure in International Publication No. WO99/22849. Since the mold forms a three-dimensional structure on one surface, various lithography methods can be used depending on the size of the structure and the resolution specifications thereof. Electron beam and X-ray lithography are commonly used for structural dimensions up to 300 nm. Laser direct exposure and UV lithography are used for larger structures. Regarding the photon imprint method, the releasability of the mold and the hardenable composition for photon imprinting is extremely important, and the surface treatment of the mold and the mold, specifically, 'hydrogenated sesquioxane, fluorinated ethylene propylene copolymer The mold is thought to solve the problem of adhesion, etc., and it is not. Here, a photocurable resin for photon embossing will be described. The photocurable resin suitable for use in Nai-12-200923003 embossing differs depending on the reaction mechanism, and can be mostly a radical polymerization type and an ionic polymerization type, or a mixture of these. Any of the compositions can be embossed, and generally a wide range of radical polymerization types are used (F. Xu et al.: SPIE Microlithography Conference, 5374, 232 (2004)). The radical polyunsal type is generally a composition comprising a monomer having a radically polymerizable ethyl group, a (meth) acrylonitrile group (m ο η 〇 m e r) or an oligomer and a photopolymerization initiator. The irradiated light is subjected to a chain polymerization by attacking a vinyl group by a radical generated by a photopolymerization initiator to form a polymer. A crosslinked structure is obtained by using a difunctional or higher polyfunctional monomer or oligomer as a component. D.; L Resnick et al.: J. Vac. Sci. Technol. B, Vol. 21. No. 6, 2624 (2003) discloses the use of low viscosity UV hardenable monomers, capable of low pressure, room temperature imprinting Composition. 1 Describe in detail the characteristics of materials used for photon imprinting. Material Requirements The characteristics vary with the application and the procedural characteristics are unrelated to the intended use. For example, 'The latest photoresist material manual, pages 1, 103 to 104 (2005, published by the intelligence agencies), the main requirements are coating properties, substrate adhesion, low viscosity (<5 mPa · s), and peelability. , low hardening shrinkage rate, quick hardenability, etc. Especially for low-pressure stamping and the necessary use of low residual film rate, it is known that high-viscosity materials are required. The required characteristics depending on the application include, for example, the refractive index and optical transparency of the optical member, the etching resistance of the etching resist, and the thickness of the residual film being reduced. How these characteristics are controlled and the balance of characteristics is the key to material design. At least the program material and the permanent film are greatly different depending on the required characteristics, and the material must be developed according to the program and use. Materials suitable for such light nanoimprinting applications are known, and the latest photoresist materials manual, pages 1, 1 03 to 1 04 (in 2005, published by the intelligence agencies) have a viscosity of about 60 m. Photohardenable material of P a · s (2 5 t ) -13- 200923003. Similarly, C M C publication: Development and Application of Nanoimprinting, pp. 159-160 (2006) discloses a fluorine-containing photosensitive resin having a viscosity of 14.4 mPa·s as a main component of methacrylic acid monoester. Thus, there are reports on the expectation of viscosity for the composition used for photon imprinting, and the design guidelines for materials suitable for each application have not been reported. An example of a photocurable resin used for photon imprinting has been described. Japanese Laid-Open Patent Publication No. 2004-59 No. 20-A No. 2004-5-9 8 discloses a photocurable resin containing a polymer having an isocyanate group for use in a relief-type full-phase diagram or a diffraction grating. Example of grain processing. JP-A-2006- 1 1 4 8 82 discloses a curable composition for photon imprinting containing a polymer, a photopolymerization initiator, and a viscosity adjusting agent. Japanese Laid-Open Patent Publication No. 2000-144-924 discloses a pattern forming method using a fluorine-containing curable material in order to improve the releasability with a mold. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. N. Sakai et al.: J. Photopolymer Sci. Technol. Vol. 18 'No. 4, 53 1 (2005) discloses (1) functional propylene fluorene monomer, (2) functional propylene fluorene monomer, ( 3) a photocurable radical polymerizable composition combining a functional acryl monomer and a photopolymerization initiator, or a photocationic polymerizable composition containing a photocurable epoxy compound and a photoacid generator, etc., for use in a nano Embossing, an example of thermal stability and mold peelability. M. Stewart et al.: MRS Buletin, Vol. 30, No. 12, 947 (2005) Focus on improving the peelability of photocurable resins and molds, and the film after hardening. -200923003 Shrinkage, light in the presence of oxygen The problem of low sensitivity such as polymerization hindrance reveals light containing (1) a functional acryl oxime monomer, (2) a functional acryl oxime monomer, a fluorenone-containing functional acryl oxime monomer, and a photopolymerization initiator. A hardening composition for nanoimprinting. T. Beiley et al.: J. Vac. Sci. Technol. B 1 8 (6), 3 5 7 2 (2000) discloses that a monofunctional acryl oxime monomer, a fluorenone-containing functional acryl monomer, and The photopolymerization initiator is formed on a ruthenium substrate by a curable composition for photon imprinting, and a surface-treated mold is used to reduce defects after photon imprinting. B. Vratzov et al.: J. Vac. Sci. Technol. B21(6), 2760 (2003) discloses photon imprinting of an anthracene-containing monomer, a trifunctional acryl monomer and a photopolymerization initiator. The curable composition is formed on a ruthenium substrate, and the Si 〇 2 mold has a high resolution and is coated with a composition having excellent uniformity. E. K. Kim et al.: J. Vac. Sci. Technol. B22(l), 131 (2004) discloses an example in which a cationic polymerizable composition formed by combining a specific vinyl ether compound and a photoacid generator forms a 50 nm pattern size. It is described that although the viscosity is low and the curing speed is fast, the template peeling property is still a problem. For example, N. Sakai et al.: J. Photopolymer Sci. Technol. Vol. 18, No. 4 5 3 1 (2005), M. Stewart et al.: MRS Buletin, Vol. 30, No. 12, 947 (2005) T. Beiley et al.: J. Vac. Ξοΐ-Τ ech η ο 1. B 1 8 ( 6) , 3 5 7 2 ( 2 0 0 0) , B. V ratzov et al.: J · V ac . S C i. Technol. B2 1 (6), 2760 (2003), EK Kim et al.: J. Vac. Sci. Technol. B22(l), 131 (2004), although propylene oxime with different functional groups is used. Monomers, acrylonitrile-based polymers, and vinyl ether compounds are disclosed in various types of photo-curable resins which are embossed with photo-nano, and as a preferred type of composition, -15-200923003 optimum monomer type, combination of monomers, The guidelines for material design, such as the optimum viscosity of the monomer or photoresist, the physical properties of the photoresist solution, and the improvement of the photoresist coating properties, are not disclosed at all. Therefore, in fact, in the case of photon imprinting, it is possible to make the composition of the composition widely used, and the photon nano-imprint resist composition which is practically satisfactory is still not proposed. B. Vratzov et al.: J. Vac. Sci. Technol. B2 1 (6), 2760 (2003), Ε·K. Kim et al.: J. Vac. Sci. Technol. B22(l) In the composition of 131 (2004), although there is a low viscosity, the pattern is photohardened, and the transmittance of the cured film is low (coloring) after heat treatment, and the hardness is insufficient, so that it cannot be used as a permanent film. The composition is not known.

Proc. SPIE Int. S oc. Opt. Eng., H 6151, Pt2, 61512F (2006), Science and Industry, Vol. 80, No. 7, 322 (20 06) Proposal, by optical function An inorganic/organic hybrid material composed of a mixture of a vermiculite sol, a (meth) acrylonitrile monomer, and a photopolymerization initiator, which has been treated with a combination material, has been reported for use in photon imprinting. Opc. SPIE Int. Soc. Opt. Eng•, Volume 6151, Pt2, 61512F (2006), Science and Industry, Vol. 80, No. 7, 3 22 (2006) Reporting 200nm line patterns of imprinted materials An example is formed, and as a mold material, it can be patterned to a line width of 600 nm. However, problems such as peeling property from the mold and insufficient hardness of the cured film may not be satisfactory.

Proc. SPIE Int. Soc. Opt. Eng., No. 6151, Pt2 '615 12F (2006), Science and Industry, Vol. 80, No. 7, 322 (2006) Viscosity, but all are light hardened to form a pattern, followed by heat treatment, the cured film has a low transmittance, that is, it has been colored, and the hardness is insufficient. In particular, it is useful to use as a permanent film. Japanese Laid-Open Patent Publication No. 2000-143-92 discloses a hard coating composition containing a surface-treated colloidal vermiculite, a specific (meth)acrylonitrile monomer, a leveling agent, and a photopolymerization initiator, and reports a film. Hardness and low hardening shrinkage are applied to optical discs, but the peelability of these compositions from the mold and the poor coatability of the substrate are difficult to apply to photon imprinting. Further, after the light is cured, the transmittance at the time of heat treatment is low, that is, it is colored, and it is unbearable as a permanent film. JP-A-2007- 1 865-70 discloses a report on a composition for etching photoresist having a ring structure of (meth) acrylate, and these compositions are light-transmitted, and have a low transmittance after heat treatment. That is, it has been colored, and it has a problem that it is unbearable for use as a permanent film, and the hardness and solvent resistance of the cured film are insufficient, which is unsuitable for practical use. In order to improve the hardness and mechanical strength of the cured film, it can be achieved by using a polyfunctional monomer which imparts a high crosslinking density, but these polyfunctional single-system high-viscosity compounds have a poorly cured film property under low viscosity. Further, when the polyfunctional monomer is polymerized at the time of irradiation with light, when a resin mold is used, there is a problem that residue remains. f International Publication No. WO2004/099272 has a report on the use of a curable composition for inkjet which has a photopolymerization site and a thermal reaction site in the same molecule. This invention is not directly applicable to the composition because of its high viscosity. Light nano embossing. Further, the color of the cured film is also large. There is a problem in the transparency of the protective film for the liquid crystal color filter, and the improvement method has not been disclosed. JP-A-2005-25 5 854 discloses a report of a hardenable composition of an acrylate monomer having a vinyl ether group in the same molecule. The invention has low viscosity and can be applied to photon embossing, but the hardness of the cured film is insufficient, and the improvement method is not disclosed. -17- 200923003 As such, the live system is not available and can be used as a permanent film for the proposal of photo-resist composition of photo-nano-imprinted. The main problems of the permanent film include pattern accuracy, adhesion, permeability after heat treatment at over 200 °C, high mechanical properties (strength to external pressure), scratch resistance, flattening properties, and solvent resistance. And many problems such as reduced gas release during heat treatment. When the curable composition for anodic imprinting is used as a permanent film, as in the conventional use of photoresist such as acryl resin, (1) uniformity of the coating film. (2) permeability after heat treatment (3) The imparting of scratch resistance is extremely important. At the same time, as the curable composition for photon imprinting, it is necessary to consider the following (4) and (5) in addition to the above (1) to (3), and the composition design technique is more difficult. (4) It is important to ensure the fluidity of the photoresist to the concave portion of the mold without solvent or low viscosity with a small amount of solvent. (5) After photohardening, it is easy to peel off from the mold and does not adhere to the mold. In the case of the curable composition for photon imprinting for nanoimprinting, there are various materials disclosed, and the composition for inkjet or the known composition for the protective film for magneto-optical discs has hitherto been used. The curable composition for etching photoresist, the hardenable composition for light nanoimprinting, and the curable composition for photo-nanoimprint for permanent film, have a common portion in materials, high-temperature heat treatment, mechanical strength, etc. There is a difference between the 'photo-curing resin for inkjet and optical disk, and the photo-curable resin for etching photoresist. If it is directly used as a photoresist for permanent film, it is transparent, mechanical strength, solvent resistance, etc. After all, it is not practical. High penetration -18- 200923003 People who have sex are particularly in need. DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a curable composition for nanoimprint which is excellent in photocurability and excellent in transparency. Further, it is intended to provide a hardenable composition for nanoimprinting which is suitable for a permanent film such as a flat panel display. In particular, it is intended to provide a composition excellent in permeability, releasability, and pattern accuracy after heat curing. In order to solve the problem, the international publication W02004/099272 is carefully explored, and it is known that two or more kinds of hardening functional groups having different reactivity in the same molecule, such as a monomer of a photopolymerization site and a thermal reaction site, are used. In the case of having a viscosity suitable for nanoimprinting, it is possible to impart satisfactory physical properties of the cured film, and it is semi-hardened in photopolymerization, and an inexpensive resin mold has almost no residue remaining. Based on this finding, it is found that the above problems can be solved by the following means. (1) A curable composition containing (A) a monomer having at least two kinds of sclerosing functional groups having different reactivity in the same molecule, and (C) an antioxidant for nanoimprinting. (2) A curable composition for nanoimprinting according to (1), wherein at least one of the curable functional groups is an α,/3-unsaturated ester group. (3) The curable composition for nanoimprinting according to (1) or (2), further comprising (Β) a surfactant. (4) The curable composition for nanoimprinting according to any one of (1) to (3), wherein the viscosity of the composition is in the range of 3 to 18 mPa·s. (5) containing at least (A) two or more kinds of curable functional groups having different reactivity in the same molecule, and at least one of the curable functional groups is a single α,/3-unsaturated ester-19-200923003 (B) a surfactant, and (C) a hardening composition for nanoimprinting of an antioxidant, wherein the viscosity of the composition is in the range of 3 to 18 m P a · s. (6) The curable composition for nanoimprinting according to any one of (1) to (5), wherein the single system is represented by the following general formula (1). •^γ-5-〇·\-χ-(-Υ)η General formula (1)

R1 L (in general formula (1), 'R1 represents a hydrogen atom or a hydroxymethyl group, Χ is an organic group; 111 is an integer of Tables 1-3, η is an integer of Tables 1-4; Υ has a carbon-carbon unsaturated bond a curable functional group, a hardenable functional group having a carbon-nitrogen unsaturated bond, a hardening functional group having a cyclic group containing an oxygen atom, or a group represented by the following general formula (2)—(-Si(OR2) 〉3) _ General formula (2) ' (R2 each alkyl group or aryl group) (7) The hardening composition for nanoimprint of (6), wherein at least one of Y in general formula (1) Selected from vinyl ether, allyl ether, allyl ester, cyclohexenyl, cyclopentenyl, dicyclopentenyl 'styryl, methacryloxy, methacrylamido, propylene a group of amidino group, a vinyl fluorenyl group, an N-ethylene heterocyclic group, and a maleimide group. (8) A hardening composition for nanoimprinting as in (6), wherein the general formula (1) At least one of Y in the group is selected from the group consisting of an allyl ether group, a cyclohexenyl group, a cyclopentenyl group, and a dicyclopentanyl group. (9) A hardening composition for nanoimprinting as in (6), wherein At least one of the olefins of Y in the general formula (1) The base, the sum of η and m. (10) The hardenable composition for nanoimprint of (6), wherein at least one of the isocyanate groups or the nitrile group of Y in the general formula (1). 200923003 (11) The hardenable composition for nanoimprint of (6) wherein at least one of Y in the general formula (1) is selected from the group consisting of a epoxidized ring, an epoxy group, and an ethylene carbonate group. (12) The curable composition for nanoimprinting according to any one of (6) to (1), wherein the general formula (1) has an organic group having a total carbon number of 3 to 9 in the X form. 13) The curable composition for nanoimprinting of (6) wherein the compound represented by the general formula (1) is any one or more of the following general formulas (3) to (5).

General formula (5)

(In general formula (3) to (5), each of R3's hydrogen atom or methyl group 'r4' is methyl or B'4) is hardened by nanoimprinting of any of (1) to (1 3) The composition 'containing a polymerizable monomer other than the monomer (A)' and a photopolymerization initiator. (15) The curable composition for nanoimprinting according to any one of (1) to (14) wherein the antioxidant is at least selected from the group consisting of a hindered lanthanide antioxidant or a hindered amine-based antioxidant. (16) The curable composition for nanoimprinting according to any one of (1) to (1), wherein the content of the antioxidant is 1% by mass or less. (17) A hardenable composition for nanoimprinting according to any one of (1) to (16), wherein -21 - 200923003 does not contain a compound having a molecular weight of more than 1,000. (18) The curable composition for nanoimprinting according to any one of (1) to (17), wherein the surface tension of the composition is in the range of 18 to 30 mN/m. (19) A curable composition for nanoimprinting according to any one of (1) to (18) which is cured by irradiation light and heat. (20) A cured product obtained by curing the curable composition for nanoimprinting according to any one of (1) to (19). (21) A method for producing a cured product obtained by curing light and heating by a plurality of hardening compositions r for nanoimprinting according to any one of (1) to (19). (22) A member for a liquid crystal display device using the cured product of (20). (23) A method for producing a member for a liquid crystal display device in which a curable composition for nanoimprinting according to any one of (1) to (19) is cured by performing a plurality of irradiation lights and heating. According to the present invention, it is possible to provide a curable composition for nanoimprint which can obtain a cured product excellent in transmittance. [Embodiment] The content of the present invention will be described in detail below. In the present specification, "~" is used to mean the number of 値 before and after it is used as the lower limit and upper limit 値. The invention is described in detail below. In the present specification, (meth) acrylate acrylate and methacrylate, (meth) propylene propylene and methacryl fluorene, (meth) propylene fluorenyl propylene and methacryl . In the present invention, the monomer is different from the oligomer and the polymer, and refers to a compound having a molecular weight of 1, 〇〇〇 or less. In the present specification, a functional group means a group which participates in polymerization. The so-called nanoimprinting in the present invention refers to a pattern transfer of about -22 to 200923003, which is about several micrometers to several tens of nanometers, and is of course not limited to the nanometer. The curable composition for photonic embossing of the present invention (hereinafter, simply referred to as "the composition of the present invention") has high permeability before curing, and is excellent in the ability to form fine concavo-convex patterns, and can be coated and other processing suitability. Excellent things. And it has excellent hardness after hardening, and it can obtain comprehensive and excellent film properties in other aspects. Thus, the composition of the present invention can be widely used for photon imprinting. That is, the composition of the present invention can have the following characteristics when used for photon imprinting. (1) Since the fluidity of the room temperature solution is excellent, the composition easily flows into the cavity of the mold, and the valve is not broken due to the difficulty of inhaling the atmosphere, and the residue of the convex portion and the concave portion of the mold is hard to be left after the light is hardened. (2) The cured film after hardening is excellent in mechanical properties, and the adhesion between the coating film and the substrate is excellent, and the peeling property between the coating film and the mold is excellent, so that the pattern is not broken at the time of peeling the mold, and the surface of the coating film is roughened due to drawing. A good pattern can be formed. (3) It is suitable for coating on large substrates and microfabrication fields because of excellent coating uniformity. (4) It is suitable for various permanent films because it has mechanical properties such as light transmittance, residual film properties, and scratch resistance, and has high solvent resistance. For example, the composition of the present invention is suitable for a semiconductor integrated circuit and a member for a liquid crystal display device which are difficult to expand up to now (especially a thin film transistor of a liquid crystal display, a protective film of a liquid crystal color filter, a spacer, and other liquid crystal display). Other applications, such as magnetic wall materials for plasma display panels, flat screens, microelectromechanical systems (MEMS), sensor components, optical discs, high-density memory discs, etc. Optical components such as diffraction gratings and relief-type full-phase diagrams, and should be widely used in micro devices, optical elements -23-200923003, optical films, polarizing elements, organic transistors, color filters, top coats, columns Fabrics, liquid crystal alignment ribs, microlens arrays, immunoassay wafers, DNA separation wafers, microreactors, nanotechnology devices, optical waveguides, filters, photonic liquid crystals, and the like. The viscosity of the composition of the present invention is illustrated. In the present invention, the viscosity means a viscosity at 25 ° C unless otherwise specified. The composition of the present invention preferably has a viscosity of 3 to 18 mPa·s at 25 ° C, more preferably 5 to 15 mPa·s, and particularly preferably 7 to 12 mPa·s. When the viscosity of the composition of the present invention is 3 mPa·s or more, there is a problem that the substrate coating property is less likely to occur. 'The mechanical strength of the film tends to decrease. Specifically, when the viscosity is 3 mPa·s or more, unevenness occurs on the surface of the coating composition, and the tendency of the composition to flow out from the substrate during coating can be suppressed. On the other hand, when the viscosity of the composition of the present invention is 18 mPa·s or less, when the composition is adhered to the mold having the fine concavo-convex pattern, the composition can also flow into the cavity of the mold. It is not easy to cause bubble defects, and it is not easy to leave a residue in the convex portion of the mold after photohardening, which is preferable. The composition of the present invention contains (A) a monomer having two or more kinds of curable functional groups having different reactivity in the same molecule, and (C) an antioxidant. The present invention may also contain (B) a surfactant. (A) The monomer may be used alone or in combination of two or more. The composition of the present invention is preferably 10 to 99% by mass of the (A) monomer, more preferably 20 to 80% by mass. The composition of the present invention may contain other polymerizable monomers, photopolymerization initiators and the like. These are described in detail below. First, a compound (hereinafter referred to as "monomer in the present invention") having two or more kinds of curable functional groups having different reactivity in the same molecule of the composition of the present invention will be described. Here, the two types of curable functional groups having different reactivity can be distinguished as follows, for example. The first example is polymerized (reacted) when irradiated with light, and -24-200923003 is different in reactivity of its functional groups. Such a curable functional group is an acrylate group, an N-vinyl group, a (meth) acrylamide group or the like. The second example has a group in which polymerization (reaction) is carried out by heating while reacting with light. Specifically, the group which does not react upon light irradiation is a vinyl ether group, an allyl ether group, an allyl ester group, a cyclohexenyl group, a cyclopentenyl group, a dicyclopentenyl group, a styryl group, a methacryloyloxy group. Base, vinyl decyl and maleimide. The methacryloxy group and the styryl-vinyl ether group are usually subjected to radical polymerization, and polymerization is carried out at room temperature in the case of light irradiation, so that these polymerizable groups do not react and are polymerized by heating. In the present invention, at least one of the single-system hardening functional groups is preferably a monomer having an unsaturated ester group, and more preferably a monomer of the general formula (1).

General formula (1) (In the general formula (1), R1 represents a hydrogen atom or a hydroxymethyl group, X represents an organic group; 111 an integer of Tables 1-3, η is an integer of Tables 1-4; Υ has carbon·carbon a curable functional group having an 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 a group of the following general formula (2): (2) (R2 each represents an alkyl group or an aryl group) The organic group represented by X is an organic group having a valence of 2 to 7 and an organic group having a valence of 3 to 6 is more preferable. It may be aliphatic or aromatic, and the total number of carbon atoms is preferably 2 to 20, more preferably 3 to 9. When the total number of carbon atoms is from 3 to 9, the density of the functional group is high, the crosslinking density of the cured film can be increased, and the molecular weight is designed to be low, so that the viscosity of the composition of the present invention can be in a preferable range. The organic group may also be separated by an oxygen atom, a sulfur atom, an ester group or a urethane group. Specifically, there are an alkyl chain having 3 to 9 carbon atoms, a C-25-200923003 triol skeleton, a pentaerythritol skeleton, a cyclohexane ring, a cyclopentane ring, and the like, and a benzene skeleton. The hardening functional group having a carbon-carbon unsaturated bond represented by γ may be a double bond or a triple bond, or may have a substituent in the unsaturated bond, and may be a chain or a ring. The total number of carbon atoms is preferably from 2 to 18. Y may be a vinyl ether group, an allyl group, a dipropyl acrylate group, a cyclohexyl group, a cyclopentyl group, a biscyclopentyl group, a styrene group, a methyl propyl decyloxy group, a methacrylamide a base, an acrylamide group, a vinyl fluorenyl group, an N-ethylene heterocyclic group and a maleimide group; an allyl ether group, a cyclohexenyl group and a dicyclopentenyl group are preferred; an allyl ether group; The allyl ester group is more preferred. The curable functional group having a carbon-nitrogen unsaturated bond represented by Y is an isocyanate group or a nitrile group. The curable functional group containing a cyclic group containing an oxygen atom represented by Y is an oxane ring, a propylene oxide ring or an ethylene carbonate group. Preferred are aeroxane ring and epoxidized ring. Preferably, m is 1 to 3, 1 or 2 is better, and preferably 11 is 1 to 4, and 1 to 3 is more preferable. When the m system is 2 or more, the plural R1 may be the same or different. When the n system is 2 or more, the plural numbers may be the same or different. The alkyl group represented by R2 is preferably one having a carbon number of from 1 to 8. Such alkyl groups are methyl, ethyl, propyl, butyl, hexyl or benzyl. The aryl group is preferably a carbon atom number of 6 to 12. Such aryl groups are phenyl, p-tolyl, p-chlorophenyl. In the present invention, in particular, at least one of the allyl ether or allyl ester groups, and the combination of η and m is preferably 3 to 6; at least one of the allyl ether or allyl ester groups is The sum of η and m is 3~6' X. The organic group having 3 to 9 total carbon atoms is -26-200923003. By using such a monomer, the crosslinking density of the cured film can be increased, the mechanical properties and solvent resistance of the cured film can be improved, and the viscosity of the composition can be set in a preferred range, and the effect of pattern precision can be improved. The compound of the formula (1) is preferably a compound of any one of the following general formulas (3) to (5).

General formula (5) (in the general formulae (3) to (5), each of R3 represents a hydrogen atom or a methyl group, and R4 each represents a methyl group or an ethyl group. Here, a preferred example of the monomer in the present invention is shown, of course, the present invention does not Limited to these. -27- 200923003

-28 200923003

NCO M-22

M-23

M-24

M-25

a 0 28 -I, M-31a,

M-26 M-27 ^5i(0Me)3 Μ·29 M-30 ^0- M-32 0 M-33

M-34

0^0 M-36

M-40 M-41 M-42 \ M-44 M-43 Other polymerizable monomer The composition of the present invention may contain other polymerizable monomers for the purpose of improving composition viscosity, film hardness, flexibility, and the like. Preferably, a polymerizable unsaturated monomer (monofunctional polymerizable unsaturated monomer) having one group having an ethylenic group other than a -29-200923003 saturated bond is used. Specifically, there are, for example, 2-propenyloxyethyl phthalate, 2-propenyl-2-hydroxyethyl phthalate, 2-propylene oxirane hexahydrophthalate, 2-propene oxime citrate Ester, 2-ethyl-2-butylpropanediol acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylhexacarbitol (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ( 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, (meth) acrylate 4-hydroxybutyl ester, acrylic acid dimer, (meth)acrylic acid f. phenylmethyl ester, butanediol-(meth)acrylate '(meth)acrylic acid butoxyethyl V. ester, (meth)acrylic acid Butyl ester, cetyl (meth)acrylate, ethylene oxide (hereinafter referred to as EO) modified cresol (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate Ester, ethyl (meth)acrylate, isoamyl (meth)acrylate, isobutyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylic acid Cyclohexyl ester, isodecyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentaoxyethyl (meth)acrylate, isotetradecyl (meth)acrylate, lauryl (meth)acrylate , methoxydipropylene glycol (meth) / acrylate, methoxytripropylene glycol (meth) acrylate, methoxy polyethylene glycol (methyl) propyl acrylate, methoxy triethylene glycol (meth) acrylate , (meth)acrylic acid methyl vinegar, neopentyl glycol benzoate (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polypropylene glycol (meth) acrylate Ester, (meth) propyl octanoate, p-cumyl phenoxy glycol (meth) acrylate, epichlorohydrin (below ECH) modified phenoxy acrylate, benzene (meth) acrylate Oxyethyl ester, phenoxy diglycol (meth) acrylate, phenoxy hexaethylene glycol (meth) acrylate vinegar, oxytetraethylene glycol (meth) acrylate, polyethylene glycol (methyl) Acrylic acid vinegar, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol-30- 200923003 (meth) propylene Ester, stearyl (meth) acrylate, EO modified succinic acid (meth) acrylate, tertiary (meth) acrylate, tribromophenyl (meth) acrylate, E0 modified (methyl) Tribromophenyl acrylate, tris(dodecyl)(meth) acrylate, p-isopropenol, styrene, α-methylstyrene, acrylonitrile, vinyl carbazole, urethane (meth) acrylate. A polyfunctional polymerizable unsaturated monomer having two or more groups containing an ethylenically unsaturated bond is also preferably used as the other polymerizable monomer. Difunctional polymerizable unsaturated monomers having two groups containing an ethylenically unsaturated bond suitable for use in the present invention are, for example, diethylene glycol monoethyl ether (meth) acrylate, dimethylol dichloropentane (methyl) Acrylate, di(meth)acrylonitrile deuterated isocyanurate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, Ε0 Modified 1,6-hexanediol di(meth)acrylate, ECH modified 1,6-hexanediol di(meth)acrylate, allyloxy polyethylene glycol acrylate, 1,9-anthracene Diol (meth) acrylate, bismuth bisphenol quinone di(meth) acrylate, P0 modified bisphenol A di(meth) acrylate, modified bisphenol A di(meth) acrylate Ester, E0 modified bisphenol F di(meth) acrylate, ECH modified hexahydrophthalic acid diacrylate, hydroxytrimethyl acetic acid neopentyl glycol di(meth) acrylate, neopentyl glycol di Methyl) acrylate, E 〇 modified neopentyl glycol diacrylate, propylene oxide (lower p〇) modified neopentyl glycol diacrylate, caprolactone modified hydroxy trimethyl acetic acid Ester neopentyl glycol, stearic acid modified neopentyl alcohol di(meth) acrylate, ECH modified bis (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) II Methyl) acrylate, poly(propylene glycol-tetramethylene glycol) di(meth) acrylate, polyester (di) acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol di(methyl) ) acrylate, gCH modified propylene glycol di(meth) acrylate, fluorenone di(meth) acrylate, tri-31 - 200923003 glycol di(meth) acrylate, tetraethylene glycol di(methyl) Acrylate, dimethylol tricyclodecane di(meth) acrylate, neopentyl glycol modified trimethylolpropane di(meth) acrylate, tripropylene glycol di(meth) acrylate, EO modification Tripropylene glycol di(meth)acrylate, triglycerin di(meth)acrylate, dipropylene glycol di(meth)acrylate, diethylene acetal, divinyl acetal, urethane (meth) acrylate . Among these, 'new pentanediol di(meth) acrylate, 1,9-nonanediol di(meth) acrylate, tripropylene glycol di(meth) acrylate, tetraethylene glycol di(meth) acrylate Esters, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and the like are particularly suitable for use in the present invention. The polyfunctional polymerizable unsaturated monomer having three or more ethylenically unsaturated bond-containing groups is, for example, ECH-modified glycerol tri(meth)acrylate, EO-modified glycerol tri(meth)acrylate, P〇. Modified triglyceride (meth) acrylate, neopentyl alcohol triacrylate, EO modified phosphoric acid triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane three (Meth) acrylate, E 0 modified trimethylolpropane tri(meth) acrylate, p 〇 modified trimethylolpropane tri (meth) acrylate, ginseng (propylene oxyethyl) heterotrimer Cyanate ester, dipentaerythritol hexa(meth) acrylate, caprolactone modified dipentaerythritol hexa(meth) acrylate diamyl pentoxide hydroxy penta (meth) acrylate vinegar, hospital Base modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly(methyl) bis-succinic acid ester, alkyl modified dine pentaerythritol tris (meth) acrylate vinegar, two ( Di-methyl)propane tetra(meth)acrylate, neopentyl alcohol ethoxytetra(meth)acrylate, neopentyl alcohol Tetra (meth) acrylate, urethane (meth) acrylate, and the like. Tracing t' EO to change glycerol di(methyl) propylene vinegar, p 〇 modified gan-32- 200923003 oil tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, E Rhodium-modified trimethylolpropane tri(meth)acrylate' PO modified trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, neopentyl alcohol ethoxylate Tetrakis (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, urethane (meth) acrylate, etc. are particularly suitable for use in the present invention. The urethane (meth) acrylate is available as a (meth) acrylate or a polyfunctional acrylate. Specific compounds include U-2PPA, UA-4100, UA-5 20 1, U-4H, U-4HA, U-6HA, U-15HA, etc., manufactured by Shin-Nakamura Chemical Co., Ltd. In the composition of the present invention, in order to further increase the crosslinking density, a polyfunctional oligomer or a polymer having a molecular weight larger than that of the above polyfunctional polymerizable monomer can be blended in an amount which can achieve the object of the present invention. The polyfunctional oligomer having photo-radical polymerizability includes various acrylate oligomers such as polyester acrylate, urethane acrylate, polyether acrylate, and polyepoxy acrylate. The other polymerizable monomer used in the present invention may be a compound having an oxirane ring. The compound having an oxirane ring is, for example, a polyglycidyl ester of a polybasic acid, a polyglycidyl ether of a polyhydric alcohol, a polyglycidyl ether of a polyoxyalkylene glycol, or a polycondensation of an aromatic polyhydric alcohol. Hydrogenated compounds of epoxidized ethers, urethane polyepoxides, and epoxidized polybutadienes. These compounds may be used alone or in combination of two or more. For the compound containing epoxy propyl group, commercially available products include UVR-6216 (manufactured by Union Carbide Co., Ltd.), dehydrated glycerin, AOEX24, CYCLOMER A200 (manufactured by DAICEL Chemical Industry Co., Ltd.), EPIKOTE 828, EPIKOTE 812, EPIKOTE 1031, EPIKOTE 872 ' EPIKOTE CT5 08 (above the oily SHELL (share) system), KRM-2400, KRM-2410, KRM-2408 'KRM-2490, KRM-2720, KRM-275 0C or above Asahi Chemical Industry Co., Ltd. System) -33- 200923003 and so on. These may be used alone or in combination of two or more. The preparation method of these compounds having an oxirane ring is not particularly limited, and can be referred to, for example, 'Jishan KK Publishing, Fourth Edition Experimental Chemistry Lecture 20 Organic Synthesis 11 ' 21 3 ~ 4 Years' Ed. by Alfred Hasiner, The chemistry Of heterocyclic compounds-Small Ring Heterocycles part 3 Oxiranes, John Wiley & Sons, An Interscience Publication,

New York, 1985, Yoshimura, then, 29 volumes No. 12, 32, 1985, Yoshimura, then, 30 volumes No. 5, 42, 1986 'Yoshimura, then, 30 volumes, No. 7, 42, 1 986 'Special Kaiping 1 1 - Japanese Patent No. 2906245, Japanese Patent No. 2926262, and the like are synthesized. A vinyl ether compound can also be used as the other polymerizable monomer used in the present invention. 1 The vinyl ether compound may be appropriately selected, for example, 2-ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, triethylene glycol diethyl storage Ether, 1,2-propanediol divinyl ether, iota, 3-propylene glycol 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, tetraethylene glycol divinyl ether, neopentyl alcohol-ethylene ether, new Pentaerythritol diethylene acid, neopentyl alcohol tetraethylene ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene ethyl ether, triethylene glycol diethylene vinyl ether, B Diol propyl vinyl ether, triethylene glycol diethyl ether, trimethylolpropane triethyl ether, trimethylolpropane diethyl vinyl ether, neopentyl alcohol diethylene ethyl Ether, neopentyl alcohol tri-ethyl vinyl ether, neopentyl alcohol tetraethyl ether, 1,1,1-gin[4-(2-ethoxyethoxyethoxy)phenyl] Double 酣 a diethylene oxyethyl ether - 34- 200923003 and so on. These vinyl styrene compounds can be reacted, for example, by a method described by Stephen C. Lapin, Polymers Paint Colour Journal, 1 79 (4237), 3 2 1 (1 98 8), that is, by reacting a polyhydric alcohol or a polyhydric phenol with acetylene, or The reaction of the polyol or the polyhydric phenol with the halogenated alkyl vinyl ether is carried out; these may be used alone or in combination of two or more. A styrene derivative can also be used as the other polymerizable monomer used in the present invention. The styrene derivative is, for example, p-methoxystyrene, p-methoxy-0-methylstyrene, p-nonylstyrene or the like.

A styrene derivative which can be used with a functional polymer of the present invention is, for example, styrene, p-methylstyrene, p-methoxystyrene, /3-methylstyrene, p-methylenevinylene, ?-toluene. Ethylene, p-methoxy-methylstyrene, p-benzoic acid, etc.; vinylnaphthalene derivatives are, for example, 1-vinylnaphthalene, α-methyl-1-ethene-cai- θ'-Shenyl-1-vinylnaphthalene, 4- Methyl-1-vinylnaphthalene, 4-methoxy-1-vinylnaphthalene, and the like. Gastrointestinal peeling and mold peelability, coating properties, can also be used (meth) propylene _ =, (meth) acrylate pentafluoroethyl ester, (meth) acrylic acid (perfluoro TS) ethyl vinegar, perfluorobutyl Base-hydroxypropyl (meth) acrylate, (meth)acrylic acid (all-gas 5-yl) ethyl ester, (meth)acrylic acid octafluoropentyl ester, (meth)acrylic acid all-gas octyl hydrazine, (methyl A compound having a fluorine atom such as tetrafluoropropyl acrylate. Further, propylene ether and butenyl ether may be blended as the other polymerizable monomer used in the present invention. Suitable for use are, for example, anthracene-dodecyl-fluorene-propene ether, anthracene-dodecylbutyric acid, anthracene·butenoxymethyl-2nordecene, 1,4-bis(1-butenyloxy) Butane, (butoxy) brothel, 1,4 -1 (1-butoxymethyl) cyclohexyl, 200923003 monoglycol bis(1-butenyl) ether, 1,2,3-three (1-butoxy)propane, propylene ether propyl carbonate, and the like. The other polymerizable single system is preferably contained in the composition of 2~9〇% by mass in terms of preferably '20 to 80% by mass. Next, a preferred blending form of the monomer and other polymerizable monomers (hereinafter referred to as "polymerizable unsaturated monomers") in the present invention will be described. The composition of the present invention contains two or more kinds of curable functional groups having different reactivity in the same molecule, and at least one of the monofunctional α0-unsaturated ester groups of the curable functional group is an essential component. It is preferred to contain other polymerizable monomers. The monofunctional polymerizable unsaturated monomer is usually used as a reactive diluent. It is effective for lowering the viscosity of the composition of the present invention, and is usually added at 15% by mass or more of all the polymerizable unsaturated monomers. 2 0 to 8 0% by mass is preferable, 25 to 70% by mass is more preferable, and 30 to 60% by mass is particularly preferable. The monofunctional polymerizable unsaturated monomer is preferably used as a reactive diluent, and is preferably added in an amount of 15% by mass or more based on the total of the polymerizable unsaturated monomers. The monomer having two groups containing an unsaturated bond (difunctional polymerizable unsaturated monomer) is added in an amount of 90% by mass or less based on all of the polymerizable unsaturated monomers, and 80% by mass or less is preferably 70% by mass or less. The following is especially good. The addition ratio of the monofunctional and difunctional polymerizable unsaturated monomers is from 1 to 95% by mass based on the total of the polymerizable unsaturated monomers, preferably from 3 to 9.5 mass%, more preferably from 5 to 90% by mass. A preferred addition ratio of the polyfunctional polymerizable unsaturated monomer having three or more groups containing an unsaturated bond is 80% by mass or less, more preferably 70% by mass or less, and particularly preferably 60% by mass or less. good. When the ratio of the polymerizable unsaturated monomer having three or more groups containing a polymerizable unsaturated bond is 80% by mass or less, the viscosity of the composition can be lowered, which is preferable. -36- 200923003 The composition of the present invention preferably has a surface tension of 18 to 30 mN/m and more preferably 20 to 28 mN/m. In such a range, the effect of improving surface smoothness can be obtained. In the composition of the present invention, the water content at the time of preparation is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and still more preferably 1.0% by mass or less. When the water content at the time of preparation is 2.0% by mass or less, the composition of the present invention can be more stably stored. In the composition of the present invention, the organic solvent content is preferably 3% by mass or less based on the total composition. That is, the composition of the present invention preferably contains, as a reactive diluent, another monomer having one or more of the above functions, and it is not necessary to contain an organic solvent to dissolve the component of the present invention. If the organic solvent is not contained, the baking step of the volatile solvent is not necessary, and the procedure can be simplified, which is advantageous. Therefore, in the composition of the present invention, the organic solvent content is preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably not included. As described above, the composition of the present invention does not necessarily contain an organic solvent, and the reactive diluent can be arbitrarily added when the insoluble compound or the like is dissolved as a component of the present invention or when the viscosity is finely adjusted. A preferred organic solvent type which can be used in the composition of the present invention is a solvent which is generally used for a photocurable composition for photonic imprinting, and a photoresist which is capable of dissolving and uniformly dispersing the compound used in the present invention. And if it does not react with these components, there is no particular limitation. The organic solvent is, for example, an alcohol such as methanol or ethanol; an ether such as tetraoxane; a glycol such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether or ethylene glycol monoethyl ether. Ethers; ethylene glycol acetate such as acesulfame acetate, ethyl acesulfame acetate; diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diglyme, diethylene glycol ethyl Diethylene glycol such as dimethyl ether, diethylene glycol monoethyl ether, digan-37-200923003 alcohol monobutyl ether; propylene glycol alkyl ether acetate such as propylene glycol methyl ether acetate or propylene glycol ethyl ether; aromatics such as toluene and xylene Alkaloids; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanyl ketones such as j '2-pentanone; ethyl 2-hydroxypropionate, Methyl 2-hydroxy-2-methylpropanoate, 2-ri·2_ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxymethylbutyrate, 3-methoxypropionic acid Esters such as ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, etc. class. Also, Ν-methylformamide, hydrazine, hydrazine-dimethylformamide, hydrazine-methylmethalamine benzene, hydrazine-methylacetamide, hydrazine, hydrazine-dimethylacetamide may be added. , Ν_methyl-port pyrrolidone, dimethyl hydrazine, benzyl ether, dihexyl ether, acetamidine, isophorone, caproic acid, octanoic acid, octyl alcohol, 1-nonanol, benzyl alcohol, High boiling point solvents such as benzyl acetate, ethyl benzoate, diethyl oxalate, ethyl maleate, r-butyrolactone, ethyl carbonate, propyl carbonate, and benzoquinone acetate. These may be used alone or in combination of two or more. Among these, 'methoxypropanediol acetate, ethyl 2-hydroxypropionate, methyl 3-hydroxydicarboxylate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone Methyl isobutyl ketone, 2-heptanone, etc. are particularly preferred. The composition of the present invention preferably contains a compound having a molecular weight of more than 1,000. For such a composition, the viscosity of the composition can be suppressed from increasing. The molecular weight, the structure-determined compound is calculated from a molecular formula, such as a compound of a compound having a complex structure of a polymer compound, and means a molecular weight measured by a GPC method (polystyrene conversion). Photopolymerization Initiator The composition of the present invention is preferably a photopolymerization initiator. The 200923003 photopolymerization initiator used in the present invention is preferably contained in the total composition of, for example, 0.1 to 15 mass%, more preferably 0.2 to 12% by mass, more preferably 0.3 to 10% by mass. When two or more kinds of photopolymerization initiators are used, the total amount thereof is in this range. When the ratio of the photopolymerization initiator is 0.1% by mass or more, the sensitivity (speed hardenability), the resolution, the edge roughness, and the 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 coloring property, the removability, and the like tend to be improved. In the inkjet composition containing a dye and/or a pigment, and the composition for a color filter of a liquid crystal display, the amount of a photopolymerization initiator and/or a photoacid generator to be added has been variously discussed. The addition amount of a preferred photopolymerization initiator and/or photoacid generator for the curable composition for photon nanoimprint for nanoimprinting has not been reported. That is, in a system containing a dye and/or a pigment, these are used as a radical scavenger, and do not affect photopolymerization and sensitivity. In view of this, in these applications, the amount of the photopolymerization initiator added is optimized. On the other hand, the composition of the present invention does not contain a dye and/or a pigment as an essential component, and the optimum range of the photopolymerization initiator may be different from those of an inkjet composition, a liquid crystal display color filter composition, and the like. The photopolymerization initiator used in the present invention is used in combination with an active material for the wavelength of the light source used to promote the production of an appropriate active species. The photopolymerization initiator used in the present invention may be, for example, a commercially available initiator. These include, for example, Irgacure (registered trademark) 2959 (1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-propyl-propyl) available from Ciba Corporation, Irgacure ( Registered trademark) 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure (registered trademark) 500 (1-hydroxycyclohexyl phenyl ketone, diphenyl ketone), Irgacure (registered trademark) 651 (2, 2-dimethyl Oxy-1,2-diphenylethyl-1-one), -39- 200923003

Irgacure (registered trademark) 369 (2-benzyl-2- dimethylamine-1-(4-morpholine phenyl) butanone-1), Irgacure (registered trademark) 907 (2-A-l- [4 -Methylthiophenyl]-2-carbolinepropyl-1-one), Irgacure (registered trademark) 819 (bis(2,4,6-trimethylphenylmethyl)phenylphosphine oxide), Irgacure (registered trademark) 1800 (bis(2,6-dimethoxybenzyl)-2,4,4-trimethylpentanephosphine, 1-hydroxycyclohexyl phenyl ketone), Irgacure (registered trademark) 1 800 (oxidized double ( 2,6-Dimethoxybenzhydryl)-2,4,4-trimethylpentanephosphine, 2-hydroxy-2-methyl-1-phenyl-1-propyl-1-one), Irgacure (registered trademark) OXE01 (1,2-octanedione), 1-[4-(phenylthio)phenyl]-2-(0-benzoquinone), Darocur (registered trademark) 1173 (2-hydroxy- 2-methyl-1-phenyl-1-propyl-1-one), Darocur (registered trademark) 1116, 1398, 1174 and 1 020, CGI242 (ethanone, 1-[9-ethyl-6-( 2-toluamyl)-9H-indazol-3-yl]-1-(0-acetamidine), Lucirin TPO available from BASF (oxidized 2,4,6-trimethylbenzenediphenyl) Phosphine), L ucir ι η TPO-L (oxidized 2,4,6-trimethylmethylmercaptoethoxyphenylphosphine), ESACURE 1001Μ(1-[4-benzoylphenyl)phenyl]-2-methyl-2-(4-methylbenzyl)propyl-1-one) available from ESACUR Japan SiberHegner, N-1414 ADEKA 〇PT0MER (registered trademark) N-1414 (carbazole benzophenone), ADEKA OPTOMER (registered trademark) N-17 17 (acridine), ADEKA 0PT0MER (registered trademark) N- 1 606 (triple well), tri-chemical TFE-three tillage (2-[2-(furan-2-yl)phenyl]-4,6-bis(trichloromethyl)-1, 3,5-Triple), Sanhe Chemical Dinghe £-Triple (2-[2-(5-methylfuran-2-yl)phenyl]-4,6-bis(trichloromethyl)- 1,3,5-triazine), tri-chemical MP-tripod (2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triad ), green chemical system TAZ-113 (2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triad) , TAZ-108 (2-(3,4-dimethyl-40-200923003 oxyphenyl)-4,6-bis(trichloromethyl)-^5-triad), diphenyl _, ,, — bis-diethylamine diphenyl ketone, methyl 2 - diphenyl ketone, 4 — benzamidine — methyl — chloro-9 — oxo sulphur phenyl sulfide benzene Ketone, ethyl mitoxanone, 2-methyl-9-oxosulfonate, 2-isopropyl-9-oxosulfonate [I star, 4-isopropyl-9-oxo-sulfur Dilj Comet, 2,4-diethyl-9-oxosulfonium, sputum-chlorine-deducted propane gas, and -9-oxo-sulphur-sucking, 2-methyl-9-oxo-sulphur 9-oxosulfonium ammonium salt, benzoin, * 4, dimethyl benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzo Dimethyl ketal, 1, hydrazine, trichloroacetophenone dioxo acetophenone and cycloheptanone, methyl phthalic acid benzoate, 2 methyl carbaryl, 4-benzyl quinone biphenyl , 4-benzylidene diphenyl ether 'i,4-benzoyl benzene, ~~~ this brew, 1 〇-butyl-2-chloroacridone' [4-(tolylthio)phenyl] Benzene Institute - ζ - ethyl waking, 2,2-bis(2-chlorophenyl)-4,5,4,,5' _肆(3,4,5-trimethoxyphenyl η,〗, -biimidazole, 2,2-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1ι2 (4-diimidazole, cis-methylamine phenyl)methane, 4-(dimethyl Ethyl benzoate ethyl ester, benzoic acid 2·(dimethylamino)ethyl ester, 4-(dimethylamino)benzoic acid butyl Oxyethyl ester and the like. In addition to the photopolymerization initiator, the composition of the present invention may be added with a photosensitizer to adjust the wavelength of the UV range. Typical sensitizers useful in the present invention are disclosed in Crivello [JVCrivell®, Adv. in P〇lymer Sci, 62, 丄 (1 9 84)]; specifically, 芘'茈, acridine orange' 9 _Oxygen sulphur 嗤, 2_ chloro-9-oxosulfonate, benzoxanthin, N-vinyl hydrazine D sitting, 9,10-dibutoxyxanthine, awakening, oxacillin, keto-encain Phenanthrene, camphor sputum, and morphine trap derivatives. Surfactant The composition of the present invention contains a surfactant. The surfactant used in the present invention contains, for example, 〇. 0 0 1 to 5 mass% ' 〇 _ 0 0 2 4 4% by mass, more preferably 0.005 to 3% by mass. When two or more kinds of interfaces are used - 41 - 200923003 When the agent is used, the total amount is in this range. When the surfactant is less than 0.001% by mass in the composition, the coating uniformity effect is insufficient, and if it exceeds 5% by mass, the transfer characteristics of the mold are deteriorated. The surfactant is preferably at least one of a fluorine-containing surfactant, an anthrone-based surfactant, and a fluoroneketone-based surfactant, and both a fluorine-containing surfactant and an anthrone-based surfactant. Or a fluorine-fluorenone-based surfactant is more preferable, and a fluorine-containing anthrone-based surfactant is preferred. Here, the 'fluoroneketone-based surfactant is a requirement of both a fluorine-based surfactant and an anthrone-based surfactant. By using such a surfactant, the composition of the present invention is applied to a tantalum wafer for manufacturing a semiconductor element, and a glass square substrate for manufacturing a liquid crystal element is formed with a chromium film, a molybdenum film, a molybdenum alloy film, a giant film, and a combination gold. A striated or scaly pattern produced on a substrate of various films such as a film, a tantalum nitride film, an amorphous germanium film, an indium oxide (ITO) film doped with tin oxide, or a tin oxide film (drying of the photoresist film) The problem of coating loss such as spotting can be solved, and the fluidity of the composition into the cavity of the mold can be improved, the peeling property between the mold and the photoresist can be improved, the adhesion between the photoresist and the substrate can be improved, and the viscosity of the composition can be lowered. Wait. In particular, the composition of the present invention can be greatly improved in coating uniformity by the addition of the surfactant, and good coating suitability irrespective of the substrate size can be obtained by coating with a spin coater or a slit coater. The non-ionic fluorine-based surfactant used in the present invention is, for example, trade name FLUORAD FC-430, FC-431 (manufactured by Sumitomo 3M Co., Ltd.), trade name SURFLON S-3 82 (made by Asahi Glass Co., Ltd.), EFTOP EF-122A, 122B. , 122C, EF-121, EF-126, EF-127, MF-100 (manufactured by TOCHEM PRODUCTS), trade name PF-636, PF-6320, PF-656 'PF-6520 (both are -42- 200923003 OMNOVA Company), the product name FUTAGENT FT250, FT25 Bu DFX18 (both are 'NE〇S (share) system), the trade name UNIDAIN DS-401, DS-403, DS-451 (all are DAIKIN industrial (share) system), goods MEGAFAC 171' 172, 173, 178K, and 178A (all manufactured by Dainippon Ink and Chemicals Co., Ltd.); Non-ionic fluorine-based surfactants, for example, trade name SI-10 series (made by Takemoto Oil Co., Ltd.), MEG AFAC PAINT ADD 31 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The fluoroneketone-based surfactants to be used in the present invention are, for example, trade names f Χ-70-090, Χ-70-091, Χ-70-092, Χ-70-093 (all manufactured by Shin-Etsu Chemical Co., Ltd.) , trade names MEGAFAC R-08, XRB-4 (all manufactured by Dainippon Ink Chemical Industry Co., Ltd.). Antioxidant The composition of the present invention contains a conventional antioxidant. The content of the antioxidant used in the present invention is preferably 10% by mass or less based on the total composition, more preferably 0.01 to 10% by mass, and particularly preferably 0.2 to 5% by mass. When two or more kinds of antioxidants are used, the total amount thereof is in this range. Antioxidants are those which are caused by various oxidizing gases such as ozone, active oxygen, ξV N 〇 x, and S Ο x (X-type integer), which are suppressed by heat and fading. In the present invention, an antioxidant may be added to prevent coloration of the cured film. It also has the advantage of reducing the film thickness reduction caused by decomposition. Such antioxidants are hydrazines, hindered amine antioxidants, nitrogen-containing heterocyclic guanidine compounds, thioether antioxidants, hindered phenolic antioxidants, ascorbic acid, zinc sulfate, thiocyanates, thiourea derivatives. A substance, a saccharide, a nitrite, a sulfite, a thiosulfate, a hydroxylamine derivative or the like. From the viewpoint of improving the permeability of the cured film and the reduction of the film thickness, the present invention is preferably a hindered phenol-based antioxidant, a hindered amine-based antioxidant, or a thioether-based antioxidant, and a hindered phenol-based antioxidant and hindered from the viewpoint of the present invention-43-200923003. Amine antioxidants are preferred. Commercial products of antioxidants include Irganoxl〇i〇, 1〇35, 1 076, 1 222 (above Ciba Jaki), Antigene P, 3C, FR, SUMILIZER S, SUMILIZER GA80 (Sumitomo Chemical Industry) ), ADEKASTAB AO70, AO80, AO503 (made by ADEKA), etc. These can be used alone or in combination. Other components In addition to the above components, the composition of the present invention may be added with a release agent, a decane coupling agent, a polymerization inhibitor 'UV absorber', a light stabilizer, an aging inhibitor, a plasticizer, a adhesion promoter, and a heat. A polymerization initiator, a colorant, an elastomer particle, a photoacid proliferation agent, a photobase generator, a basic compound, a flow regulator, an antifoaming agent, a dispersing agent, and the like. In order to improve the heat resistance and strength of the surface structure having the fine uneven pattern or the adhesion to the metal deposition layer, an organic metal coupling agent may be blended in the composition of the present invention. The organometallic coupling agent has an effect of promoting a thermosetting reaction. As the organometallic coupling agent, various coupling agents such as a decane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and a tin coupling agent can be used. The organometallic coupling agent can be arbitrarily blended in a ratio of 〇.〇〇丨1% by mass of the total solid content of the curable composition for photon imprinting. When the ratio of the organometallic affinity agent is 〇·〇 01% by mass or more, it is more effective in improving heat resistance, strength, and adhesion to the vapor deposition layer. On the other hand, when the ratio of the organometallic coupling agent is 1% by mass or less, it tends to suppress the loss of the composition in terms of stability and film formability. Commercial products of UV absorbers are Tinuvin P' 234, 320, 326, -44-200923003 3 27, 3 2 8, 213 (above Ciba Jaki), SumisorbllO, 130, 140 '220, 250 , 300, 320, 340, 350, 400 (above Sumitomo Chemical Industries). The ultraviolet absorber is preferably blended at a ratio of from 0.01 to 10% by mass based on the total amount of the curable composition for the photon imprint. Commercial products of light stabilizers are Tinuvin 292, 144, 622LD (above Ciba Jaki (share)), SANOL LS-770, 765, 292, 2626, 1114, 7 44 (above the three common chemical industry) )Wait. The photosensitizer is preferably blended at a ratio of from 0.01 to 10% by mass based on the total amount of the composition. Commercial products of the anti-aging agent include Antigene W, S'P, 3C, 6C, RD-G, FR, AW (manufactured by Sumitomo Chemical Industries, Ltd.). The aging preventive agent is preferably blended at a ratio of from 0.01 to 10% by mass based on the total amount of the composition. In order to adjust the adhesion to the substrate, the flexibility of the film, the hardness, and the like, a plasticizer may be added to the composition of the present invention. Specific examples of preferred plasticizers are dioctyl phthalate, di(didecanoate), triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, adipic acid Octyl ester, dibutyl sebacate, triethylene glycol glycerin, dimethyl adipate, di-n-butyl adipate, dimethyl succinate, diethyl succinate, di-n-butyl succinate, and the like. The plasticizer may be arbitrarily added in an amount of 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. 01质量质量以上以上。 Preferably, in order to obtain a plasticizer, preferably 0.1% by mass or more. In order to harden the composition of the present invention, a thermal polymerization initiator may be added as necessary. Preferred thermal polymerization initiators are, for example, peroxides and azo compounds. Specifically, there are benzammonium peroxide, butyl peroxybenzoate, azoisobutyronitrile, and the like. In order to adjust the shape, sensitivity, and the like of the pattern, a photobase generator may be added to the composition of the present invention as necessary. Preferred are, for example, 2-nifedicyclohexylamine formate, -45 - 200923003 triphenylmethanol, 0-amine formazan hydroxyguanamine, hydrazine-amine formazan, [[(2,6-di) Nifedimethyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexa-1,6-diamine, 4-(methylthiobenzyl)- 1-methyl-1-tyrosine ethane, (4-glycine benzhydryl)-1-benzyl-1-dimethylamine propane, N-(2-nitrobenzyloxycarbonyl) pyrrolidine, ginseng (tritylboronic acid) hexaammonium cobalt (111), 2-benzoyl-2-dimethylamine-1-(4-morpholinylphenyl)butanone, 2,6-dimethyl-3,5-di Ethylene-4-(2'-nitrophenyl)-1,4-dihydropyridine, 2,6-dimethyl-3,5-diethylhydrazine- 4.(2',4'-dinitrophenyl )-1,4-dihydropyridine and the like. f may be any coloring agent added to the composition of the present invention for the purpose of enhancing the visibility of the coating film. The coloring agent can use a pigment or a dye used for a composition such as a UV inkjet composition, a color filter composition, a CCD image sensor, or the like, without departing from the object of the present invention. The pigments which can be used in the present invention are various inorganic pigments or organic pigments. The inorganic pigment is a metal compound such as a metal oxide or a metal salt, and specifically includes an oxide of a metal such as iron, gu, m, tin, copper, zinc, titanium, magnesium, chromium, zinc or lanthanum, and a metal composite oxide. Organic pigments are, for example, C.I. Pigment Yellow 11, 24, 31, 53, 83, , 99, 108, 109, 110, 138, 139, 15 154, 167, C.I. Pigment 'k,

Orange 36, 38, 43' CI Pigment Red 105, 122, 149, 150, 155, 171, 175 '176 '177, 209, CI Pigment V1〇let 19, 23, 32, 39, CIPigmentBluel, 2, 15, 16, 22, 60, 66, CI Pigment Green 7 '36, 37 ' CI Pigment Brown 25 ' 28, C. I · P igment B 1 ack 1, 7, and carbon black. The colorant is preferably blended at a ratio of 0.001 to 2% by mass based on the total amount of the composition. For the purpose of improving mechanical strength, flexibility, and the like, elastomer particles may be added as an optional component to the composition of the present invention. -46- 200923003 The composition of the present invention may be added as an elastomer particle of an optional component, and the average particle size is preferably 10 to 700 nm, more preferably 30 to 300 nm. For example, polybutadiene, polyisoprene, butadiene/acrylonitrile copolymer, styrene/butadiene copolymer, styrene/isobutyl copolymer, ethylene/propylene copolymer 'ethylene/α-olefin copolymer , ethylene/α-olefin/polyene copolymer' propylene rubber, butadiene/(meth) acrylate copolymer, styrene/butadiene block copolymer, styrene/isoblock copolymer, etc. Particles of elastomer. These core particles may be coated with a core/shell type particle coated with a methyl methacrylate polymer, a methyl methacrylate/glycidyl methacrylate copolymer or the like. The elastic particles may also have a crosslinked structure. These elastomer particles may be used alone or in combination of two or more. The composition ratio of the elastomer particles in the composition of the present invention is preferably from 1 to 35 % by mass, more preferably from 2 to 30% by mass, particularly preferably from 3 to 20% by mass. The basic compound may be optionally added to the composition of the present invention for the purpose of suppressing the hardening shrinkage and improving the thermal stability. The basic compound may be an amine or a nitrogen-containing heterocyclic compound such as a quinoline or a hydrazine trap, a basic alkali metal compound or a basic alkaline earth metal compound. Among these, an amine is preferred because it is compatible with a photopolymerizable monomer, and examples thereof include octylamine, naphthylamine, xylene diamine, diphenylmethylamine, diphenylamine, dibutylamine, dioctylamine, and Toluidine, azide, tributylamine, trioctylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine, hexamethylenetetramine and triethanolamine. In order to enhance photocurability, a chain transfer agent may also be added to the composition of the present invention. Specifically, there are 4-bis(3-indolyloxy)butane, 1,3,5-gin(3-indolyloxy)-1,3,5-trisole-2,4,6 (1Η) , 3Η, 5Η) triketone, pentaerythritol bismuth (3-indolyl butyrate). -47- 200923003 Next, a method of forming a pattern (especially a fine uneven pattern) using the composition of the present invention will be described. In the present invention, the composition of the present invention is coated and hardened to form a pattern. Here, the composition of the present invention is usually irradiated with light or heat, preferably by light and heat. Specifically, at least a pattern forming layer composed of the composition of the present invention is applied onto a substrate or a support, and if necessary, dried to form a layer (pattern forming layer) composed of the composition of the present invention, and a pattern acceptor is pressed. The pattern of the pattern receptor forms the surface of the layer, performs transfer processing of the mold pattern, and hardens the fine uneven layer formation layer by light and heat. It is usually necessary to perform multiple times of illumination and heating. In the pattern forming method of the present invention, photoimprint lithography can be used for lamination, multiple patterning, or in combination with conventional hot stamping. The composition of the present invention may be applied by coating the composition of the present invention on a substrate or a support, exposing and hardening the layer formed of the composition, and drying (baking) if necessary to prepare a top coat and insulation. Permanent film such as film. For permanent film (such as photoresist for structural components) for liquid crystal display (LCD), in order to prevent the display from acting, it is best to avoid metal or organic ionic impurities from being mixed into the photoresist. The concentration must be less than 100 ppm, less than 100 ppm. Better. A pattern forming method and a pattern transfer method using the composition of the present invention will be described below. The composition of the present invention can be formed by a conventional coating method such as a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a concave roll coating method, an extrusion coating method, a spin coating method, or the like. . The film thickness of the layer composed of the composition of the present invention varies depending on the use, and is 0.05 to 30 μm. The composition of the present invention can also be multi-coated. -48- 200923003 The substrate or support for coating the composition of the present invention includes quartz, glass, optical film, ceramic material, vapor deposited film, magnetic film, reflective film, metal substrate such as Νι, Cu, Cr, Fe, paper,聚合物G, polyester film polycarbonate film, polymer substrate such as polyimide film, TFT array substrate, pDp electrode plate, glass, transparent plastic substrate, conductive substrate such as germanium, metal, insulating substrate There are no particular restrictions on semiconductor substrates such as tantalum, tantalum nitride, polycrystalline germanium, germanium oxide, and amorphous germanium. The substrate may be in the form of a plate or a roll. The light for hardening the composition of the present invention is not particularly limited, and has high-energy ionization f radiation, near-ultraviolet rays, far ultraviolet rays, visible light, infrared light, and the like. High-energy ionizing radiation has electron beams accelerated by accelerators such as Krakow accelerators, Vandergrave accelerators, linear accelerators, beta accelerators, cyclotrons, etc., which is the most convenient and economical for industrial use. Radiations such as T-lines, X-rays, α-lines, neutron beams, and proton beams of isotopes and atomic furnaces can also be used. Examples of ultraviolet sources include ultraviolet fluorescent lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, carbon arc lamps, and solar lamps. The radiation contains, for example, microwaves, ΕυV. : Laser light for semiconductor microfabrication, such as LED, semiconductor laser light, or 248 nm KrF excimer laser light, I93 nm ArF excimer laser, is also suitable for use in the present invention. These lights may be monochromatic or may be light of a plurality of different wavelengths (mixed light). Exposure should be 1 mW/cm2 to 50 mW/cm2. When the exposure time is lmW/cm2 or more, the productivity is improved, and if it is 50 mW/cm2 or less, it is preferable to suppress deterioration of permanent film characteristics due to side reactions. The exposure amount is preferably 5 mJ/cm 2 to 1000 m; T/cm 2 . If it is less than 5mJ/cm2, the exposure margin is narrow, the photohardening is insufficient, and it is easy to have unreacted substances attached to the mold. -49-200923003 occurs. On the other hand, if it exceeds 100 〇ml/cm2, the composition is decomposed and the permanent film is degraded. At the time of exposure, the anti-oxidation is resistant to the radical polymerization, and the inert gas such as nitrogen can be flowed, and the oxygen concentration is controlled to be less than 10 mg/L. The curing temperature of the composition of the present invention is 150~ 2 80 °C is better '200~250 °C better. The heating time is preferably 5 to 60 minutes, and more preferably 15 to 45 minutes. Next, a mold material which can be used in the present invention will be described. The photon imprinting using the composition of the present invention must be such that at least one of the mold material and/or the substrate is selected from a light transmissive material. The photoimprint lithography system of the present invention is applied to a substrate for coating a curable composition for photon imprinting on a substrate, and is pressed by a translucent mold to illuminate the back surface of the mold to form a hardening composition for photon imprinting. Hardening of matter. Further, a curable composition for photon imprinting can be applied to a light-transmitting substrate, and pressed by a mold to illuminate the back surface of the mold to harden the curable composition for photon imprinting. The illuminating may be carried out in a state where the mold is attached, or may be carried out after the mold is peeled off, and the present invention is preferably carried out in a state where the mold is adhered. The mold which can be used in the present invention is a mold having a pattern to be transferred. The mold can be formed into a pattern by the lithography, the electron beam drawing method or the like, for example, in accordance with the desired processing precision. The mold pattern forming method of the present invention is not particularly limited. The light-transmitting mold material used in the present invention is not particularly limited, and is preferably excellent in strength and durability. Specifically, there are, for example, a transparent resin such as glass, quartz, pmma or polycarbonate resin, a transparent metal deposited film, a soft film such as polydimethyl siloxane, a photocured film, a metal film or the like. The non-transmissive mold material used in the use of the transparent substrate of the present invention is not limited to a specific strength, and is preferably a specific strength. Specifically, for example, a ceramic material, a vapor deposited film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, or Fe, SiC, tantalum, nitrided sand, polycrystalline sand, oxidized sand, amorphous sand substrate, or the like, Special restrictions. The shape can be either a plate shape or a roll shape. Rollers are especially useful when continuous production is required. The mold used in the present invention described above can be used for mold release treatment in order to improve the peelability of the curable composition for photon imprinting from the mold. For the treatment of decane coupling agents such as anthrone or fluorine, for example, commercially available release agents such as OTOCO Industrial Co., Ltd., OPXOL, DSX, and Sumitomo 3M Novec EGC-1720 are also suitable. In the case of photoimprint lithography according to the present invention, the mold pressure is usually preferably 10 or less. When the mold pressure is below 10 atm, the mold and the substrate are not easily deformed, the pattern accuracy can be improved, and the device can be shrunk and reduced because of low pressure. The mold pressure is preferably selected in the range of ensuring uniformity of transfer of the mold in a range in which the residual film of the curable composition for the light embossing of the mold convex portion is small. In the present invention, the illumination of the photoimprint lithography is preferably greater than the amount of illumination required for hardening. The amount of irradiation required for hardening is determined by the amount of the unsaturated bond of the hardenable composition of the photon nanoimprint and the viscosity of the cured film. The photoimprint lithography which is suitable for use in the present invention is usually at a normal temperature when the light is irradiated, and can be heated while being heated to improve the reactivity. When the front part of the illuminating light is in a vacuum state, the reactivity of the air bubbles can be effectively prevented from being mixed, the reactivity caused by the mixing of oxygen is suppressed, and the adhesion between the mold and the hardenable composition for the photon imprinting is improved. Light in the state. In the present invention, the preferred degree of vacuum is from 10 MPa to atmospheric pressure. The composition of the present invention may be prepared by mixing the above components, and filtering the solution by, for example, a filter having a pore diameter of -51 - 200923003 0.05 / / m - 5.0 / / m. The mixing of the hardenable composition for photon imprinting. Dissolution is usually carried out in the range of 〇 °C ~ 1 0 0 t:. Filtration can be carried out in multiple stages or repeated many times. The filtered liquid can be filtered again. The material used for the filtration may be a polyethylene resin, a polypropylene resin, a fluororesin, a nylon resin, or the like, and is not particularly limited. A permanent film (resistance for a structural member) used for a liquid crystal display (LCD) is bottled in a gallon bottle or a quart bottle after being manufactured, and is stored and preserved. In this case, it is inactivated in the container. Substituted by nitrogen or argon. When transporting and storing, it can be kept at room temperature to prevent deterioration of the permanent film, and the temperature can be controlled at _2〇 °c ~ 0 °c. Of course, it must be shaded to the extent that it does not respond. The composition of the present invention is also suitable for use as an etching resistor for a semiconductor integrated circuit, a recording material, or a flat panel display. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amount, the ratio, the processing contents, the processing order, and the like shown in the following examples can be appropriately changed without departing from the scope of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. <Evaluation of Photon Imprint> Each of the compositions obtained in the examples and the comparative examples was measured and evaluated according to the following evaluation method. <Viscosity measurement> The viscosity measurement was carried out at 25 ± 0.2 °C using a RE-80L rotary viscometer manufactured by Toki Sangyo Co., Ltd. The number of revolutions at the time of measurement is '〇.5mPa.s or less and less than 5mPa.s. l〇〇r -52- 200923003 5mPa·s or less is less than 10mPa·s for 50rpm, lOmPa·s or less is less than 30mPa·s for 20rpm. , 30mPa. s or less is less than 60mPa·s, lOrpm, 60mPa. s or less is less than 120mPa. s is 5rpm, 120mPa. s is lrpm or 0 · 5 rpm. <Observation of Pattern Accuracy> Each of the components of the following Tables 1 to 7, a photopolymerization initiator, a surfactant, and an antioxidant was prepared and spin-coated on a glass substrate to have a film thickness of 3.0 # m . Place the spin-coated base film on a nano-imprinting device with a high-pressure mercury lamp (lamp power 2000mW/cm2) made by ORC, with a mold pressure of 0.8kN, and the vacuum degree in the exposure is i〇Torr. Line/space pattern of 10//m, polydimethyl methoxy oxane with a depth of 4.0 // m (made by Toray Dow Corning, SILPOT184 hardened at 80 °C for 60 minutes) with a mold surface of 240 ml/ The condition of cm2 is exposed, and after exposure, it is separated from the mold to obtain a photoresist pattern. The resulting photoresist pattern was completely cured by heating in an oven at 203 °C for 30 minutes. The shape of the pattern after transfer was observed with a scanning electron microscope or an optical microscope, and the shape of the pattern was evaluated as follows. A: The pattern shape of the mold is almost the same as that of the original pattern. B: The pattern shape of the mold is partially different from the original pattern shape (less than 10% difference from the original) C: The pattern shape of the mold is partially different from the original pattern shape (with the original) D: 10% or more is less than 20%) D: The pattern shape of the mold is significantly different from the original pattern, or the pattern thickness is different from the original pattern by more than 20% <Evaluation of peelability> -53- 200923003 The sample for observation of pattern accuracy was observed by a scanning electron microscope or an optical microscope to see whether or not a composition component adhered to a mold used for patterning, and the peelability was evaluated as follows. A: There is a hardening composition adhesion when the mold is completely absent B: Sometimes the hardening composition adheres to the mold C: When the mold is clearly visible, there is adhesion of the hardening composition <Evaluation of hardness> Spin coating composition The film thickness on the glass substrate can be 3~10 0 m, not pressed by the mold, exposed to an exposure amount of 240 m/cm 2 under a nitrogen atmosphere, and then heated at 230 ° C for 30 minutes in an oven to obtain a cured film. The dynamic hardness was measured by a micro hardness tester manufactured by Shimadzu Corporation. The measurement conditions were a triangular pyramid indenter with a load of 1 mN and a holding time of 1 second. Dynamic hardness A: 32 or more B: 2 8 or more is less than 3 2 , C: 25 or less is less than 28 D: less than 25 < evaluation of transmittance > Spin coating each composition on a glass substrate to a film thickness of 3.0 // m, not pressed by the mold, exposed to 240m/cm2 under nitrogen atmosphere, and then cured in an oven at 270 °C for 270 minutes to obtain a cured film, manufactured by Shimadzu Corporation UV - 2 4 0 0 The PC measured the transmittance at 400 nm. Transmittance A: 97% or more B: 9 5 % or more is less than 9 7 % -54 - 200923003 C : 9 0 % or more is less than 9 5 % D : less than 90% <solvent resistance test> Spin coating Each composition was made to have a film thickness of 3.0/m on a glass substrate, not pressed by a mold, exposed to an exposure amount of 240 m/cm 2 in a nitrogen atmosphere, and then heated at 230 ° C for 30 minutes in an oven to obtain a cured film. Soaked in N-methylpyrrole at 25 ° C; c ketone solvent for 30 minutes, the change of the cured film before and after soaking was evaluated as follows. A: film thickness change is less than 1% f B : film thickness change is 1% or more, less than 2% C: film thickness change is 2% or more, less than 10% D: surface roughness < different reactivity in the same molecule Monomer of two or more kinds of curable functional groups> Q-1: Compound (M-12) biscyclopentenyl acrylate (FA-511AS: manufactured by Hitachi Chemical Co., Ltd.) Q-2: Compound (Μ-1 3) acrylic double ring Ethyl oxyethyl ester (FA-5 1 2AS: manufactured by Lihua Chemical Co., Ltd.) 'Q-3 : Compound (M-32) 3-cyclohexene methyl acrylate Q-4 : Compound (M-22) isocyanide Acetyl propylene oxide (Karenz AOI: manufactured by Showa Denko)

Q-5: Compound (M-24) 3-ethyl-3-glycidyl acrylate (VISCOAT OXE 10: manufactured by Osaka Organic Chemical Industry Co., Ltd.) Q-6: Compound (M-29) 3-trimethoxy acrylate Propyl propyl ester (KBM-5103: manufactured by Shin-Etsu Chemical Co., Ltd.) Q-7: Compound (M-30) allyl acrylate (a reagent manufactured by Aldrich Co., Ltd.) -55- 200923003 Q-8: Compound (M-33) acrylic acid 2-propenyloxy-3-allyloxypropyl propyl ester Q - 9 : compound (Μ - 4) 2,3-diallyloxypropyl acrylate Q -1 0 : compound (Μ - 3 4) acrylic acid 3,5 -diallyloxycyclohexyl ester oxime-11: compound ^-38) 3,5-bis(allyloxycarbonyl)phenyl acrylate Q-12: compound (Μ-39) 4-allyloxycarbonyl phenyl acrylate Q-13: Compound (Μ-40) allyloxycarbonyl-3,5-bis(acryloxy)benzene Q-14: Compound (Μ-41) bis propylene methoxy methoxypropionate Q -15: compound (Μ-42) bisallyloxycarbonylethyl acrylate, Q-16 : compound (Μ-43) allyloxycarbonyl methacrylate f ^ Q-17: compound (M-44 Allyloxycarbonylethyl acrylate <other monofunctional monomer> R-1: benzyl acrylate (VISCOAT #160: Osaka has Machine Chemical Co., Ltd.) R - 2 : 2-naphthyl acrylate R-3 : 1-naphthyl methacrylate <other difunctional monomer > S-01 : neopentyl glycol diacrylate <Other trifunctional or higher Monomer> S-10: Trimethylolpropane triacrylate (ARON IX M-3 09: manufactured by Toagosei Co., Ltd.) s-ll: 1,3,5-paraben oxime oxime <Other trifunctional or higher Monomer > s -1 2 : Tetrafunctional urethane acrylate (U - 4 Η A: manufactured by Shin-Nakamura Chemical Co., Ltd.) <Other polymerizable monomers> S-23: HOA-MS (succinic acid 2- Propylene oxime ethyl ester 'Kyoeisha Chemical Co., Ltd. -56- 200923003 <Photopolymerization initiator> P-1: Oxidation of 2,4,6-trimethylglyoximeyl phenylphosphine (LucirinTPO-L) : BASF Corporation) <Interacting Agent> W-1: Non-fluorine-based surfactant (made by Takeshiba Oil & Fats Co., Ltd.: PIONIN D6315) W-2: Fluorine-based surfactant (DIC: MEGAFAC) F7 80F) <Antioxidant> Al: Sumilizer GA80, hindered phenolic system (Sumitomo Chemical Co., Ltd.)

, A-2 : ADEKASTAB AO 5 0 3, hindered phenolic system + thioether system (made by ADEKA JAPAN Co., Ltd.) A-3: Irganox 1035FF, hindered phenolic system + thioether system (manufactured by Steam Bart Chemical Co., Ltd.) A-4 : ADEKASTAB LA-57 > Hindered amine 'system (made by ADEKA Co., Ltd.) A-5: TINUVIN 144, hindered amine system + hindered phenol system (manufactured by Vapart Chemical Co., Ltd.) <nonanone oil> X-1 : X -22-3 7 1 0 (Shin-Etsu Chemical Co., Ltd.) -57- 200923003 Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Compound mass % Compound mass % Compound mass % Compound mass % Compound mass % 0-1 48.2 0-2 48.2 0-3 38.6 Q-4 38.6 0-5 16.4 S-01 48.2 S-01 48.2 S-01 57.8 S-01 28.9 S-01 28.9 Polymeric Unsaturated S-10 28.9 S -10 28.9 Monomer R-1 22.2 Photopolymerization initiator P-1 0.5 P-1 0.5 P-1 0.5 P-1 0.5 P-1 0.5 Surfactant W-1 0.1 W-1 0.1 W-1 0.1 W- 1 0.1 W-1 0,1 W-2 0.04 W-2 0.04 W-2 0.04 W-2 0.04 W-2 0.04 Antioxidant A-1 1 A-1 1 A-1 1 A-1 1 A-1 1 A-2 2 A-2 2 A-2 2 A-2 2 A-2 2 Table 2 Example 6 Example 7 Example 8 Example 9 Example 10 Compound mass % Compound mass % Compound mass % Compound mass % Compound mass % Q-6 38.6 0-7 38.6 0-1 19.3 0-2 19.3 0-1 19.3 S-01 28.9 S-01 28.9 S- 01 28.9 S-01 28.9 S-01 19.3 Polymeric Unsaturated S-10 28.9 S-10 28.9 R-1 12.5 R-1 12.5 S-10 19.3 Monomer 0-5 35.7 0-5 35.7 R-1 16.4 0- 5 22.1 Photopolymerization initiator P-1 0.5 P-1 0.5 P-1 0.5 P-1 0.5 P-1 0.5 Surfactant W-1 0.1 W-1 0.1 W-1 0.1 W-1 0.1 W-1 0.1 W -2 0.04 W-2 0.04 W-2 0.04 W-2 0.04 W-2 0.04 Antioxidant A-1 1 A-1 1 A-1 1 A-1 1 A-1 1 A-2 2 A-2 2 A -2 2 A-2 2 A-2 2 -58- 200923003 Table 3 Implementation / Example 11 Implementation 1 A 12 Implementation 1 Net 13 Compound mass % Compound mass % Compound mass % Polymerizable unsaturated monomer 0-5 16.1 0- 5 16.1 0-5 16.1 0-8 28.9 0-9 28,9 Q-10 28.9 S-10 28.9 S-10 28.9 S-10 28.9 R-1 22.5 R-1 22.5 R-1 22.5 Photopolymerization initiator P- 1 0.5 P-1 0.5 P-1 0.5 Surfactant W-1 0.1 W-1 0.1 W-1 0.1 W-2 0.04 W-2 0.04 W-2 0.04 Antioxidant A-1 1 A-1 1 A-1 1 A-2 2 A-2 2 A-2 2 Table 4 Example 14 Example 15 Example 16 Example π Example 18 Compound mass % Compound mass % Compound mass % Compound mass % Compound mass % Q-6 10 Q -6 10 Q-6 10 Q-6 10 Q-6 10 Q-5 18.8 Q-12 29.2 Q-13 17.2 R-3 17.2 S-ll 17.2 Polymerizable Unsaturated R-1 23.2 R-1 23.3 R-1 23.3 R-1 23.3 R-1 23.3 Monomer S-10 26.6 S-10 22.4 Q-5 23.2 0-5 23.2 0-5 23.2 S-01 17.1 R-2 11.4 S-10 22.6 S-10 22.6 0-11 22.6 S-23 0.5 Photopolymerization initiator Ρ·1 0.5 P-1 0.5 P-1 0.5 P-1 0.5 P-1 0.5 Surfactant W-1 0.1 W-1 0.1 W-1 0.1 W-1 0.1 W- 1 0.1 W-2 0.04 W-2 0.04 W-2 0.04 W-2 0.04 W-2 0.04 Antioxidant A-1 1 A-1 1 A-1 1 A-1 A-1 1 A-2 2 A-2 2 A-2 2 A-2 2 A-2 2 fluorenone oil Xl 0.1 Xl 0.1 Xl 0.1 Xl 0.1 Xl 0.1 -59- 200923003 Table 5 Implementation 1 Net 19 Implementation 1 Column 20 Implementation 1 Net 21 Compound mass 0 / 〇 compound Mass % Compound mass 1 Polymerizable unsaturated monomer R-1 22.1 R-1 23.3 R-1 23 0-5 18.1 Q-5 19.1 Q-5 18.6 S-01 16.5 S-01 17.2 S-01 26.2 S-10 2 5.4 S-10 26.7 Q-12 16.8 S-12 4.73 S-12 3 Q-6 6.8 Q-6 9.5 Q-6 7 S-12 4.9 Photopolymerization Initiator P-1 0.48 P-1 0.5 P-1 0.44 Interface Active agent W-1 0.1 W-1 0.1 W-1 0.1 W-2 0.04 W-2 0.04 W-2 0.04 Antioxidant A-1 1.91 A-1 1.96 A-1 2 A-3 0.95 A-3 1 A- 3 1 fluorenone oil X-1 0.19 X-1 0.1 X-1 0.12 Table 6 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Compound mass % Compound mass % Compound mass 〇 / 〇 compound mass % Compound mass % Compound mass % Polymerizable unsaturated monomer Q-6 10 Q-6 10 Q-6 20 Q-6 20 Q-6 10 Q-6 10 0-5 19.8 Q-12 29.2 Q-14 47.3 Q -15 47.3 Q-16 52.3 Q-17 52.3 R-1 23.2 R-1 23.3 S-10 30 S-10 30 S-10 35 S-10 35 S-10 26.6 S-10 22.4 S-01 17.1 R-2 11.4 S-23 0.5 Photopolymerization initiator P-1 0.5 P-1 0.5 P-1 0.5 P-1 0.5 P-1 0.5 PI 0.5 Surfactant W-1 0.1 W-1 0.1 W-1 0.1 W-1 0.1 W-1 0.1 W-1 0.1 W-2 0.04 W-2 0.04 W-2 0.04 W-2 0.04 W-2 0.04 W-2 0.04 Antioxidant A-4 2 A-5 3 A-4 2 A-4 2 A-4 2 A-4 2 Anthrone oil X-1 0.1 X-1 0.1 X-1 0.1 X-1 0.1 X-1 0.1 X-1 0.1 -60- 200923003 Table 7 Implementation 1 Column 28 Implementation 1 Net 29 Implementation 1 Column 30 Compound Mass % Compound Quality % Compound mass % Polymerizable unsaturated monomer 0-6 10 Q-6 10 Q-6 10 〇-12 5 〇-12 5 Q-12 5 0-5 17 0-5 17 Q-5 17 R-1 21.8 R-1 21.8 R-1 21.8 S-01 10.2 Q-14 10.2 Q-15 10.2 S-10 26.7 S-10 26.7 S-10 26.7 S-23 0.5 S-23 0.5 S-23 0.5 S-12 5 S- 12 5 S-12 5 Photopolymerization initiation Qi P P 0.5 0.5 P-1 0.5 P-1 0.5 Interfacial activity 剤W-1 0.1 W-1 0.1 W-1 0.1 W-2 0.04 W-2 0.04 W-2 0.04 Antioxidant A-1 2 A-1 2 A-1 2 A-3 1 A-3 1 A-3 1 Anthrone oil X-1 0.2 X-1 0.2 X-1 0.2 According to the composition of the above table, the above monomers are compounded. The composition of the examples was prepared, and the viscosity, pattern accuracy, peelability, hardness, transmittance, and solvent resistance were measured. The results are shown in Table 9. Comparative Example 1 The composition described in Example 6 of the ink-jet composition disclosed in International Publication No. WO2004/099272 was subjected to the measurement of the pattern precision, peelability, hardness, transmittance, and solvent resistance as in the present example. . The composition of the composition is shown in Table 8, and the test results are shown in Table 9. -61 - 200923003 Comparative Example 2 The composition described in Example 1 of the composition for nanoimprint disclosed in JP-A-2007-84625, as shown in the present example, was used to measure pattern accuracy, peelability, hardness, and Transmittance, solvent resistance. The composition of the composition is shown in Table 8, and the test results are shown in Table 9. Comparative Example 3 The composition described in Example 3 of the photocurable composition disclosed in JP-A-2005-255 85-4 was subjected to the measurement of the pattern, degree, hardness, transmittance, and solvent resistance as in the present example. Sex. The composition of the composition is shown in Table 8, and the test results are shown in Table 9. Comparative Example 4 The composition described in Example 2 of the photocurable composition disclosed in JP-A-2007- 1 865 70 was measured in the same manner as in the present example, and the pattern precision, hardness, and transmittance were measured. The composition of the composition is shown in Table 8, and the test results are shown in Table 9. Comparative Example 5 The composition described in Example 6 of the photocurable composition disclosed in JP-A-2007- 1 865 70 was measured in the same manner as in the present example, and the pattern precision, hardness, and transmittance were measured. The composition of the composition is shown in Table 8, and the test results are shown in Table 9. None of the comparative examples 1 to 5 contained an antioxidant. Comparative Example 2 and Comparative Example 4 did not contain two or more kinds of curable functional groups having different reactivity. -62- 200923003 Comparative Example 5 Mass % cK 28.5 Ο) t-< Os 28.5 Compound BPE-500 LITE ESTER 1G 1 FA-511 A 卜 £ cd 茗MEGA FAC R08 BPE-500 LITE ESTER 1G FA-511 A Compare Example 4 Mass % 28.5 Os inch · o 28.5 Compound BPE-500 LITE ESTER 1G LITE ESTER BZ s cd dan MEGA FAC R08 BPE-500 LITE ESTER 1G LITE ESTER BZ Comparative Example 3 Mass % 3 ro Compound Acrylic 2-Ethylene ethoxylate Ethyl acetate isobutyl ester Irgacure 184 _i ADEKASTABAO30 Comparative Example 2 Mass % 00 CN — 5 Compound u-> s α (U N-vinylpyrrolidone t 瑁 & ^ &- EV g: ;s Λ ^ fr w (N MEGA FAC R08 Comparative Example 1 Mass % 〇V-) (N compound propylene glycol acrylate propyl hydroxypropyl triacrylate isopropyl isophthalate N-vinyl-2-pyrrolidone oxime 3-ethyl- 3-Phenyloxypropylene oxide (N a 1 1 11 Φ # El· (N ADEKAOPTOMER SP-152 200923003 Table 9

Viscosity pattern precision peelability Hardness transmittance Solvent resistance Example 1 9.9 AAAAB Example 2 9.9 AABAB Example 3 10.0 AAAAB Example 4 5.8 AAAAB Example 5 8.7 AAAAB Example 6 6.6 AAAAB Example 7 5.5 AAAAB Example 8 8.5 AAAAB Example 9 9.4 AAAAB Example 10 8.7 AAAAB Example 11 8.0 AAAAA Example 12 7.8 AAAAA Example 13 9.8 AAAAA Example 14 6.8 AABAA Example 15 9.1 > AABAA Example 16 8.5 AABAA Example 17 7.5 AABAA Example 18 15.2 AABAA Example 19 8.3 AABAB Example 20 8 AABAA Example 21 10 AABAA Example 22 7.2 AABAA Example 23 9.5 AABAA Example 24 16 AAAAA Example 25 14 AAAAA Example 26 10 AABAA Example 27 11 AABAA Example 28 9.1 AABAA Example 29 11 AAAAA Example 30 11 AAAAA Comparative Example 1 19.5 CCCDB Comparative Example 2 11.4 ABDDC Comparative Example 3 7.0 ACDAD Comparative Example 4 5.6 ABDDD Comparative Example 5 16.4 ABBDC -64 - 2 00923003 The composition of the present invention is excellent in pattern accuracy, peelability, hardness, and transmittance. The composition of the comparative example was poor in hardness. In Comparative Example 1, the pattern accuracy and the transmittance were poor. Industrial Applicability According to the present invention, it is possible to provide a composition excellent in permeability, mechanical strength, releasability, pattern shape, applicability, and solvent resistance after heat curing as a permanent film. When it is used as a permanent film such as a transparent protective film or a spacer, it is a composition having excellent mechanical properties such as residual film properties, light transmittance, and scratch resistance. [Simple description of the diagram] Μ . [Main component symbol description] te 〇 /\w -65-

Claims (1)

200923003 X. Patent application scope: 1. A hardening composition for nanoimprinting, characterized by containing (A) a monomer having at least two reactive functional groups having different reactivity in the same molecule and (C) ) Antioxidants. 2. The curable composition for nanoimprinting according to the first aspect of the invention, wherein at least one of the curable functional groups is an unsaturated ester group. 3. The curable composition for nanoimprinting according to item 1 of the patent application, further comprising (Β) a surfactant. 4. The hardenable composition for nanoimprinting according to claim 1, wherein the viscosity of the composition is in the range of 3 to 18 mPa·s. 5·—for a nanoimprint, a curable composition containing at least two or more kinds of curable functional groups having different reactivity in the same molecule, and at least one of the curable functional groups is unsaturated. A monomer for ester group, (B) a surfactant, and (C) a curable composition for nanoimprint of an antioxidant, characterized in that the viscosity of the composition is in the range of 3 to 18 mPa·s. 6. The hardenable composition for nanoimprinting according to item 1 of the patent application, wherein the single system is as shown in the following general formula (1); (In the general formula (1), R1 represents a hydrogen atom or a hydroxymethyl group, X represents an organic group; m is an integer of Tables 1-3, an integer of the !! table; and the Y table has a hardening property of a carbon-carbon unsaturated bond. An energy group, a hardening functional group having a carbon-nitrogen unsaturated bond, a hardening functional group having a cyclic group containing an oxygen atom, or a group represented by the following general formula (2) - General formula (2) -66- 200923003 (R2 each alkyl or aryl group). 7. The hardenable composition for nanoimprinting according to item 6 of the patent application, wherein at least the Y of the general formula (1) is selected from the group consisting of a vinyl ether group, an allyl ether group, an allyl ester group, Cyclohexenyl, cyclopentenyl, dicyclopentenyl, styryl, methacryloxy, methacrylamido, acrylamido, vinyl fluorenyl, N-vinyl heterocyclic and Group of maleimide groups. 8. The hardenable composition for nanoimprinting according to item 6 of the patent application, wherein at least one of Y in the general formula (1) is selected from the group consisting of allyl ether groups, cyclohexenyl groups, and cyclopentenyl groups. And dicyclopentenyl. 9. The hardenable composition for nanoimprinting according to item 6 of the patent application, wherein at least one of the allyl ether groups of Y in the general formula (1), and the sum of η and m are 3 to 6. 10. The hardenable composition for nanoimprinting according to item 6 of the patent application, wherein at least one of the isocyanate groups or nitrile groups of Y in the general formula (1). 1 1 . The hardenable composition for nanoimprinting according to item 6 of the patent application, wherein at least one of Y in the general formula (1) is selected from the group consisting of a epoxidized ring, an epoxy ring, and a carbonic acid a group of ester groups. 1 2 · $D is a hardening composition for nanoimprinting according to item 6 of the patent application, wherein an organic group having a total carbon number of 3 to 9 in the formula X (1). 1 3 - The curable composition for nanoimprinting according to item 6 of the patent application, wherein the compound represented by the general formula (1) is any one of the following general formulas (3) to (5); 67- 200923003 °γ° *^R3 General formula (3) general formula (4) 0"^\-^Si(0R4)3 General formula (5) (in the general formulas (3) to (5), each of the hydrogen atoms or methyl groups of r3, and each methyl or ethyl group of R4). (1) The curable composition for nanoimprinting according to the first aspect of the invention, which comprises a polymerizable monomer other than the monomer (A) and a photopolymerization initiator. The hardenable composition for nanoimprinting according to the ninth aspect of the invention, wherein the antioxidant is at least selected from the group consisting of a hindered phenol-based antioxidant or a hindered amine-based antioxidant. In the case of the curable composition for nanoimprinting according to the first aspect of the patent application, the content of the antioxidant is 10% by mass or less. 17. The hardenable composition for nanoimprinting according to item 1 of the patent application, which does not contain a compound having a molecular weight of more than 1,000. 18. The hardenable composition for nanoimprinting according to the ninth aspect of the invention, wherein the surface tension of the composition is in the range of 18 to 30 mN/m. 1 9. The hardenable composition for nanoimprinting according to the first aspect of the patent application, wherein the hardening composition is cured by irradiation and heating. A cured product obtained by hardening a hardenable composition for nanoimprinting according to any one of claims 1 to 19. -68-200923003 2 1 - A method for producing a cured product, which comprises irradiating a hardening composition for nanoimprinting according to any one of claims 1 to 19 by a plurality of times Hardened by heating. A member for a liquid crystal display device characterized by using a cured product as in item 20 of the patent application. And a method for producing a member for a liquid crystal display device, comprising: performing a plurality of irradiation lights by using a hardening composition for nanoimprinting according to any one of claims 1 to 19; Hardened by heating. -69- 200923003 VII. Designation of representative representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ. ^ 1 f \ VIII. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: