KR101463849B1 - Curable composition for optical nanoimprint lithography and pattern forming method using the same - Google Patents

Abstract

(I), the coating property (II), and the etching suitability of the composition of the present invention.

Wherein the polymerizable unsaturated monomer comprises from 88 to 99% by mass of a polymerizable unsaturated monomer, from 0.1 to 11% by mass of a photopolymerization initiator and from 0.001 to 5% by mass of at least one of a fluorinated surfactant, a silicone surfactant and a fluorinated silicone surfactant, Characterized in that one kind of monofunctional polymerizable unsaturated monomer containing a moiety having an ethylenic unsaturated bond in the molecule and a moiety having at least one hetero atom as a monomer is contained in an amount of 10 mass% or more in the above polymerizable unsaturated monomer A curable composition for a photo-nanoimprint lithography was employed.

Curable composition for optical nanoimprint lithography, pattern forming method

Description

Technical Field [0001] The present invention relates to a curable composition for optical nanoimprint lithography, and a method of forming a pattern using the same. BACKGROUND OF THE INVENTION [0002]

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

The nanoimprint method develops emboss technology, which is well known in optical disk manufacturing, and dynamically deforms a mold (usually called a mold, a stamper, or a template) having a concave / convex pattern formed thereon by pressing it onto a resist to precisely transfer the fine pattern Technology. Since a nano structure can be easily and repeatedly formed by molding a mold once, it is economical and has a nano processing technology with few harmful disposal and emission. Therefore, application to various fields is expected in recent years.

In the nanoimprint method, when a thermoplastic resin is used as a material to be processed (S. Chou et al., Appl. Phys. Lett. Vol. 67, 3141 (1995)) and a curable composition for optical nanoimprint lithography , Proc. SPIE, Vol. 3667, 379 (1999)). In the case of a thermal nanoimprint, a mold is pressed onto a high molecular weight resin heated to a glass transition temperature or higher, and the mold is released after cooling to transfer the microstructure onto the resin on the substrate. Since it can be applied to various resin materials and glass materials, applications in various directions are expected. U.S. Patent No. 5,772,905 and U.S. Patent No. 5,956,216 disclose a nanoimprint method of forming a nanopattern at low cost using a thermoplastic resin.

On the other hand, in the photo-nanoimprint method in which light is irradiated through a transparent mold and the curable composition for photo-nanoimprint lithography is photo-cured, imprinting at room temperature becomes possible. In recent years, new developments such as a nano-casting method combining the merits of both of them and a reverse imprint method of producing a three-dimensional laminated structure have been reported. In the nanoimprint method, the following applications are considered. The first is that the molded shape itself has a function and can be applied as an element part or a structural member of various nanotechnologies. It can be applied to various micro / nano optical elements, high-precision recording media, optical films, And the like. The second is to construct a laminated structure by forming a microstructure and a nanostructure simultaneously, or by simple interlayer positioning, and to apply it to the fabrication of a μ-TAS or a biochip. Third, the present invention is intended to be applied to manufacturing of a high-density semiconductor integrated circuit or a transistor of a liquid crystal display instead of conventional lithography by high-precision alignment and high integration. In recent years, efforts to commercialize the nanoimprint method for these applications have become more active.

As an application example of the nanoimprint method, an application example to manufacture a high-density semiconductor integrated circuit will be described. 2. Description of the Related Art In recent years, miniaturization and integration of a semiconductor integrated circuit have been progressing, and as a pattern transfer technique for realizing the fine processing, the precision of a photolithography apparatus has been advanced. However, the processing method is close to the wavelength of the light source of the light exposure, and the lithography technique has come close to the limit. For this reason, an electron beam drawing apparatus, which is one type of charged particle beam apparatus, has been used instead of the lithography technique in order to proceed with new miniaturization and high precision. Unlike the batch exposure method in forming a pattern using an i-line or an excimer laser or the like, the pattern formation using the electron beam employs a method of drawing a mask pattern, so that the greater the number of patterns to be drawn, And it takes a long time to form the pattern. Therefore, as the degree of integration increases dramatically at 256 megahertz, 1 gigahertz, and 4 gigahertz, the pattern formation time becomes much longer, and the throughput is significantly lowered. Therefore, development of a beam-drawing method in which masks of various shapes are combined for high-speed operation of an electron beam drawing apparatus and electron beams are collectively applied to them to form electron beams of complicated shapes are being developed. As a result, the electron beam drawing apparatus can not be enlarged, and a mechanism for controlling the mask position with higher precision is required.

On the other hand, a nanoimprint lithography proposed as a technique for forming a fine pattern at a low cost has been proposed. For example, U.S. Patent Nos. 5,772,905 and 5,259,926 disclose a nanoimprint technique in which a silicon wafer is used as a stamper to form a fine structure of 25 nm or less by transfer.

Japanese Patent Application Laid-Open No. 2005-527110 discloses a composite composition using a nanoimprint applied to the field of semiconductor microlithography. On the other hand, examination for applying nanoimprint lithography to semiconductor integrated circuits such as micro mold manufacturing technology, mold durability, molding cost, mold releasability, imprint uniformity, alignment accuracy, .

However, the resist used in nanoimprint lithography has not been thoroughly investigated in spite of the necessity of etching suitability for various substrates and peelability after etching as in the conventional photoresist for semiconductor micro-processing.

Next, applications of nanoimprint lithography to a flat display such as a liquid crystal display (LCD) or a plasma display (PDP) will be described. BACKGROUND ART [0002] In recent years, optical nanoimprint lithography has attracted particular attention as an inexpensive lithography replacing the conventional photolithography method used in the manufacture of thin film transistors (TFTs) and electrode plates, in accordance with trends of LCD and PDP substrate enlargement and high precision. Therefore, development of a photocurable resist replacing the etching photoresist used in the conventional photolithography method has been required. Etching photoresists used in the conventional photolithography method are required to have adhesiveness to various substrates, etching resistance, heat resistance, and the like with respect to high sensitivity, film uniformity, and resist saving, and also to a photo nanoimprint resist A characteristic is required.

As for the uniformity of coating film, there is an increasing demand for various aspects such as uniformity of coating film thickness at the center and periphery of the substrate, dimensional uniformity due to high resolution, film thickness, and shape in enlarging the substrate. Conventionally, as a method of applying a resist in a liquid crystal display device manufacturing field using a small-sized glass substrate, there has been used a method of spinning after center drop (Electronic Journal 121-123 No. 8 (2002)). In the case of a large-sized substrate of, for example, a 1-m square type, the amount of resist discarded by swirling at the time of spinning (spinning) becomes very large, There arises a problem of cracking of the substrate and securing a tact time. In addition, since the coating performance in the method of spinning after the center drop depends on the rotational speed at the time of spinning and the amount of resist applied, there is no universal motor that can obtain the required acceleration when it is applied to the fifth generation substrate, There is a problem that the cost of parts is increased by special order. In addition, even when the substrate size or the apparatus size is enlarged, the required performance in the coating process hardly changes, such as the coating uniformity of 3% and the tact time of 60 to 70 seconds / sheet, It has become difficult to respond to demands other than uniformity. From this situation, a resist coating method based on a discharge nozzle method has been proposed as a new resist coating method applicable to a large-sized substrate after the fourth generation substrate, especially after the fifth generation substrate. The resist coating method by the discharge nozzle method is a method of applying the photoresist composition to the entire surface of the substrate by moving the discharge nozzle and the substrate relative to each other. For example, the resist coating method is a method in which a plurality of nozzle holes are arranged in a row, A method of using a discharge nozzle capable of discharging the photoresist composition in a strip shape, and the like are proposed. There is also proposed a method of coating a photoresist composition on the entire surface of a substrate coated with a discharge nozzle, and then spinning the substrate to adjust the film thickness. Therefore, in order to apply the resist of the conventional photolithography to the field of manufacturing liquid crystal display devices instead of the nanoimprint composition, uniformity of application to the substrate becomes important.

A fluorine-based and / or a silicon-based surfactant such as a positive type photoresist used for manufacturing a semiconductor integrated circuit or a liquid crystal display or a pigment dispersion photoresist for forming a color filter may be added to improve the coating properties, It is widely known to solve the problem of coating failure such as a scaly shape (dry deviation of a resist film) (JP-A-7-230165, JP-A 2000-181055, JP-A 2004-94241 report). In order to improve the abrasiveness and coatability of a protective film such as a compact disk or a magneto-optical disk, it has been disclosed to add a fluorine-based surfactant or a silicon-based surfactant to a solventless photo-curable composition (Japanese Patent Laid-Open Publication No. 2004-94241 Japanese Patent Application Laid-Open Nos. 4-149280, 7-62043, and 2001-93192). Similarly, in JP-A-2005-8759, it is known to add a non-ionic fluorine-based surfactant to improve the ink discharge stability of an inkjet composition. Japanese Unexamined Patent Application Publication No. 2003-165930 discloses a method for embossing a painting composition coated with a thickener such as a brush, a brush and a bar coater in a mold for hologram processing, wherein the polymerizable unsaturated double bond-containing surfactant is contained in an amount of 1% % Or more to improve the water swelling property of the cured film. The technique of improving the coatability by adding a surfactant to a protective film such as a positive type photoresist, a pigment dispersing photoresist for forming a color filter and a magneto-optical disk is a well known technique. Also, as shown in the examples of the inkjet or painting composition, a technique of adding a surfactant to a solvent-free photo-curable resin and adding a surfactant for improving the characteristics in each application is also widely known. However, a method for improving the substrate coatability of a photo-curable nanoimprinted resist composition which does not contain a pigment, a dye, or an organic solvent as an essential component has not been known heretofore.

Further, in the field of flat panel display, when the conventional photolithography is changed to a nanoimprint lithography process, the constituent components of the curable composition for photo-nanoimprint lithography are not volatilized during coating, exposure, mold peeling, and heating (post baking) It is strongly expected. The photopolymerizable unsaturated monomer component of the curable composition for photo-nanoimprint lithography, which is generally used in the process of photo-nanoimprint lithography, has a smaller molecular weight as compared with the novolak resin or naphthoquinone diazide photosensitive agent conventionally used in photolithography, (Evaporation). When the components of the curable composition for optical nanoimprint lithography are volatilized, not only the process con- dition termination is caused to deteriorate the yield at the time of manufacturing the display, but also the worker burns when the operator sucks or touches the volatilized vapor. It also affects safety. From this point of view, a component of the curable composition for use in nanoimprint lithography of the nanoimprint is preferably a material which is hardly volatilized.

Further, when a photo-nanoimprint resist containing an organic solvent is applied, it is necessary to volatilize the solvent after application. Therefore, in the case of using a composition containing an organic solvent, development of a composition containing no organic solvent is strongly expected, because it is disadvantageous to safety of an operator due to suction of a volatilized solvent or simplification of the number of process steps.

The prior art related to the optical nanoimprint, which is the application range of the present invention, will be described in more detail. The optical nanoimprint lithography can be performed by dropping a liquid curable composition for optical nanoimprint lithography on a substrate such as a silicon wafer, quartz, glass, film or other materials such as a ceramic material, metal, or polymer, And a mold having fine irregularities of a pattern size of about several tens of nanometers to several tens of micrometers is pressed and pressed, and the composition is cured by light irradiation in a pressurized state, and then the mold is released from the coating film to form a transferred pattern The method of obtaining is common. Therefore, in the case of optical nanoimprint lithography, at least one of the substrate and the mold needs to be transparent for the purpose of performing light irradiation. Usually, light is generally irradiated from the mold side, and an inorganic material or a light-transmitting resin that transmits UV light such as quartz or sapphire is used for the mold material.

(2) imprinting at low pressure is possible because of the use of a liquid composition; (3) thermal expansion is caused by the thermal expansion of the liquid nanoimprinting method; (4) the mold is transparent and alignment is easy, and (5) a hardened three-dimensional cross-linked body is obtained after curing. Particularly, the flat panel display structural member is suitable for use in semiconductor microfabrication for which alignment accuracy is required, semiconductor microfabrication in the field of flat panel display, or structural member required for flat panel display. Specific flat panel display structural members are disclosed in Japanese Patent Application Laid-Open No. 2005-197699, An interlayer insulating film on a TFT element formed on a TFT (thin film transistor) substrate described in Japanese Patent Application Laid-Open No. 2005-301289, a flattening layer on a color filter substrate, a spacer, and the like.

Another feature of the optical nanoimprinting method is that it does not require an expensive device such as a stepper or an electron beam drawing apparatus even in the fine processing of a nanometer order since the resolution does not depend on the wavelength of a light source as compared with a conventional optical lithography to be. On the other hand, the photo-nanoimprint method requires a cubic mold, and since the mold and the resin are in contact with each other, there is a concern about the durability and cost of the mold. Further, in the photo-nanoimprint lithography process, a residual film (a portion where the convexity of the mold is pressed against the curable composition for photo-nanoimprint lithography) is apt to occur. The thinner this residual film layer is, the more preferable the structure that can be formed by using the nanoimprint is more accurate. Further, if the number of the remaining films is large, line width control in etching and etching residues tend to occur. Of course, in applications such as the above-described interlayer insulating film, planarizing layer, etc., there is a case where a film is finally left, and in this case, the problem concerning the residual film becomes small.

Thus, in order to imprint a nanometer-sized pattern onto a large area by applying a thermal and / or optical nanoimprint method, not only the uniformity of the pressing pressure and the flatness of the original mold (mold) are required, It is also necessary to control the behavior of the substrate. In the conventional semiconductor technology, a region not used as an element can be arbitrarily set on a wafer, so that a resist outflow portion can be provided outside the imprint portion by using a small disk. Further, in the semiconductor, the imprint defective portion can be prevented from being used as a defective element. However, for example, in the application to a hard disk or the like, special research that does not cause imprint defects is required because the entire surface functions as a device.

Molds used in optical nanoimprint lithography can be made of a variety of materials, such as metals, semiconductors, ceramics, spin on glass (SOG), or certain plastics. For example, a flexible polydimethylsiloxane mold having the desired microstructure described in International Publication WO99 / 22849 pamphlet has been proposed. In order to form a three-dimensional structure on one surface of the mold, various lithography methods can be used depending on the size of the structure and the specifications for its resolution. Electron beam and X-ray lithography is typically used for structural dimensions less than 300 nm. Direct laser exposure and UV lithography are used in larger structures.

With regard to the photo-nanoimprint method, the releasability of a mold and a curable composition for a photo-nanoimprint lithography is important, and the surface treatment of a mold or a mold, specifically, a hydrogen silsesquioxane or a fluorinated ethylene propylene copolymer mold, And so on.

Here, the photocurable resin used in the photo-nanoimprint lithography will be described. Photocurable resins to be applied to the nanoimprint can roughly be classified into a radical polymerization type and an ionic polymerization type or a hybrid type thereof from the difference in reaction mechanism. Radical polymerization types, which can be any composition or imprintable but have a wide selection of materials, are generally used (F.Xu et al .: SPIE Microlithography Conference, 5374, 232 (2004)). The radical polymerization type is generally a composition containing a radical polymerizable vinyl group, a monomer (monomer) having a (meth) acrylic group or an oligomer and a photopolymerization initiator. When irradiated with light, the radical generated by the photopolymerization initiator attacks vinyl groups and chain polymerization proceeds to form a polymer. When a bifunctional or multifunctional monomer or oligomer is used as a component, a crosslinked structure is obtained. DJResnick et al., J. Vac. Sci. Technol. B, Vol. 21, No. 6, 2624 (2003) disclose a composition capable of imprinting at low pressure and at room temperature by using a UV- .

The characteristics of the materials used in the photo-nanoimprint lithography will be described in detail. The required properties of the material depend on the application to which it is applied, but the demands on the process characteristics are common regardless of the application. For example, the main requirement items shown in the latest resist material handbook, P1, 103-104 (2005, Information Technology Publication), are the coating properties, substrate adhesion, low viscosity (<5 mPa · s), releasability, , Fast curability. In particular, it is known that there is a strong demand for a low viscosity material in applications requiring low pressure imprinting and reduction of the film residual rate. On the other hand, when the required characteristics are found for each application, for example, the refractive index and the light transmittance for the optical member, and the etching resistance and the thickness of the residual film for the etching resist. The key to material design is how to control these demand characteristics and to balance various characteristics. At least for process materials and permanent membranes, the required properties are very different, so the material needs to be developed according to the process or application. A photocurable material having a viscosity of about 60 mPa · s (25 ° C) has been disclosed in the latest resist material handbook, P1, 103-104 (2005, Information and Instrumentation Publication) as a material to be applied to such a photo-nanoimprint lithography application It is widely known. Likewise, CMC Publications: Nanoimprint Development and Applications P159 to 160 (2006) disclose fluorine-containing photosensitive resins having monomethacrylate as a main component and having improved viscosity of 14.4 mPa · s.

Although there is a description of viscosity requirements, there has been no report of design guidelines for materials suitable for each application, as far as the composition used in such a photo-nanoimprint is concerned.

An example of a photocurable resin applied to optical nanoimprint lithography has been described so far. Japanese Patent Laid-Open Nos. 2004-59820 and 2004-59822 disclose an embossing process using a photo-curable resin containing a relief-type hologram or a polymer having an isocyanate group for producing a diffraction grating. Also, US-A-2004/110856 discloses a curable composition for a photo-nanoimprint lithography for imprinting comprising a polymer, a photopolymerization initiator, and a viscosity adjuster.

Japanese Patent Application Laid-Open No. 2006-114882 discloses a pattern forming method using a fluorine-containing curable material in order to improve releasability with a mold.

N.Sakai et al., J. Photopolymer Sci. Technol. Vol. 18, No. 4, 531 (2005), discloses a process for the preparation of (1) functional acrylic monomers, (2) functional acrylic monomers, (3) Discloses an example in which a photo-curable radical polymerizable composition in combination with an initiator, a photo cationic polymerizable composition containing a photo-curable epoxy compound and a photoacid generator, and the like are applied to nanoimprint lithography to investigate thermal stability and mold releasability.

M. Stewart et al .: MRS Buletin, Vol. 30, No. 12, 947 (2005) proposes a method for improving the peelability of a photocurable resin and a mold, film shrinkability after curing, and reduction in sensitivity due to photopolymerization inhibition in the presence of oxygen (1) a functional acrylic monomer, (2) a functional acrylic monomer, a silicon-containing monofunctional acrylic monomer, and a photopolymerization initiator.

T.Beiley et al .: J. Vacc. Sci. Technol. B 18 (6), 3572 (2000) discloses a curable composition for optical nanoimprint lithography comprising a monofunctional acrylic monomer, a silicon- containing monofunctional monomer and a photopolymerization initiator, It has been disclosed that defects after molding in a photo-nanoimprint lithography are reduced using a mold formed on a substrate and a surface-treated mold.

B. Vratzov et al .: J. Vacc. Sci. Technol. B 21 (6), 2760 (2003) discloses a curable composition for photo-nanoimprint lithography which comprises a silicone monomer, a trifunctional acrylic monomer and a photopolymerization initiator, , And a composition excellent in high resolution and uniformity of application by a SiO ₂ mold is disclosed.

EKKim et al., J. Vacc. Sci. Technol. B22 (1), 131 (2004) disclose an example in which a pattern size of 50 nm is formed by a cationic polymerizable composition comprising a combination of a specific vinyl ether compound and a photo- . Has a low viscosity and a high curing speed, but it is described that the template peelability is a problem.

By the way, N.Sakai et al. : J. Photopolymer Sci. Technol. Vol. 18, No. 4, 531 (2005), M. Stewart et al. : MRS Buletin, Vol. 30, No. 12, 947 (2005), T.Beiley et al. : J. Vacc. Sci. Technol. B 18 (6), 3572 (2000), B. Vratzov et al. : J. Vacc. Sci. Technol. B21 (6), 2760 (2003), E.Kim et al. : As shown in J. Vacc. Sci. Technol., B22 (1), 131 (2004), photo-curing resins to which photo-nanoimprint lithography employs acrylic monomers, acrylic polymers and vinyl ether compounds having different functional groups However, no guidance on the design of materials such as a preferable kind as a composition, a combination of an optimum monomer species and a monomer, an optimum viscosity of a monomer or a resist, a desirable solution property of a resist, . Therefore, a photo-nanoimprinted resist composition which can never satisfy a desired composition for widely applying a composition for use in photo-nanoimprint lithography has never been proposed.

Application to an etching resist for substrate processing will be described in detail. The etching resist is not an element to be left as it is, but merely a copy of a semiconductor or a transistor circuit pattern. In order to produce a circuit pattern, it is necessary to transfer these resist patterns to various layers including a device. A method of transferring a pattern is performed by an etching process for selectively removing a portion not covered with a resist. For example, in the manufacture of a TFT array substrate or an electrode plate of a PDP, an etching resist is coated on a conductive substrate or an insulating substrate sputtered on a glass substrate or a transparent plastic substrate, followed by drying, pattern exposure, development, etching, Is performed on the thin film of each layer. As a conventional etching resist, a positive type photoresist has been widely used. In particular, chemically amplified resists comprising alkali-soluble phenol novolac resins and 1,2-quinonediazide compounds as main components and chemically amplified resists using (poly) hydroxystyrene as a polymer have high etching resistance and are easily peeled off An etching photoresist of a semiconductor or a TFT transistor is widely used, and many knowledge has been accumulated. There are a wet etching method in which various liquid etchants are used for the etching and a dry etching method in which the film on the substrate is vaporized and removed by using ions or radicals (active species) generated by decomposing the gas by plasma in the decompression apparatus. Etching is an important process that greatly affects device design precision, transistor characteristics, yield, and cost. Etch resist requires materials and process suitability that can be applied to either dry etching or wet etching. In order to apply the composition used in the photo-nanoimprint lithography to the resist field used in these conventional photolithography, etching properties such as that of a conventional photoresist are required, but they have not been thoroughly investigated and various problems have arisen in the etching process .

A major technical problem as an etching resist is to improve the processing precision of the pattern, to improve the controllability of the tapering process (to improve the undercut shape), to improve the etching uniformity in the large substrate, to improve the etching selectivity with the substrate, There are many problems such as ensuring safety of collective etching property, waste liquid, waste gas, etc., and improvement of film defects (particles, residues) after etching. When the curable composition for photo-nanoimprint lithography is applied as an etching resist, like the conventional positive type photoresist,

(1) an etchant selected according to the type of the barrier, aptitude for the etching gas,

(2) the adhesion of the pattern to the etched substrate in order to avoid occurrence of undercut,

(3) The wettability of the etching solution and the resist is important to obtain dimensional controllability of the pattern before and after the etching.

However, the curable composition for use in a photo-nanoimprint lithography has a further technical difficulty in view of the following points (4), (5) and (6) in addition to the points (1) to (3).

(4) When the resist film is made hydrophobic in order to improve the peeling property with the mold, the wettability of the etching solution and the resist is further deteriorated,

(5) Since the curable composition for a photo-nanoimprint lithography has a three-dimensional mesh structure, it is difficult to peel off as compared with a positive resist, and when the mesh structure is made stronger, the etching resistance is improved but the peeling becomes further difficult,

(6) Compared to conventional photolithography, photo-nanoimprint lithography is susceptible to residue after etching because residues are likely to be formed at portions to be etched away after mold release.

Various materials have been disclosed for the curable composition for nanoimprint lithography for nanoimprinting. However, there is a need for a curable composition for nano-imprint lithography that discloses a nanoimprint material that can be suitably used in any of the photolithography process, etching process, Design guidelines have never existed before. In the curable composition for use in photo-nanoimprint lithography, which has been heretofore known as a composition for an ink jet or a protective film for a magneto-optical disk, the photolithography process has a common part in the material, but it differs greatly from the etching resist in that there is no etching step or peeling step . Therefore, when the photo-curable resin used for these uses is directly applied as an etching resist, many problems are often caused in the etching step and the peeling step.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a curable composition for optical nanoimprint lithography which is excellent in novel photocurability. It is an object of the present invention to provide a composition which is excellent in both light curability, adhesion, releasability, retentivity, pattern shape, coatability and etching suitability.

As a result of intensive studies by the inventor under the above-mentioned problems, it has been found that the above problems can be solved by the following means.

(1) A photosensitive composition comprising (1) from 88 to 99% by mass of a polymerizable unsaturated monomer, from 0.1 to 11% by mass of a photopolymerization initiator, and from 0.001 to 5% by mass of at least one of a fluorinated surfactant, a silicone surfactant and a fluorinated silicone surfactant, Characterized in that at least 10% by mass of one or more monofunctional polymerizable unsaturated monomers containing an ethylenic unsaturated bond in the molecule and a moiety having at least one hetero atom in the molecule is contained as the unsaturated monomer in the polymerizable unsaturated monomer Wherein the curable composition is a curable composition for optical nanoimprint lithography.

(2) The curable composition for optical nanoimprint lithography as described in (1), wherein the monofunctional polymerizable unsaturated monomer contains at least one compound selected from the following (a), (b) and (c).

(a) a polymerizable unsaturated monomer having an aliphatic cyclic moiety containing a hetero atom and a moiety having an ethylenic unsaturated bond in one molecule

(b) a polymerizable unsaturated monomer having an ethylenic unsaturated bond in one molecule and a moiety having -C (= O) - bond and NR bond (R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

(c) a monofunctional polymerizable unsaturated monomer containing a moiety having an ethylenic unsaturated bond in the molecule and a moiety having at least one heteroatom, wherein the moiety has an ethylenically unsaturated bond in one molecule and a moiety having 6 to 12 carbon atoms The polymerizable unsaturated monomer having an aliphatic cyclic moiety

(3) The process for producing the above-mentioned monofunctional polymerizable unsaturated monomer according to any one of (1) to (3), wherein the monofunctional polymerizable unsaturated monomer comprises at least one polymerizable unsaturated monomer having an ethylenic unsaturated bond in one molecule and an aliphatic cyclic moiety containing a hetero atom, (1), wherein the heteroatom of the monofunctional polymerizable unsaturated monomer of the polymerizable unsaturated monomer is in the form of any one of O, N, and S. The curable composition for optical nanoimprint lithography according to claim 1,

(4) a photosensitive composition containing from 88 to 99% by mass of a polymerizable unsaturated monomer, from 0.1 to 11% by mass of a photopolymerization initiator, and from 0.001 to 5% by mass of at least one of a fluorinated surfactant, a silicone surfactant and a fluorinated silicone surfactant, A curable composition for optical nanoimprint lithography, which contains at least one monofunctional polymerizable unsaturated monomer selected from the following formulas (I) to (VIII) as an unsaturated monomer.

&Lt; General Formula (I) >

(Wherein R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring); R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each represent a hydrogen atom, N1 represents 1 or 2, and m1 represents any one of 0, 1 and 2. Z ¹¹ represents an alkylene group having 1 to 6 carbon atoms (which may form a ring) or an alkoxy group having 1 to 6 carbon atoms, ., represents an oxygen atom or -NH-, 2 of Z ¹¹ are different and W ¹¹ is -C (= O) - or -SO ₂ -. R ¹² represents an R ¹³ and and R ¹⁴ and R ¹⁵ are each They may be combined with each other to form a ring.)

&Lt; General Formula (II) >

(In the general formula (II), R ²¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (which may form a ring); R ²² , R ²³ , R ²⁴ and R ²⁵ each represent a hydrogen atom, A halogen atom and an alkoxy group having 1 to 6 carbon atoms, R ²² and R ^23, and R ²⁴ and R ²⁵ may be bonded to each other to form a ring, n 2 is 1, 2 and 3, and m2 represents any one of 0, 1, and 2. Y ²¹ represents an alkylene group having 1 to 6 carbon atoms or an oxygen atom.

&Lt; General Formula (III) >

(In the general formula (III), R ³² , R ³³ , R ³⁴ and R ³⁵ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (may form a ring), a halogen atom or an alkoxy group having 1 to 6 carbon atoms. n3 is any one of 1, 2, 3, m3 represents 0, 1, any one of 2 X ³¹ is -C (= O) -., represents an alkylene group having 1 to 6 carbon atoms, 2 X ³¹ Y ³² represents an alkylene group having 1 to 6 carbon atoms or an oxygen atom.

&Lt; General Formula (IV) >

(In the general formula (IV), R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (which may form a ring), R ⁴² and R ⁴³ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms A halogen atom or an alkoxy group having 1 to 6 carbon atoms, W ⁴¹ represents a single bond or -C (= O) -, and n4 represents any one of 2, 3 and 4. X ⁴² Represents an alkylene group of -C (= O) - or an alkylene group of 1 to 6 carbon atoms, and each X ⁴² may be the same or different, M ⁴¹ represents a hydrocarbon linking group having 1 to 4 carbon atoms, an oxygen atom or a nitrogen atom, Each M ⁴¹ may be the same or different.)

&Lt; General Formula (V) >

(In the general formula (V), R ⁵¹ represents a bond, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (which may form a ring), Z ⁵² represents an oxygen atom, -CH = N-, represents an alkylene group. W ⁵² is (as may form a ring), an alkyl group having 1 to 6 carbon atoms represents a alkylene group or an oxygen atom. R ⁵⁴ and R ⁵⁵ are each a hydrogen atom, a group having 1 to 6 carbon atoms, a halogen atom, And R ⁵⁴ and R ⁵⁵ may be bonded to each other to form a ring, and when X ⁵¹ represents a single bond or a non-bond and R ⁵¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms X ⁵¹ represents a single bond, R ⁵¹ if the non-bond X ⁵¹ represents a non-bonded. m5 is 0, 1, is any one of ^{2. W 52, Z 52,} R 54, R 55 1 out of more than Containing an oxygen atom or a nitrogen atom.

&Lt; General Formula (VI) >

(Wherein R ⁶¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ⁶² and R ⁶³ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a (CH 3) _{2 N- (CH 2) m6 -} (m6 is 1, 2 or _{3), CH 3 CO- (CR} 64 R 65) p6 - (R 64 and R ⁶⁵ each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (F represents a search may form), p6 is either of 1, 2 or _{3), (CH 3) 2} -N- (CH 2) p6 -. (p6 is either of 1, 2 or 3). = CO group, and R ⁶² and R ⁶³ are not simultaneously hydrogen atoms, and X ⁶ represents -CO-, -COCH ₂ -, -COCH ₂ CH ₂ -, -COCH ₂ CH ₂ CH ₂ -, -COOCH ₂ CH ₂ -).

&Lt; General Formula (VII) >

(In the general formula (VII), R ⁷¹ and R ⁷² are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring), and R ⁷³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms ).

&Lt; General Formula (VIII) >

(In the general formula (VIII), R ⁸¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (may form a ring), or a hydroxyalkyl group having 1 to 6 carbon atoms. R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ At least two of R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ are bonded to each other to form a ring, and R 1 and R 2 each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms (which may form a ring), or a hydroxyalkyl group having 1 to 6 carbon atoms; W ⁸¹ is an alkylene group having 1 to 6 carbon atoms, -NH- group, -N-CH ₂ - group or -NC ₂ H ₄ - group, W ⁸² is a single bond or -C (= O) - When W ⁸² is a single bond, R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ are not all hydrogen atoms, and n 7 represents an integer of 0 to 8.

(5) A photosensitive composition which comprises 88 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 11% by mass of a photopolymerization initiator, and 0.001 to 5% by mass of at least one of a fluorinated surfactant, a silicone surfactant, and a fluorinated silicone surfactant, A curable composition for light-nanoimprint lithography comprising a monofunctional polymerizable unsaturated monomer represented by the following general formula (I) as a polymerizable unsaturated monomer.

&Lt; General Formula (I) >

(In the general formula (I), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring); R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each represent a hydrogen atom, Or an alkoxy group having 1 to 6 carbon atoms, n1 is 1 or 2, m1 is 0 or 1. Z ¹¹ is an alkylene group having 1 to 6 carbon atoms, an oxygen atom or -NH - denotes a group, the two Z ¹¹ are different from each other, at least one of Z ¹¹ is oxygen atom W ¹¹ is -C (= O) -.. a is R ¹² and R ¹³ and R ¹⁴ and R ¹⁵ respectively each other It may be combined to form a ring.)

(6) A photosensitive composition which contains 88 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 11% by mass of a photopolymerization initiator, and 0.001 to 5% by mass of at least one of a fluorochemical surfactant, a silicone surfactant and a fluorochemical silicone surfactant, A curable composition for a photo-nanoimprint lithography comprising a monofunctional polymerizable unsaturated monomer represented by the following formula (II) as a polymerizable unsaturated monomer.

&Lt; General Formula (II) >

(In the general formula (II), R ²¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring), and R ²² , R ²³ , R ²⁴ and R ²⁵ each represent a hydrogen atom, A halogen atom and an alkoxy group having 1 to 6 carbon atoms, R ²² and R ^23, and R ²⁴ and R ²⁵ may be bonded to each other to form a ring, n 2 is 1 or 2 , And m is 0 or 1. Y ²¹ represents an alkylene group having 1 to 6 carbon atoms or an oxygen atom.

(7) A photosensitive resin composition which comprises 88 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 11% by mass of a photopolymerization initiator, 0.001 to 5% by mass of at least one of a fluorinated surfactant, a silicone surfactant and a fluorinated silicone surfactant, 1. A curable composition for optical nanoimprint lithography comprising a monofunctional polymerizable unsaturated monomer represented by the following general formula (III) as an unsaturated monomer.

&Lt; General Formula (III) >

(In the general formula (III), R ³² , R ³³ , R ³⁴ and R ³⁵ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (may form a ring), a halogen atom or an alkoxy group having 1 to 6 carbon atoms. n3 is any one of 1, 2, 3, m3 represents 0, 1, any one of 2 X ³¹ is -C (= O) -., represents an alkylene group having 1 to 6 carbon atoms, 2 X ³¹ Y ³² represents an alkylene group having 1 to 6 carbon atoms or an oxygen atom.

(8) A photosensitive composition which contains 88 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 11% by mass of a photopolymerization initiator, and 0.001 to 5% by mass of at least one of a fluorinated surfactant, a silicone surfactant, and a fluorinated silicone surfactant, Wherein the polymerizable unsaturated monomer contains 10 to 80% by mass of a monofunctional polymerizable unsaturated monomer represented by the following general formula (IV) in the above polymerizable unsaturated monomer, and further contains 10 to 80% by mass of 1,9- And polyethylene glycol di (meth) acrylate. The curable composition for light nanoimprint lithography according to claim 1,

&Lt; General Formula (IV) >

(In the general formula (IV), R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring), R ⁴² and R ⁴³ each represent a hydrogen atom, W ⁴¹ represents a single bond or -C (= O) -, n4 represents any one of 2, 3 and 4. X ⁴² represents -C (= O) - or an alkylene group having 1 to 6 carbon atoms, and each X ⁴² is the same or different M ⁴¹ represents a hydrocarbon group having 1 to 4 carbon atoms, an oxygen atom or a nitrogen atom, and each M ⁴¹ may be the same or different.)

(9) A photosensitive composition which contains 88 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 11% by mass of a photopolymerization initiator, and 0.001 to 5% by mass of at least one of a fluorinated surfactant, a silicone surfactant and a fluorinated silicone surfactant, A curable composition for optical nanoimprint lithography comprising a monofunctional polymerizable unsaturated monomer represented by the following general formula (V) as a polymerizable unsaturated monomer.

&Lt; General Formula (V) >

(In the general formula (V), R ⁵¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring). Z ⁵² represents an oxygen atom, -CH = N- or an alkylene group having 1 to 6 carbon atoms , W ⁵² represents an alkylene group having 1 to 6 carbon atoms or an oxygen atom, R ⁵⁴ and R ⁵⁵ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (may form a ring), a halogen atom, of an alkoxy group, it may be R ⁵⁴ and R ⁵⁵ may be bonded to each other to form a ring. X ⁵¹ represents a single bond. m5 is 0, 1, is any one of ^{2. W 52, Z 52,} R 54, R 55 And at least one of them contains an oxygen atom or a nitrogen atom.

(10) A photosensitive resin composition which contains 88 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 11% by mass of a photopolymerization initiator, 0.001 to 5% by mass of at least one of a fluorinated surfactant, a silicone surfactant and a fluorinated silicone surfactant, 1. A curable composition for optical nanoimprint lithography comprising a monofunctional polymerizable unsaturated monomer represented by the following general formula (VI) as an unsaturated monomer.

&Lt; General Formula (VI) >

(Wherein R ⁶¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ⁶² and R ⁶³ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a (CH ₃ ) _{2 N- (CH 2) m6 -} (m6 is 1, 2 or _{3), CH 3 CO- (CR} 64 R 65) p6 - (R 64 and R ⁶⁵ each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (F represents a search may form), p6 is either of 1, 2 or _{3), (CH 3) 2} -N- (CH 2) p6 -. (p6 is either of 1, 2 or 3). = CO group, and R ⁶² and R ⁶³ are not simultaneously hydrogen atoms, and X ⁶ represents -CO-, -COCH ₂ -, -COCH ₂ CH ₂ -, -COCH ₂ CH ₂ CH ₂ -, -COOCH ₂ CH ₂ -).

(11) A photosensitive resin composition which contains 88 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 11% by mass of a photopolymerization initiator, 0.001 to 5% by mass of at least one of a fluorinated surfactant, a silicone surfactant and a fluorinated silicone surfactant, 1. A curable composition for optical nanoimprint lithography comprising a monofunctional polymerizable unsaturated monomer represented by the following general formula (VII) as an unsaturated monomer.

&Lt; General Formula (VII) >

(In the general formula (VII), R ⁷¹ and R ⁷² are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring), and R ⁷³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms ).

(12) A photosensitive resin composition which contains 88 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 11% by mass of a photopolymerization initiator, 0.001 to 5% by mass of at least one of a fluorinated surfactant, a silicone surfactant and a fluorinated silicone surfactant, 1. A curable composition for light-nanoimprint lithography comprising a monofunctional polymerizable unsaturated monomer represented by the following general formula (VIII) as an unsaturated monomer.

&Lt; General Formula (VIII) >

(In the general formula (VIII), R ⁸¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (may form a ring), or a hydroxyalkyl group having 1 to 6 carbon atoms. R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ At least two of R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ are bonded to each other to form a ring, and R 1 and R 2 each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms (which may form a ring), or a hydroxyalkyl group having 1 to 6 carbon atoms; W ⁸¹ is an alkylene group having 1 to 6 carbon atoms, -NH- group, -N-CH ₂ - group or -NC ₂ H ₄ - group, W ⁸² is a single bond or -C (= O) - When W ⁸² is a single bond, R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ are not all hydrogen atoms, and n 7 represents an integer of 0 to 8.

(13) The photo-nanoimprint as described in (1), further comprising at least 0.1% by mass of at least one of the moiety having at least one ethylenic unsaturated bond and the second polymerizable unsaturated monomer containing a silicon atom and / or a phosphorus atom A curable composition for lithography.

(14) The photo-nanoimprint according to (3), further comprising at least 0.1% by mass of at least one of the moiety having at least one ethylenic unsaturated bond and the second polymerizable unsaturated monomer containing a silicon atom and / or a phosphorus atom A curable composition for lithography.

(15) A process for applying the curable composition for photo-nanoimprint lithography as described in any one of (1) to (14), comprising the steps of pressing a light-transmissive mold onto a resist layer on a substrate to modify the curable composition for the photo- A step of irradiating light from the back surface of the mold or the back surface of the substrate to form a resist pattern for curing the coating film to fit the desired pattern; and a step of detaching the light-transmitting mold from the coating film.

(Effects of the Invention)

According to the present invention, it has become possible to provide a composition which is excellent in photo-curability, adhesion, releasability, retentivity, pattern shape, coatability, and etching suitability.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, &quot; ~ &quot; is used to mean that the numerical values described before and after the lower limit and the upper limit are included.

Hereinafter, the present invention will be described in detail. In the present specification, the term &quot; meta (acrylate) &quot; denotes acrylate and methacrylate, the term &quot; methacrylate &quot; denotes acrylate and methacrylate, . In the present specification, monomers and monomers are the same. The monomers in the present invention are distinguished from oligomers and polymers and mean compounds having a mass average molecular weight of 1,000 or less. In the present specification, the functional group refers to a group involved in polymerization.

The term &quot; nanoimprinted pattern transfer &quot; in the present invention refers to a pattern transfer of a size of several micrometers to several tens of nanometers.

The expression &quot; carbon number A to B &quot; in this specification does not include the carbon number of the substituent unless otherwise stated. For example, in the case of "an aliphatic cyclic moiety having 6 to 12 carbon atoms", it means that the number of carbon atoms forming the cyclic skeleton is 6 to 12.

The curable composition for a photo-nanoimprint lithography of the present invention (hereinafter sometimes simply referred to as &quot; the composition of the present invention &quot;) has a high light transmittance before curing and is excellent in the ability to form a fine uneven pattern, (Fast curability), resolution, line edge roughness, film strength, peelability with a mold, residual film characteristics, etching resistance, low curing shrinkability, substrate adhesion, or various other properties after curing It can be widely used for the optical nanoimprint lithography in which excellent physical properties of the coating film can be obtained comprehensively.

That is, the composition of the present invention can have the following characteristics when used in a photo-nanoimprint lithography.

(1) Since the solution is excellent in fluidity at room temperature, the composition tends to flow into the cavity of the mold recess, and since it is difficult to introduce air into the cavity, the bubble defect is not caused, It is difficult to leave a residue after the fire.

(2) Since the cured film after curing has excellent mechanical properties, excellent adhesion between the coating film and the substrate, and excellent releasability of the coating film and the mold, the pattern collapses when the mold is peeled off, It is possible to form a good pattern.

(3) Since the volume shrinkage after photo-curing is small and the mold transfer property is excellent, accurate formation of fine patterns is possible.

(4) Excellent uniformity of application, which is suitable for coating and fine processing in large-sized substrates.

(5) Since the photocuring speed of the film is high, the productivity is high.

(6) Since it is excellent in etching processing precision and etching resistance, it can be preferably used as an etching resist for substrate processing of semiconductor devices and transistors.

(7) Since the resist peelability after etching is excellent, no residue is generated, and thus it can be preferably used as an etching resist.

For example, it has been difficult to develop a semiconductor integrated circuit or a thin film transistor of a liquid crystal display for fine processing. The composition of the present invention can be suitably applied to these applications and can be applied to other applications such as flat screens, microelectromechanical systems (MEMS), sensor devices, optical disks, magnetic recording media such as high density memory disks, An optical device such as an optical device or an optical device such as a light emitting diode, a light emitting diode, a light emitting diode, a light emitting diode, a light emitting diode, , Optical filters, photonic liquid crystals, and the like.

The composition of the present invention contains 88 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 11% by mass of a photopolymerization initiator, 0.001 to 5% by mass of at least one of a fluorinated surfactant, a silicone surfactant and a fluorinated silicone surfactant, As the polymerizable unsaturated monomer, one kind of monofunctional polymerizable unsaturated monomer containing a moiety having at least one of a moiety having an ethylenic unsaturated bond in the molecule and a heteroatom (for example, oxygen, nitrogen, or a sulfur atom) And 10% by mass or more, and preferably 15% by mass or more, of the polymerizable unsaturated monomer is a curable composition for light nanoimprint lithography.

The monofunctional polymerizable unsaturated monomer is preferably a compound selected from the following (a), (b) and (c).

(a) a polymerizable unsaturated monomer having an aliphatic cyclic moiety containing a site having an ethylenic unsaturated bond in one molecule and a hetero atom (preferably a hydrogen atom, a nitrogen atom or a sulfur atom)

(b) a polymerizable unsaturated monomer having an ethylenic unsaturated bond in one molecule and a moiety having -C (= O) - bond and NR bond (R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

(c) a monofunctional polymerizable unsaturated monomer containing a moiety having an ethylenic unsaturated bond in the molecule and a moiety having at least one heteroatom, wherein the moiety has an ethylenically unsaturated bond in one molecule and a moiety having 6 to 12 carbon atoms The polymerizable unsaturated monomer having an aliphatic cyclic moiety

In the present invention, it is also preferable that the polymerizable unsaturated monomer includes a monofunctional polymerizable unsaturated monomer represented by any one of the following general formulas (I) to (VIII).

&Lt; General Formula (I) >

(In the general formula (I), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring); R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each represent a hydrogen atom, Or an alkoxy group having 1 to 6 carbon atoms, n1 is 1 or 2, m1 is 0, 1 or 2. Z ¹¹ is an alkylene group having 1 to 6 carbon atoms, . represents an atomic oxygen or -NH-, 2 of Z ¹¹ are different and W ¹¹ is -C (= O) - or -SO ₂ -. R ¹² represents an R ¹³ and and R ¹⁴ and R ¹⁵ are each They may be combined with each other to form a ring.)

Here, R ¹¹ is preferably a hydrogen atom or a methyl group. Each of R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group or an ethoxy group, more preferably a hydrogen atom or a methyl group. m1 is preferably 0 or 1. Z ¹¹ is preferably a methylene group, an oxygen atom or an -NH- group, and it is more preferable that at least one of the two Z ¹¹ groups is an oxygen atom. W ¹¹ is preferably -C (= O) -.

when n1 is 2 or more R ^14, R ¹⁵ may be the same, respectively, it may be different.

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

&Lt; General Formula (II) >

(In the general formula (II), R ²¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring), and R ²² , R ²³ , R ²⁴ and R ²⁵ each represent a hydrogen atom, A halogen atom and an alkoxy group having 1 to 6 carbon atoms, R ²² and R ^23, and R ²⁴ and R ²⁵ may be bonded to each other to form a ring, n 2 is 1 or 2 , And m is any one of 0, 1, and 2. Y ²¹ represents an alkylene group having 1 to 6 carbon atoms or an oxygen atom.

R ²¹ is preferably a hydrogen atom or a methyl group. Each of R ²² , R ²³ , R ²⁴ and R ²⁵ is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group or an ethoxy group, More preferably a hydrogen atom, a methyl group or an ethyl group. n2 is preferably 1 or 2. m2 is preferably 0 or 1. Y ²¹ is preferably a methylene group or an oxygen atom.

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

&Lt; General Formula (III) >

(In the general formula (III), R ³² , R ³³ , R ³⁴ and R ³⁵ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (may form a ring), a halogen atom or an alkoxy group having 1 to 6 carbon atoms. n3 is any one of 1, 2, 3, m3 represents 0, 1, any one of 2 X ³¹ is -C (= O) -., represents an alkylene group having 1 to 6 carbon atoms, 2 X ³¹ Y ³² represents an alkylene group having 1 to 6 carbon atoms or an oxygen atom.

R ³² , R ³³ , R ³⁴ and R ³⁵ each are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group or an ethoxy group, And a hydrogen atom is more preferable. n3 is preferably 1 or 2. X ³¹ is preferably -C = O-, a methylene group, or an ethylene group. Y ³² is preferably a methylene group or an oxygen atom.

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

&Lt; General Formula (IV) >

(In the general formula (IV), R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring). R ⁴² and R ⁴³ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and being optionally), a halogen atom, an alkoxy group having a carbon number of 1 ~ 6 W ⁴¹ represents a single bond or -C (= O) -.. represents the n4 is 2, 3, 4 represents any one of X ⁴² is - C (= O) - or an alkylene group having 1 to 6 carbon atoms, and each X ⁴² may be the same or different, and M ⁴¹ represents a hydrocarbon group having 1 to 4 carbon atoms, an oxygen atom or a nitrogen atom, M ⁴¹ may be the same or different.)

R ⁴¹ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. R ⁴² and R ⁴³ are each preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group or an ethoxy group, more preferably a hydrogen atom, a methyl group or an ethyl group, . M ⁴¹ is preferably any one of a methylene group, an ethylene group, a propylene group and a butylene group. X ⁴² is preferably -C (= O) - or a methylene group.

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

&Lt; General Formula (V) >

(In the general formula (V), R ⁵¹ represents a bond, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (which may form a ring), Z ⁵² represents an oxygen atom, -CH = N-, represents an alkylene group. W ⁵² is (as may form a ring), an alkyl group having 1 to 6 carbon atoms represents a alkylene group or an oxygen atom. R ⁵⁴ and R ⁵⁵ are each a hydrogen atom, a group having 1 to 6 carbon atoms, a halogen atom, And R ⁵⁴ and R ⁵⁵ may be bonded to each other to form a ring, and when X ⁵¹ represents a single bond or a non-bond and R ⁵¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms X ⁵¹ represents a single bond, R ⁵¹ if the non-bond X ⁵¹ represents a non-bonded. m5 is 0, 1, is any one of ^{2. W 52, Z 52,} R 54, R 55 1 out of more than Containing an oxygen atom or a nitrogen atom.

R ⁵¹ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. Z ⁵² is preferably an oxygen atom, -CH = N- or a methylene group. W ⁵² is preferably a methylene group or an oxygen atom. R ⁵⁴ and R ⁵⁵ are each preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group or an ethoxy group, more preferably a hydrogen atom, a methyl group or an ethyl group, desirable. m5 is preferably 1 or 2.

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

&Lt; General Formula (VI) >

(In the general formula (VI), R ⁶¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring), R ⁶² and R ⁶³ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms search), a hydroxy alkyl group having a carbon number of _{1 ~ 6, (CH 3)} 2 N- (CH 2) m6 - (m6 is 1, 2 or _{3), CH 3 CO- (CR} 64 R 65) p6 - (R 64 And R ⁶⁵ each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (which may form a ring), and p6 is any one of 1, 2, and 3), (CH ₃ ) ₂ -N- (CH ₂ ) _p6 - (. _p6 is either of 1, 2 or 3), a group having a group = CO, R ⁶² and R ⁶³ are not hydrogen atoms at the same time what is X ⁶ is -CO-, -COCH ₂ -., -COCH ₂ CH ₂ -, -COCH ₂ CH ₂ CH ₂ -, or -COOCH ₂ CH ₂ -.)

R ⁶¹ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. R ⁶² and R ⁶³ is _{(CH 3) 2 N- (CH} 2) m6 -hydroxyethyl group, and are each a hydrogen atom, methyl, ethyl, propyl ^{_{-, CH 3 CO- (CR 64}} R 65) p6 -, (CH ₃ ) a group having ₂ -N- (CH ₂ ) _{p 6} -, = CO group.

R ⁶⁴ and R ⁶⁵ are each preferably a hydrogen atom, a methyl group, an ethyl group or a propyl group.

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

&Lt; General Formula (VII) >

(In the general formula (VII), R ⁷¹ and R ⁷² are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring), and R ⁷³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms ).

R ⁷¹ and R ⁷² are each preferably a hydrogen atom or a methyl group, and R ⁷³ is preferably a hydrogen atom, a methyl group or an ethyl group.

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

&Lt; General Formula (VIII) >

(In the general formula (VIII), R ⁸¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (may form a ring), or a hydroxyalkyl group having 1 to 6 carbon atoms. R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ At least two of R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ are bonded to each other to form a ring, and R 1 and R 2 each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms (which may form a ring), or a hydroxyalkyl group having 1 to 6 carbon atoms; W ⁸¹ is an alkylene group having 1 to 6 carbon atoms, -NH- group, -N-CH ₂ - group or -NC ₂ H ₄ - group, W ⁸² is a single bond or -C = O) - When W ⁸² is a single bond, R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ are not all hydrogen atoms, and n 7 represents an integer of 0 to 8.

R ⁸¹ is preferably a hydrogen atom, a methyl group or a hydroxymethyl group, and more preferably a hydrogen atom. R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ each are preferably a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a propyl group and a butyl group. W ⁸¹ is preferably -CH ₂ -, -NH- group, -N-CH ₂ - group or -NC ₂ H ₄ - group.

Specific examples of the compound represented by the general formula (VIII) include the following formulas (VIII-1) to (VIII-14).

In the present invention, in addition to the above polymerizable unsaturated monomer, a polymerizable unsaturated monomer containing an ethylenic unsaturated bond and a silicon atom and / or phosphorus atom (hereinafter sometimes referred to as &quot; second polymerizable unsaturated monomer &quot; . The second polymerizable unsaturated monomer may be a monofunctional polymerizable unsaturated monomer or a polyfunctional polymerizable unsaturated monomer.

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

The composition of the present invention uses a monofunctional polymerizable unsaturated monomer containing a site having an ethylenic unsaturated bond in a molecule and a site having an oxygen, nitrogen or sulfur atom as an essential component. For the purpose of improving film hardness and flexibility, the following polymerizable unsaturated monomers having one ethylenically unsaturated bond-containing group (monofunctional polymerizable unsaturated monomer) may also be used in combination.

Specific examples of the compound that can be used in combination include 2-acryloyloxyethyl phthalate, 2-acryloyloxy-2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2- acryloyloxypropyl phthalate (Meth) acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (Meth) acrylate, butoxy (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, Ethylene oxide modification (hereinafter referred to as &quot; (Meth) acrylate, isopropyl (meth) acrylate, isoamyl (meth) acrylate, isobutyl (meth) acrylate, Acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, isomyl (meth) acrylate, Acrylate, methoxypolyethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol Nonylphenoxypolypropylene glycol (meth) acrylate, octyl (meth) acrylate, para-cumylphenoxyethylglycol (meth) acrylate, epichlorohydrate (Meth) acrylate, phenoxyethyleneglycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (hereinafter referred to as &quot; ECH &quot;) modified phenoxy acrylate, phenoxyethyl (Meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, tribromophenyl (meth) acrylate, EO modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate, p-isopropenylphenol, styrene, (meth) acrylate, isocyanatoethyl (meth) acrylate, isocyanate n-propyl (meth) acrylate, (Meth) acrylate, isocyanate isopropyl (meth) acrylate, isocyanate n-butyl (meth) acrylate, isocyanate isobutyl (meth) acrylate, isocyanate sec- Isocyanatoalkyl (meth) acrylates such as acrylate; Acryloyl isopropyl acrylate, (meth) acryloyl methyl isocyanate, (meth) acryloyl ethyl isocyanate, (meth) acryloyl n-propyl isocyanate, (meth) acryloyl isopropyl isocyanate, (Meth) acryloyl isocyanate such as (meth) acryloyl isobutyl isocyanate, (meth) acryloyl sec-butyl isocyanate and (meth) acryloyl tert-butyl isocyanate.

It is preferable to use a multifunctional polymerizable unsaturated monomer having two or more ethylenic unsaturated bond-containing groups in the composition of the present invention.

Examples of the bifunctional polymerizable unsaturated monomer having two ethylenically unsaturated bond-containing groups that can be preferably used in the present invention include diethylene glycol monoethyl ether (metha) acrylate, dimethyrol dicyclopentanedi (meth) acrylate , Di (meth) acrylated isocyanurate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, EO-modified 1,6- (Meth) acrylate, EO-modified bisphenol A di (meth) acrylate, EO-modified 1,6-hexanediol di (meth) acrylate, allyloxypolyethylene glycol acrylate, 1,9- Modified bisphenol F di (meth) acrylate, ECH modified hexahydrophthalic acid diacrylate, hydroxypivalic neopentyl glycol di (meth) acrylate, modified bisphenol A di (meth) acrylate, acryl (Hereinafter referred to as &quot; PO &quot;) -modified neopentyl glycol diacrylate, caprolactone-modified hydroxypivalic acid esters neopentyl (meth) acrylate, EO- Poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol-tetramethylene glycol) di (meth) acrylate, glycol, stearic acid modified pentaerythritol di (meth) acrylate, ECH modified phthalic acid di (Meth) acrylate, polyester diacrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ECH-modified propylene glycol di , Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tricyclodecane dimethanol (Meth) acrylate, tripropylene glycol di (meth) acrylate, EO-modified tripropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di Propylene glycol di (meth) acrylate, divinylethylene urea, and divinylpropylene urea.

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

Examples of multifunctional polymerizable unsaturated monomers having three or more ethylenically unsaturated bond-containing groups include ECH-modified glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, pentaerythritol (Meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythole hexa (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol Acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, And the like.

Among them, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, trimethylol propane tri (meth) acrylate, EO- Pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like are preferably used in the present invention.

When a compound having two or more photopolymerizable functionalities in one molecule is used, since a large amount of photopolymerizable functional groups are introduced into the composition as described above, the crosslinking density of the composition becomes very large and the effect of improving various physical properties after curing is high. Among various physical properties after curing, in particular, heat resistance and durability (wear resistance, chemical resistance, water resistance) are improved by an increase in cross-link density, and deformation, disappearance, and damage of the fine uneven pattern are hardly caused even when exposed to high heat, friction or solvent.

In the composition of the present invention, a polyfunctional oligomer or polymer having a molecular weight larger than that of the above-mentioned polyfunctional polymerizable unsaturated monomer may be added within the range to achieve the object of the present invention, for the purpose of further increasing the crosslinking density. Examples of polyfunctional oligomers having photo radical polymerizability include various acrylate oligomers such as polyester acrylate, polyurethane acrylate, polyether acrylate and polyepoxyacrylate, phosphazene skeleton, adamantane skeleton, cardo skeleton, nor And oligomers or polymers having a bulky structure such as a vinylene skeleton.

As the polymerizable unsaturated monomer used in the present invention, a compound having an oxirane ring can also be employed. Examples of the compound having an oxirane ring include polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, polyglycidyl esters of aromatic polyols Esters, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds, and epoxidized polybutadienes. These compounds may be used singly or in a mixture of two or more kinds thereof.

Examples of commercially available products that can be preferably used as the glycidyl group-containing compound include UVR-6216 (manufactured by Union Carbide), glycidol, AOEX24, Cychroma A200 (manufactured by Daicel Chemical Industries, Ltd.) (Available from Yucca Shell Co., Ltd.), KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2720 and KRM-2750 , Manufactured by Asahi Denka Kogyo Co., Ltd.). These may be used singly or in combination of two or more.

The compound having an oxirane ring may be prepared by any method known in the art, for example, from Maruzen KK Publishing Co., Ltd., Experimental Chemistry Lecture 20, Organic Synthesis II, 213 ~, 1992, Ed.by Alfred Hasfner, The chemistry of heterocyclic Yoshimura, Adhesion, Vol. 29, No. 12, 32, 1985, Yoshimura, Adhesion, Vol. 30, No. 5, No. 42, 1986, Yoshimura, "Interscience Publication, New York, 1985 , Adhesion, Vol. 30, No. 7, No. 42, 1986, Japanese Patent Application Laid-Open No. 11-100378, Japanese Patent No. 2906245, and Japanese Patent No. 2926262.

A vinyl ether compound may be used in combination as the polymerizable compound used in the present invention. The vinyl ether compound may be appropriately selected and examples thereof include 2-ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, diethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, Ethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether , Neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylol ethane trivinyl ether, hexane diol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, penta Erythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol penta vinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol di Ethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene vinyl ether, trimethylol propane triethylene vinyl ether, trimethylol propane diethylene vinyl ether, pentaerythritol diethylene vinyl ether, pentaerythritol triethylene vinyl ether , Pentaerythritol tetraethylene vinyl ether, 1,1,1-tris [4- (2-vinyloxyethoxy) phenyl] ethane, and bisphenol A divinyloxyethyl ether.

These vinyl ether compounds can be produced by the method described in, for example, Stephen C. Capin, Polymers Paint Color Journal, 197 (4237), 321 (1988), that is, the reaction of polyhydric alcohol or polyhydric phenol with acetylene, Can be synthesized by reacting a polyhydric phenol with a halogenated alkyl vinyl ether, and these can be used singly or in combination of two or more kinds.

Examples of the polymerizable compound used in the present invention include styrene derivatives. Examples of the styrene derivative include styrene derivatives such as styrene, p-methylstyrene, p-methoxystyrene, p-methylstyrene, p-methyl-p-methylstyrene, p-hydroxystyrene. Examples of the vinyl naphthalene derivative include 1-vinylnaphthalene,? -methyl-1-vinylnaphthalene,? -methyl-1-vinylnaphthalene, , 4-methoxy-1-vinylnaphthalene, and the like.

(Meth) acrylate, perfluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, perfluoro (meth) acrylate, (Meth) acrylate, perfluorohexyl (meth) acrylate, perfluorooctyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, (Meth) acrylate can also be used in combination.

As the polymerizable compound used in the present invention, propenyl ether and butenyl ether can be blended. Dodecyl-1-butenyl ether, 1-butenoxymethyl-2-norbornene, 1-4-di (1-butenoxy) Butane, 1,10-di (1-butenoxy) decane, 1,4-di (1-butenoxymethyl) cyclohexane, diethylene glycol di Tri (1-butenoxy) propane, propenyl ether propylene carbonate, and the like.

Next, preferred blend forms of the polymerizable unsaturated monomers in the composition of the present invention will be described. The composition of the present invention preferably contains a monofunctional polymerizable unsaturated monomer selected from the above (a), (b) and (c) as essential components and further contains a multifunctional polymerizable unsaturated monomer.

The monofunctional polymerizable unsaturated monomer selected from the above (a), (b) and (c) is usually used as a reactive diluent and is effective for lowering the viscosity of the composition of the present invention. do. Preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and particularly preferably 30 to 60% by mass.

When the proportion of the monofunctional polymerizable unsaturated monomer selected from (a), (b) and (c) is 80% by mass or less, the cured film obtained by curing the composition of the present invention has mechanical strength, etching resistance, And when it is used as a mold material for a photo-nanoimprint, the mold tends to be swollen and the mold tends to be prevented from deteriorating, which is preferable. On the other hand, the monofunctional polymerizable unsaturated monomer selected from the above (a), (b) and (c) is preferable as a reactive diluent, and therefore it is preferable that 10 mass% or more of the total polymerizable compound is added.

The monomer (bifunctional polymerizable unsaturated monomer) having two unsaturated bond-containing groups preferably accounts for 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less of the total polymerizable compound . The ratio of the monofunctional and bifunctional polymerizable unsaturated monomer is preferably in the range of 1 to 95 mass%, more preferably 3 to 95 mass%, and particularly preferably 5 to 90 mass%, of the total polymerizable compound . The proportion of the multifunctional polymerizable unsaturated monomer having three or more unsaturated bond-containing groups is preferably 80% by mass or less, more preferably 70% by mass or less, and particularly preferably 60% by mass or less of the total polymerizable unsaturated monomer Lt; / RTI &gt; It is preferable that the proportion of the polymerizable unsaturated monomer having three or more polymerizable unsaturated bond-containing groups is 80% by mass or less, because the viscosity of the composition can be lowered.

In particular, in the composition of the present invention, the polymerizable compound component preferably comprises 10 to 80 mass% of monofunctional polymerizable unsaturated monomer, 1 to 60 mass% of bifunctional polymerizable unsaturated monomer, 1 to 60 mass% of trifunctional or more polyfunctional polymerizable unsaturated monomer , And it is preferably composed of 15 to 70% by mass of a monofunctional polymerizable unsaturated monomer, 2 to 50% by mass of a bifunctional polymerizable unsaturated monomer, and 2 to 50% by mass of a polyfunctional polymerizable unsaturated monomer having three or more functionalities It is more preferable that it is constituted.

In particular, in the composition of the present invention, a polymerizable unsaturated monomer containing a silicon atom and / or a phosphorus atom (second polymerizable unsaturated monomer) may be blended with a site having at least one ethylenic unsaturated bond. The second polymerizable unsaturated monomer is usually added in an amount of 0.1% by mass or more based on the total polymerizable compound for the purpose of improving the peelability with the mold and the adhesion to the base. Preferably 0.2 to 10% by mass, more preferably 0.3 to 7% by mass, and particularly preferably 0.5 to 5% by mass. The number of sites having an ethylenically unsaturated bond (the number of functional groups) is preferably from 1 to 3.

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, and still more preferably 1.0% by mass or less. When the water content in the preparation is 2.0 mass% or less, the storage stability of the composition of the present invention can be more stabilized.

In addition, the composition of the present invention preferably has an organic solvent content of 3 mass% or less in the total composition. That is, the composition of the present invention preferably contains a specific monofunctional or bifunctional monomer as a reactive diluent, so that it is not necessary to necessarily contain an organic solvent for dissolving the components of the composition of the present invention. In addition, if the organic solvent is not contained, a baking step for volatilizing the solvent is not required, which is advantageous in simplifying the process. Therefore, in the composition of the present invention, the content of the organic solvent is preferably 3 mass% or less, and more preferably 2 mass% or less, and it is particularly preferable that the organic solvent is not contained. Thus, the composition of the present invention does not necessarily contain an organic solvent but may be optionally added, for example, when dissolving a compound or the like which is insoluble in the reactive diluent as the composition of the present invention, or when finely adjusting the viscosity. The organic solvent that can be preferably used in the composition of the present invention is a solvent generally used in a curable composition for a photo-nanoimprint lithography or a photoresist, and it is only required to dissolve and uniformly disperse the compound used in the present invention, Is not particularly limited as long as it does not react with the component.

Examples of the organic solvent include alcohols such as methanol and ethanol; Ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycol such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and 2-heptanone; Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy- , Esters such as esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate .

The organic solvent may be selected from the group consisting of N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, Octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, gamma -butyrolactone , High-boiling solvents such as ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate may be added. These may be used singly or in combination of two or more.

Of these, methoxypropylene glycol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, methyl isobutyl ketone and 2- .

A photopolymerization initiator is used in the composition of the present invention. The photopolymerization initiator used in the present invention is contained in an amount of 0.1 to 11 mass%, preferably 0.2 to 10 mass%, and more preferably 0.3 to 10 mass% in the total composition. However, when they are used in combination with other photopolymerization initiators, their total amount falls within the above range.

When the proportion of the photopolymerization initiator is less than 0.1% by mass, sensitivity (fast curability), resolution, line edge roughness and film strength are lowered, which is not preferable. On the other hand, if the proportion of the photopolymerization initiator exceeds 11% by mass, the light transmittance, coloring property, handling property, etc. are deteriorated. The amount of the photo-polymerization initiator and / or photo-acid generator to be added to the ink-jet composition or the composition for a liquid crystal display color filter containing the dye and / or pigment has been variously investigated so far. For the photo- The addition amount of the preferable photopolymerization initiator and / or photoacid generator to the curable composition is not reported. That is, in systems containing dyes and / or pigments, they may act as radical trapping agents, thereby affecting photopolymerization and sensitivity. In consideration of this point, the amount of the photopolymerization initiator to be added is optimized in these applications. On the other hand, in the composition of the present invention, the dye and / or pigment are not indispensable components, and the optimum range of the photopolymerization initiator may be different from that of the inkjet composition or composition for a liquid crystal display color filter.

The photopolymerization initiator used in the present invention is one which is blended with an active substance to the wavelength of the light source to be used and generates a suitable active species. The photopolymerization initiator may be used singly or in combination of two or more.

As the radical photopolymerization initiator used in the present invention, for example, commercially available initiators can be used. Examples thereof include Irgacure (registered trademark) 2959 (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one available from Ciba, Irgacure (1-hydroxycyclohexyl phenyl ketone), Irgacure (registered trademark) 500 (1-hydroxycyclohexyl phenyl ketone, benzophenone), Irgacure (registered trademark) 651 (2,2-dimethoxy- Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Irgacure (R) 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Irgacure (R) (Registered trademark) 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 1 -hydroxy-cyclohexylphenyl-ketone), Irgacure (registered trademark) 1800 2-methyl-1-phenyl-1-propan-1-one), Irg (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, acure 占 OXE01 (1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O- benzoyloxime), Darocur 占 1173 (2-hydroxy- 1-propan-1-one), Darocur 占 1116,1398, 1174 and 1020, CGI242 (ethanone, 1- [9-ethyl- 6- (2- methylbenzoyl) -9H- 3-yl] -1- (O-acetyloxime), Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) available from BASF, Lucirin TPO-L (2,4,6 (Trimethylbenzoyl phenyl ethoxyphosphine oxide), ESACURE 1001M (1- [4- benzoylphenylsulfanyl] phenyl] -2-methyl-2- (4- methylphenylsulfonyl) propane- 1-one, N-1414 Adeka Optomer (registered trademark) N-1414 (carbazole-phenone type), Adeka Optomer (registered trademark) N-1717 (acridine type) available from Asahi Denka, N-1606 (triazine system), TFE-triazine (2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) - 1, 3, 5-triazine), TME-triazine (2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) 3,5-triazine), MP-triazine (2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine) (Trichloromethyl) -1,3,5-triazine), Midorikagaku TAZ-113 (2- [2- (3,4-dimethoxyphenyl) ethenyl] -108 (2- (3,4-dimethoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine), benzophenone, 4,4'-bisdiethylaminobenzophenone , Methyl-2-benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 4-phenylbenzophenone, ethylmihiller ketone, 2- chlorothioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, thioxanthone ammonium salt, benzoin, 4 , 4'-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin iso Benzyl isobutyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetophenone, diethoxyacetophenone and dibenzosuberone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl Benzoylbenzene, benzyl, 10-butyl-2-chloroacridone, [4- (methylphenylthio) phenyl] phenylmethane), 2-ethyl anthraquinone, 2,2 -Bis (2-chlorophenyl) 4,5,4 ', 5'-tetrakis (3,4,5-trimethoxyphenyl) Phenyl) 4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, tris (4-dimethylaminophenyl) methane, ethyl 4- (dimethylamino) benzoate, 2- ) Ethyl benzoate, butoxyethyl-4- (dimethylamino) benzoate, and the like.

In addition to the photopolymerization initiator and / or the photo acid generator, the composition of the present invention may further comprise a photosensitizer to adjust the wavelength of the UV region. Typical sensitizers which can be used in the present invention include those disclosed in JV Crivello, Adv.in Polymer Sci, 62, 1 (1984), and specific examples thereof include pyrene, perylene, acridine Anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives such as benzothiophene, benzothiophene, benzothiophene, And the like.

Light for initiation of polymerization of the present invention includes not only light having wavelengths in the range of ultraviolet light, near ultraviolet light, extraneous light, visible light, infrared light, or electromagnetic waves but also radiation. Examples of the radiation include microwave, electron beam, EUV, X Line. Further, a laser beam such as a 248 nm excimer laser, a 193 nm excimer laser, or a 172 nm excimer laser can also be used. These lights may be monochromatic light (single wavelength light) passed through an optical filter, or may be lights of different wavelengths (composite light). Exposure can also be performed by multiple exposures, and after pattern formation for the purpose of enhancing the film strength and etching resistance, the entire surface can be exposed.

The photopolymerization initiator used in the present invention needs to be selected in a timely manner with respect to the wavelength of the light source to be used, but it is preferable that the photopolymerization initiator does not generate gas during the pressurization and exposure of the mold. When the gas is generated, the mold is contaminated. Therefore, the mold must be frequently cleaned, or the curable composition for optical nanoimprint lithography is deformed in the mold to deteriorate the transfer pattern accuracy. It is preferable that the gas is not generated because the mold is not easily contaminated and the cleaning frequency of the mold is reduced and it is difficult for the curable composition for optical nanoimprint lithography to be deformed in the mold so that it is difficult to deteriorate the transfer pattern accuracy.

The composition of the present invention contains 0.001 to 5 mass% of at least one of a fluorine-based surfactant, a silicon-based surfactant and a fluorine-silicon-based surfactant. The proportion of the surfactant in the composition is preferably 0.002 to 4% by mass, more preferably 0.005 to 3% by mass.

When the amount of the fluorine surfactant, the silicone surfactant and the fluorine silicone surfactant is less than 0.001, the effect of the uniformity of the coating is insufficient. On the other hand, when the content exceeds 5% by mass, the mold transfer characteristics are deteriorated. The fluorine-based surfactant, silicon-based surfactant and fluorine-silicon-based surfactant used in the present invention may be used alone or in combination of two or more. In the present invention, it is preferable that both of the fluorine-based surfactant and the silicon-based surfactant or the fluorine-silicon-based surfactant are contained.

It is most preferable to contain a fluorine-silicon surfactant.

Here, the fluorine-silicon surfactant refers to a fluorine surfactant and a silicone surfactant, both of which have requirements.

By using such a surfactant, the composition of the present invention can be used as a silicon wafer for semiconductor device production, a glass substrate for manufacturing a liquid crystal device, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, a tantalum alloy film, a silicon nitride film, an amorphous silicon film, Various films such as an indium tin oxide (ITO) film and a tin oxide film formed by doping with tin oxide are formed, and the problem of poor coating such as striation or scaly shape (dry deviation of the resist film) It is possible to lower the viscosity of the composition and to improve the flowability of the composition into the cavity of the mold recess and to improve the releasability between the mold and the resist and to improve the adhesion between the resist and the substrate. Particularly, in the composition of the present invention, the addition of the above surfactant makes it possible to largely improve the uniformity of coating, and in coating with a spin coater or slit scan coater, good coating applicability can be obtained regardless of the substrate size.

Examples of the nonionic fluorosurfactant used in the present invention include Fluorad FC-430, FC-431 (Sumitomo 3M), Surflon S-382 (Asahi Glass Co.), EFTOP EF- PF-6320, PF-656, and PF-6520 (all available from OMNOVA), trade names &quot; PF-631 &quot; 172, 173, 178K (trade names) manufactured by Daicheng Kogyo Co., Ltd. under the trade names of Gent FT250, FT251 and DFX18 (all manufactured by Neos Co., Ltd.), trade names Unidyne DS-401, DS-403 and DS- , 178A (all manufactured by Dainippon Ink and Chemicals, Incorporated), and examples of nonionic silicon surfactants include SI-10 series (manufactured by Takemoto Yushi), Megapac Painter 31 (manufactured by Dainippon Ink & -341 (Shinetsu Kagaku Teigyo).

Examples of the fluorine-silicon surfactant used in the present invention include trade names X-70-090, X-70-091, X-70-092, X-70-093 (all manufactured by Shin-Etsu Chemical Co., , And XRB-4 (all manufactured by Dainippon Ink and Chemicals, Incorporated).

Other nonionic surfactants may also be used in combination with the composition of the present invention for the purpose of improving the flexibility and the like of the curable composition for light-nanoimprint lithography. Examples of commercially available nonionic surfactants include polyoxyethylene (e.g., D-3110, D-3120, D-3412, D-3440, D-3510 and D-3605 of Pionin series manufactured by Takemoto Yushi Co., Alkylamine, polyoxyethylene alkyl ethers such as D-1305, D-1315, D-1405, D-1420, D-1504, D-1508 and D-1518 of Pionin series manufactured by Takemoto Yushi Co., Polyoxyethylene mono-fatty acid esters such as D-2112-A, D-2112-C and D-2123-C of Pioneer series manufactured by Yushi Co., Ltd., D-2405 of Pionin series manufactured by Takemoto Yushi Co., D-406, D-410, D-414, D-418 and the like of Pionin series manufactured by Takemoto Yushi Co., Ltd. And polyoxyethylene tetramethyldisinediol diethers such as 104S, 420, 440, 465 and 485 of the saponin series manufactured by Nisshin Chemical Industry Co., Ltd., and the like. A reactive surfactant having a polymerizable unsaturated group can also be used in combination with the surfactant used in the present invention. For example, allyloxypolyethylene glycol monomethacrylate (trade name: Blemmer PKE series by Nippon Oil Co., Ltd.), nonylphenoxy polyethylene glycol monomethacrylate (trade name: Blemmer PNE series by Nippon Oil Co., Ltd.) (Ethylene glycol-propylene glycol) monomethacrylate (trade name: BLEMMER PNEP-600 (trade name) manufactured by Nippon Oil Co., Ltd.), polypropylene glycol monomethacrylate ), Aquarone RN-10, RN-20, RN-30, RN-50, RN-2025, HS-05, HS-10 and HS-20 (manufactured by Daiichi Kogyo Seiyaku Co., have.

The composition of the present invention may contain, in addition to the above components, a releasing agent, a silane coupling agent, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, an antioxidant, a plasticizer, a adhesion promoter, a thermal polymerization initiator, An antioxidant, a photoacid generator, a photo acid generator, a photobase generator, a basic compound, a flow regulator, a defoaming agent, a dispersant, and the like may be added.

In the composition of the present invention, an organometallic coupling agent may be added to improve the heat resistance, strength, or adhesion of the surface structure having a fine uneven pattern to the metal deposition layer. The organometallic coupling agent is also effective because it has an effect of accelerating the thermosetting reaction. As the organometallic coupling agent, various coupling agents such as a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent and a tin coupling agent can be used.

The organometallic coupling agent may be optionally blended in an amount of 0.001 to 10 mass% in the total solid content of the curable composition for light-nanoimprint lithography. When the proportion of the organometallic coupling agent is 0.001% by mass or more, there is a tendency that the heat resistance, the strength, and the improvement of the adhesion to the vapor deposition layer are more effective. On the other hand, when the proportion of the organometallic coupling agent is 10 mass% or less, the stability of the composition and the deficiency of the film forming property tend to be suppressed, which is preferable.

Examples of commercially available antioxidants include Irganox 1010, 1035, 1076 and 1222 (manufactured by Chiba Chemical Industry Co., Ltd.), Antigene P, 3C, FR, Smilizer S and Smilizer GA-80 (Sumitomo Chemical Co., AO80 and AO503 (manufactured by ADEKA Corporation), which may be used alone or in combination. It is preferable that the antioxidant is blended in a proportion of 0.01 to 10 mass% with respect to the total amount of the composition.

Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350, and 350 were used as commercially available products of ultraviolet absorber, Tinuvin P, 234, 320, 326, 327, 328, 400 (manufactured by Sumitomo Chemical Industry Co., Ltd.) and the like. The ultraviolet absorber is preferably blended in an amount of 0.01 to 10% by mass, based on the total amount of the curable composition for light-nanoimprint lithography.

Examples of commercially available light stabilizers include Tinuvin 292, 144 and 622 LD (manufactured by Chiba Kagi Kogyo Co., Ltd.), Sanol LS-770, 765, 292, 2626, 1114 and 744 (manufactured by Sankyo Kasei Kogyo Co., Ltd.) . The light stabilizer is preferably blended in a proportion of 0.01 to 10 mass% with respect to the total amount of the composition.

Antigene W, S, P, 3C, 6C, RD-G, FR, and AW (manufactured by Sumitomo Chemical Industry Co., Ltd.) are examples of commercially available antioxidants. The antioxidant is preferably blended in a proportion of 0.01 to 10% by mass with respect to the total amount of the composition.

A plasticizer may be added to the composition of the present invention in order to adjust the adhesion to the substrate, the flexibility of the film, and the hardness. Specific examples of the preferable plasticizer include, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, dimethyl adipate , Di (ethyl) adipate, di (n-butyl) adipate, dimethylsuberate, diethylsberate, di . Preferably 20 mass% or less, and more preferably 10 mass% or less. In order to obtain the effect of adding the plasticizer, 0.1 mass% or more is preferable.

When the composition of the present invention is cured, a thermal polymerization initiation system may be added as needed. Preferred examples of the thermal polymerization initiator include peroxides and azo compounds. Specific examples thereof include benzoyl peroxide, tert-butyl-peroxybenzoate and azobisisobutyronitrile.

For the purpose of adjusting the pattern shape, sensitivity and the like, the composition of the present invention may be added with a photo-base generator if necessary. For example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] Hexylamine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) Benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaamine cobalt (III) tris (triphenylmethyl borate) Dimethylphenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4- (2'-nitrophenyl) -3,5-diacetyl-4- (2 ', 4'-dinitrophenyl) -1,4-dihydropyridine, and the like.

A coloring agent may optionally be added to the composition of the present invention for the purpose of improving the visibility of the coating film. The colorant may be used in a range that does not impair the purpose of the present invention, such as a pigment or a dye used in a UV inkjet composition, a composition for a color filter and a composition for a CCD image sensor. As the pigment which can be used in the present invention, various conventionally known inorganic pigments or organic pigments can be used. Specific examples of the inorganic pigments include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, . Examples of the organic pigments include CI Pigment Yellow 11,24,31,53,83,99,108,109,110,138,139,151,154,167, CI Pigment Orange 36,38,43, CI Pigment Red 105,122,149,150,155,171,175,176,177,209, CI Pigment Violet 19,23,32,39, CI Pigment Blue 1,2, 15,16,22,60,66, CI Pigment Green 7,36,37, CI Pigment Brown 25,28, CI Pigment Black 1,7, and carbon black.

The inorganic fine particles are preferably blended in a proportion of 1 to 70% by weight, particularly preferably 1 to 50% by weight, based on the total solid content of the curable composition for light-nanoimprint lithography. By maintaining the proportion of the inorganic fine particles at 1% by mass or more, the adhering, shape-retaining property and releasability of the composition of the present invention can be sufficiently improved. When the proportion of the inorganic fine particles is 70% by mass or less, .

Further, in the composition of the present invention, elastomer particles may be added as optional components for the purpose of improving mechanical strength, flexibility and the like.

The elastomer particles which can be added as optional components to the composition of the present invention have an average particle size of preferably 10 nm to 700 nm, more preferably 30 to 300 nm. Butylene copolymer, a styrene / isoprene copolymer, an ethylene / propylene copolymer, an ethylene /? - olefin copolymer, an ethylene /? - olefin / isoprene copolymer, a polybutadiene, Styrene / butadiene block copolymers, and styrene / isoprene block copolymers. The styrene / butadiene block copolymer may be used alone or in combination of two or more. It is also possible to use core / shell type particles in which these elastomer particles are coated with a methyl methacrylate polymer, a methyl methacrylate / glycidyl methacrylate copolymer or the like. The elastomer particles may have a crosslinked structure.

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

The composition of the present invention may contain a known antioxidant. The antioxidant suppresses discoloration caused by light irradiation and fading due to various oxidizing gases such as ozone, active oxygen, NO _x , and SO _x (X is an integer). Examples of such antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates, Derivatives, saccharides, nitrites, sulfites, thiosulfates, hydroxylamine derivatives and the like.

A basic compound may optionally be added to the composition of the present invention for the purpose of suppressing curing shrinkage and improving thermal stability. Examples of the basic compound include nitrogen-containing heterocyclic compounds such as amine and quinoline and quinolizine, basic alkaline metal compounds, and basic alkaline earth metal compounds. Among them, amines are preferable from the viewpoint of compatibility with the photopolymerizable monomer, and examples thereof include amines such as octylamine, naphthalamine, xylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, dimethylaniline, Triethanolamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine, hexamethylenetetramine, and triethanolamine, and the like.

To the composition of the present invention may be added a photoacid generator that initiates photopolymerization by receiving energy rays such as ultraviolet rays for the purpose of promoting the photo-curing reaction. As the photoacid generator, an arylsulfonium salt or aryl iodonium salt, which is an onium salt, can be preferably used.

Examples of commercially available products of the photo acid generator include UVI-6950, UVI-6970, UVI-6974, UVI-6990 and UVI-6992 (manufactured by Union Carbide Corp.), ADEKA OPTOMER SP-150, SP- IRGACURE OXE01, IRGACURE CGI-1397, CGI-1325, CGI-1380, CGI-1311, CGI-263, CGI-268, CGI-1371, SP-172 (manufactured by Asahi Denka Kogyo Co., -1397, CGI-1325, CGI-1380, CGI-1311 (manufactured by Chiba Specialty Chemicals Co., Ltd.), CI-2481, CI-2624, CI- 2639, CI- 103, NDS-103, TPS-103, MDS-103, MPI-103 (manufactured by Satoromer), DTS-102, DTS-103, NAT-103, CD-1010 (Manufactured by Nippon Kayaku Co., Ltd.), PHOTOINITIATOR 2074 (manufactured by Rhodia Co., Ltd.), BB-103 (manufactured by Midori Kagaku Co., Ltd.), PCI-061T, PCI- UR-1104, UR-1105, UR-1106, UR-1107, UR-1113, UR-1114, UR-1115, UR-1118, UR- 1204, UR-1205, UR-1207, UR-1401, UR-1402, UR-1403, UR-M1010, UR-M1011, UR-M10112, UR- SAIT01, UR- SAIT02, UR- UR-SAIT0 5, UR-SAIT06, UR-SAIT07, UR-SAIT08, UR-SAIT09, UR-SAIT10, UR- SAIT11, UR- SAIT12, UR- SAIT13, UR- SAIT14, UR- SAIT15, UR-SAIT30 (manufactured by URAY), and the like. Of these, UVI-6970, UVI-6974, ADEKA Optomer SP-170, SP-171, SP-172, CD-1012 and MPI-103 can exhibit high photosensitization sensitivity by a composition comprising them . These photoacid generators may be used singly or in combination of two or more.

In the present invention, the curing rate can be improved by combining a polymerization initiator that generates an acid with an energy ray and a substance that newly generates an acid in an autocatalytic manner (hereinafter, referred to as an acid growth agent) by the action of the generated acid . Examples of the acid-proliferating agent include compounds disclosed in Japanese Patent Application Laid-Open Nos. 08-248561, 10-1508, 10-1508 and 3102640, specifically, (P-toluenesulfonyloxy) cyclohexane, 1,4-bis (p-toluenesulfonyloxy) cyclohexane, cis-3- (p- toluenesulfonyloxy) Cis-3- (p-octanesulfonyloxy) -2-phenol. Commercially available compounds include ARKPREX 11M (manufactured by Nippon Keimix Co., Ltd.) and the like.

A chain transfer agent may be added to the composition of the present invention to improve photo-curability. Specific examples include 4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 1,3,5-triazine- 3H, 5H) -thione, and pentaerythritol tetrakis (3-mercaptobutyrate).

An antistatic agent may be added to the composition of the present invention if necessary.

Next, a method of forming a pattern (particularly a fine uneven pattern) using the composition of the present invention will be described. In the present invention, the composition of the present invention can be applied and cured to form a pattern. More specifically, a pattern receptor layer is formed by applying a pattern forming layer comprising at least the composition of the present invention on a substrate or a support and drying as required to form a layer (pattern forming layer) comprising the composition of the present invention, The mold is pressed against the surface of the pattern forming layer to transfer the mold pattern, and the fine uneven pattern forming layer is exposed and cured. The optical imprint lithography according to the pattern forming method of the present invention can be laminated or multi-patterned, and can be used in combination with a conventional thermal imprint.

As an application of the composition of the present invention, a permanent film such as an overcoat layer or an insulating film can be produced by applying the composition of the present invention on a substrate or a support, and then exposing, curing and drying (baking) have.

Hereinafter, a pattern forming method and a pattern transfer method using the composition of the present invention will be described. The composition of the present invention can be produced by a generally known coating method such as a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, Or the like. The thickness of the layer made of the composition of the present invention varies depending on the intended use, but is in the range of 0.05 mu m to 30 mu m. The composition of the present invention may be applied in multiple application.

The substrate or the support for applying the composition of the present invention may be a substrate such as quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG, A polymer substrate such as a polyimide film, a TFT array substrate, an electrode plate of a PDP, a glass or transparent plastic substrate, a conductive substrate such as ITO or metal, an insulating substrate, silicon, silicon nitride, polysilicon, silicon oxide, A substrate for producing a semiconductor such as silicon or the like. The shape of the substrate may be a plate shape or a roll shape.

The light for curing the composition of the present invention is not particularly limited, and examples thereof include light or radiation having a wavelength in a region of high energy ionizing radiation, extra-atmospheric, non-atomic, visible, or infrared. As the high energy ionizing radiation source, for example, electron beams accelerated by accelerators such as a cockroach type accelerator, a Bandegraph type accelerator, a linear accelerator, a betatron, and a cyclotron are industrially most conveniently and economically used, Radiation such as γ rays, X rays, α rays, neutron rays, and proton rays emitted from an atom or a reactor may be used. Examples of the ultraviolet ray source include ultraviolet fluorescent lamps, low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, xenon lamps, carbon arc lamps, and the like. Radiation includes, for example, microwave and EUV. Further, laser light used in microfabrication of semiconductors such as LED, semiconductor laser light, KrF excimer laser light of 248 nm, and 193 nm ArF excimer laser can also be preferably used in the present invention. These lights may be monochrome light, or may be lights of different wavelengths (mixed light).

Next, the mold material usable in the present invention will be described. In the photo-nanoimprint lithography using the composition of the present invention, it is necessary to select a light-transmitting material for at least one of the mold material and the substrate. In the optical imprint lithography applied to the present invention, a curable composition for optical nanoimprint lithography is applied on a substrate, a light transmitting mold is pressed, and light is irradiated from the back surface of the mold to cure the curable composition for photo nanoimprint lithography. The curable composition for photo-nanoimprint lithography may also be cured by applying a curable composition for optical nanoimprint lithography on a light-transmitting substrate, pressing the mold, and irradiating light from the back surface of the mold.

The light irradiation may be carried out while the mold is attached or after the mold release, but in the present invention, it is preferable that the mold is adhered to the mold.

The mold usable in the present invention is a mold having a pattern to be transferred. The mold can form a pattern according to desired processing precision, for example, by photolithography or electron beam lithography. However, the method of forming a mold pattern in the present invention is not particularly limited.

The light-transmissive mold material used in the present invention is not particularly limited, and any material having a predetermined strength and durability may be used. Specifically, examples thereof include light transparent resins such as glass, quartz, PMMA and polycarbonate resin, transparent metal vapor deposition films, flexible films such as polydimethylsiloxane, light-curing films, metal films and the like.

The non-light-transmitting mold material used in the case of using the transparent substrate of the present invention is not particularly limited, but any material having a predetermined strength may be used. Specifically, examples of the substrate include a ceramic material, a vapor deposition film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, Fe, SiC, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, It is not constrained. The shape may be either a plate-like mold or a roll-shaped mold. Rolled molds are especially applied when continuous productivity of the transfer is required.

The mold used in the present invention may be subjected to mold release treatment to improve the peelability of the mold and the curable composition for use in photo-nanoimprint lithography. For example, a commercially available release system such as commercially available products of Daikin Kogyo Co., Ltd. under the trade name of Optol DSX or Sumitomo Sri M emmer: Novec EGC-1720 can be preferably used.

When the optical imprint lithography is performed using the present invention, it is preferable that the pressure of the mold is normally set at 10 atm or less. When the mold pressure is less than 10 atm, the mold and the substrate are less likely to be deformed, so that the pattern accuracy tends to be improved. Further, since the pressure is low, the apparatus tends to be reduced. It is preferable that the pressure of the mold is selected in such a range that the uniformity of the mold transfer can be ensured within a range in which the residual film of the curable composition for the photo-nanoimprint lithography of the convex portion of the mold becomes smaller.

In the present invention, the light irradiation in the optical imprint lithography may be sufficiently larger than the irradiation amount required for curing. The irradiation amount required for curing is determined by examining the consumption amount of the unsaturated bond of the curable composition for the light nanoimprint lithography or the selectivity of the cured film.

Further, in the optical imprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually performed at room temperature, but light irradiation may be performed while heating to increase the reactivity. In the vacuum state before the light irradiation, light irradiation may be performed in a vacuum state since it is effective in preventing air bubble mixing, inhibiting the decrease in reactivity due to oxygen incorporation, and improving the adhesion of the curable composition for a mold and a photo-nanoimprint lithography. The preferred degree of vacuum in the present invention is in the range of 10 ^-1 Pa to the normal pressure.

The composition of the present invention can be prepared as a solution by mixing the components described above and then filtering the solution through, for example, a filter having a pore diameter of 0.05 mu m to 5.0 mu m. The mixing and dissolution of the curable composition for optical nanoimprint lithography is usually performed at a temperature in the range of 0 to 100 캜. The filtration may be performed in multiple steps or repeated a plurality of times. The filtered liquid may also be re-filtered. The material to be used for filtration may be polyethylene resin, polypropylene resin, fluorine resin, nylon resin or the like, but is not particularly limited.

The case where the composition of the present invention is applied to an etching resist will be described. The etching process may be performed by a well-selected etching process, and a thin film pattern is obtained in order to remove a portion of the substrate not covered with the resist pattern. (Wet etching) using an etching solution, or a process (dry etching) in which a reactive gas is activated by a plasma discharge under a reduced pressure.

A large number of etching solutions have been developed and used as an etching solution in the case of wet etching, with a representative example being ferric chloride / hydrochloric acid, hydrochloric acid / nitric acid, and hydrobromic acid. For Cr, a mixed solution of cerium nitrate ammonium solution, cerium nitrate · hydrogen peroxide solution, dilute hydrofluoric acid, diffuse / nitric acid mixed solution for Ti, mixed solution of ammonium solution and hydrogen peroxide solution for Ta, hydrogen peroxide solution for ammonia, ammonia water / hydrogen peroxide solution Nitric acid, a mixture of phosphoric acid and nitric acid, a mixture of phosphoric acid, nitric acid and acetic acid, a diluted water for ITO, a ferric chloride solution, hydrogen iodide, SiNx or SiO 2, a mixture of phosphoric acid and nitric acid, a mixture of phosphoric acid and nitric acid, ₂ is a mixture of hydrofluoric acid, fluoric acid and ammonium fluoride, Si and poly Si is a mixture of arsenic, nitric acid and acetic acid, W is ammonia water and hydrogen peroxide, PSG is nitric acid and hydrofluoric acid, BSG is hydrofluoric acid and ammonium fluoride Respectively.

The wet etching may be a shower method or a dip method. However, the etching rate, the uniformity in the plane, and the accuracy of the wiring width largely depend on the processing temperature. Therefore, it is necessary to optimize the conditions depending on the substrate type, application and line width. When the wet etching is performed, post baking is preferably performed in order to prevent undercut due to penetration of the etching solution. These post-baking is usually carried out at about 90 ° C to 140 ° C, but is not necessarily limited thereto.

Dry etching basically employs a parallel-plate dry etching apparatus having a pair of electrodes arranged in parallel in a vacuum apparatus, and a substrate is provided on one of the electrodes. A reactive ion etching (RIE) mode in which a high frequency power source for generating a plasma is connected to an electrode on a side where a substrate is provided or an electrode is connected to an opposite electrode, and a plasma etching (PE) Mode.

As the etchant gas used in the dry etching, a etchant gas suitable for each film type is used. (chlorine) + oxygen, tetrafluorocarbon (sulfur hexafluoride) + hydrogen chloride (chlorine) for a-Si / n + or s-Si, carbon tetrafluoride + oxygen for a- (Tetrafluoro sulfur) + oxygen for Ta, tetrafluorocarbon + oxygen for MoTa / MoW, chlorine + oxygen for Cr, boron trichloride for Al, + Chlorine, hydrogen bromide, hydrogen bromide + chlorine, hydrogen iodide, and the like. In the dry etching process, the structure of the resist is greatly altered by ionic shock or heat, which also affects the peelability.

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

The resist stripping rate greatly influences the temperature, the liquid amount, the time, the pressure, etc., and can be optimized according to the substrate type and the application. In the present invention, it is preferable to immerse the substrate (for several minutes to several tens minutes) in a temperature range of about room temperature to about 100 ° C, and rinse with a solvent rinse such as butyl acetate or water. (Water) rinse may be used from the viewpoint of improving the rinsing property, the particle removing property, and the corrosion resistance of the peeling liquid itself. The cleaning with water may be a pure shower, and the drying with air knife may be a preferable example. When amorphous silicon is exposed on the substrate, it is preferable to block the air because an oxide film is formed by the presence of water and air. Also, a method of using ashing (ashing) and peeling with a chemical liquid may be used in combination. Ashing can include plasma ashing, downflow ashing, ashing with ozone, and UV / ozone ashing. For example, when an Al substrate is processed by dry etching, a chlorine gas is generally used, but aluminum chloride, which is a product of chlorine and Al, sometimes corrodes Al. In order to prevent these, a peeling solution containing a preservative may be used.

There are no particular restrictions on the etching process, the peeling process, the rinsing process, and other processes other than the cleaning with water, and those appropriately selected from known processes for pattern formation can be cited. For example, a hardening treatment process. These may be used alone or in combination of two or more. The curing treatment process is not particularly limited and can be appropriately selected depending on the purpose. For example, the whole surface heat treatment and the whole surface exposure treatment are preferable.

As the method of the whole surface exposure treatment, for example, there is a method of exposing the entire surface of the formed pattern. Curing in the composition for forming the photosensitive layer is promoted by the entire surface exposure, and the surface of the pattern is cured, so that the etching resistance can be increased. The apparatus for performing the entire surface exposure is not particularly limited and may be appropriately selected according to the purpose. For example, a UV exposure apparatus such as an ultra-high pressure mercury lamp is preferably used.

<Examples>

Hereinafter, the present invention will be described in more detail by way of examples. The materials, amounts, ratios, processing contents, processing procedures and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

- Polymerizable unsaturated monomer -

R-1: Compound (I-2) Gammabutyrolactone acrylate (GBLA: manufactured by ENF)

R-2: Compound (I-3)? -Acryloxy-?,? -Dimethyl-? -Butyrolactone (reagent manufactured by Aldrich)

R-3: Compound (I-4) mevalonic lactone (meth) acrylate (Synthesis: synthesized according to JP 2004-2243 A)

R-4: Compound (II-3) 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane (Viscoat MEDOL10, manufactured by Osaka Yuki Kogyo Co.,

R-5: Compound (II-5) 4-acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane (Viscot HDOL10 Osaka Yuki Kagaku Co., Ltd.)

R-6: Compound (II-7) (3-methyl-3-oxetanyl) methyl acrylate (Viscot OXE10, Osaka Yukikagaku)

R-7: Compound (III-2) N-vinylsuccinimide (Synthesis)

Synthesis according to DokladyAkademiiNaukRespublikiUzbekistan (1), 39 water-49 (1993)

R-8: Compound (III-6) N-piperidinoethyl acrylate (Synthesis)

Synthesis according to Journal fuer Praktische Chemie (Leipzig), 7, 308-10 (1959)

R-9: Compound (III-7) 2-Propenoic acid 2-methyl-oxiranyl methyl ester (Synthesis)

Synthesis according to Gaofenzi Xuebao (1), 109-14, (1993)

R-10: Compound (III-8) N-morpholinoethyl acrylate (synthesized product)

Synthesis according to American Chemical Society, 71, 3164-5, (1949)

R-11: Compound (IV-1) N-vinyl-2-pyrrolidone (Aronix M-150: manufactured by Toagosei Co.,

R-12: Compound (IV-2) N-vinylcaprolactone (reagent manufactured by Aldrich)

R-13: Compound (IV-3) N-Vinylsuccinimide (Synthesis)

Synthesized according to Kunststoffe Plastics, 4, 257-64, (1957)

R-14: Compound (IV-5) 1-vinylimidazole (reagent manufactured by Aldrich)

R-15: Compound (IV-8) N-acryloylmorpholine (ACMO:

R-16: Compound (V-1) 4-vinyl-1-cyclohexene 1,2-epoxide (manufactured by Celloside Dielskag)

R-17: Compound (V-2) 2-vinyl-2-oxazoline (VOZO:

R-18: Compound (V-6) 4-vinyl 1,3-dioxolane-2-one (reagent manufactured by Aldrich)

R-19: Compound (VI-1) isobornyl acrylate (Aronix M-156: manufactured by Toagosei Co., Ltd.)

R-20: Compound (VI-9) isobornyl vinyl ether (manufactured by Daicel Chemical Industries, Ltd.)

R-21: Compound (VII-2) N-hydroxyethyl acrylamide (HEAA:

R-22: Compound (VIII-1) N-vinylformamide (Beam set 770: Arakawa Chemical Industries, Ltd.)

R-23: Compound (IX-2) Acrylic acid 3- (trimethoxysilyl) propyl ester (Tokyo Chemical Industry Co., Ltd.)

R-24: Compound (IX-20) 2-methacryloxyethyl acid phosphate (lite ester P-1M: manufactured by Kyowa Chemical Industry Co., Ltd.)

R-25: Compound (IX-23) Ethylene oxide-modified phosphoric acid dimethacrylate (Kayamer PM-21, manufactured by Nippon Kayaku Co., Ltd.)

R-26: Compound (II-8) Tetrahydrofurfuryl acrylate (Viscot # 150, Osaka Yukikagaku)

S-01: ethoxydiethylene glycol acrylate (light acrylate EC-A: manufactured by Kyowa Shikagaku Co., Ltd.)

S-02: hydroxypivalic acid neopentyl glycol diacrylate (Karajad MANDA manufactured by Nippon Kayaku Co., Ltd.)

S-03: Polyethylene glycol diacrylate (New Frontier PE-300: manufactured by Daiichi Kogyo Seiyakusa)

S-04: Tripropylene glycol diacrylate (Karajad TPGDA: manufactured by Nippon Kayaku Co., Ltd.)

S-05: Ethylene oxide-modified trimethylolpropane triacrylate (SR-454, manufactured by Kayakusa tomer)

S-06: propylene oxide-modified trimethylol propane triacrylate (New Frontier TMP-3P: manufactured by Daiichi Kogyo Seiyakusa)

S-07: pentaerythritol ethoxytetraacrylate (Ebercryl 40: manufactured by Daicel UCB)

S-08: dipentaerythol hexaacrylate (Karajad DPHA: manufactured by Nippon Kayaku Co., Ltd.)

S-09: Ethylene oxide-modified neopentyl glycol diacrylate (Photomer 4160: manufactured by Sanofo)

S-10: Benzyl acrylate (Viscot # 160: manufactured by Osaka Yuki Kagaku)

S-11: Phenoxyethyl acrylate (light acrylate PO-A: manufactured by Kyoeisha Co.)

S-12: trimethylolpropane triacrylate (Aronix M-309: manufactured by Toagosei Co., Ltd.)

S-13: 1,6-hexanediol diacrylate (Frontier HDDA: Daiichi Kogyo Seiyaku Co., Ltd.)

S-14: Ethylene oxide-modified bisphenol A diacrylate (SR-602, manufactured by Kayaku Satoru Co., Ltd.)

S-15: Epoxy acrylate (Ebecryl 3701: manufactured by Daicel UCB Co., Ltd.)

S-16: Ethylene oxide-modified bisphenol A diacrylate (Aronix M-211B: manufactured by Toagosei Co., Ltd.)

S-17: Aquarone RN-20: manufactured by Dai-ichi Kogyo Seiyakusa Co.,

The abbreviations of the photopolymerization initiators and photoacid generators used in Examples and Comparative Examples of the present invention are as follows.

<Photopolymerization initiator>

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

P-2: 2,2-dimethoxy-1,2-diphenylethan-1-one (Irgacure 651, manufactured by Ciba Specialty Chemicals)

P-3: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure 1173: manufactured by Ciba Specialty Chemicals)

P-4: A mixture of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure 4265, manufactured by Ciba Specialty Chemicals)

P-5: A mixture of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2,2-dimethoxy-1,2-diphenylethane- Irgacure 1300: manufactured by Chiba Specialty Chemicals)

P-6: 1- [4-benzoylphenylsulfanyl] phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan- 1-one (ESACUR1001M,

P-7: 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane (Irgacure- 907: manufactured by Ciba Specialty Chemicals)

P-8: Hydroxycyclohexyl phenyl ketone (Irgacure-184 manufactured by Ciba Specialty Chemicals)

The abbreviations of the surfactants and additives used in Examples and Comparative Examples of the present invention are as follows.

<Surfactant>

W-1: Fluorine-based surfactant (fluorochemical surfactant manufactured by TOKEM Product Co., Ltd.)

W-2: Silicone surfactant (Megapac Painter 31, manufactured by Dainippon Ink and Chemicals, Inc.)

W-3: Fluorine-silicone surfactant (Megapac R-08, manufactured by Dainippon Ink and Chemicals, Inc.)

W-4: Fluorine-silicone surfactant (Megapak XRB-4, manufactured by Dainippon Ink and Chemicals, Inc.)

W-5: Acetylene glycol-based nonionic surfactant (Sabinol 465 produced by Shin-Etsu Chemical Co., Ltd.)

W-6: Polyoxyethylene polyoxypropylene condensate (Pionein P-1525 manufactured by TAKEMOTO YUSHI Co., Ltd.)

W-7: Fluorine-based surfactant (F-173, manufactured by Dainippon Ink and Chemicals, Inc.)

W-8: Fluorine-based surfactant (Sumitomo 3M FC-430)

W-9: Fluorine-based surfactant (Megapack F470, manufactured by Dainippon Ink and Chemicals, Inc.)

W-10: Fluorine-based surfactant (Megapack EXP.TF907, manufactured by Dainippon Ink & Chemicals, Inc.)

<Additives>

A-01: 2-chlorothioxanthone

A-02: 9,10-dibutoxycyanthracene (manufactured by Kawasaki Kasei Co., Ltd.)

A-03: Silane coupling agent (vinyltriethoxysilane) (manufactured by Shin-Etsu Silicone Co., Ltd.)

A-04: Silicone oil (L-7001, manufactured by Nippon Unicar Co., Ltd.)

A-05: 2-Dimethylaminoethylbenzoate

A-06: benzophenone

A-07: Ethyl 4-dimethylaminobenzoate

A-08: Modified dimethylpolysiloxane (BYK-307 manufactured by Big Chemie Japan)

A-09: Red No. 225 (Sudan III)

A-10: N-ethyldiethanolamine

A-11: Propylene carbonate (manufactured by Kanto Kagaku)

A-12: Dispersant (PB822 manufactured by Ajinomoto Fine Techno Co., Ltd.)

A-13: CI Pigment Black 7 (made by client Japan)

&Lt; Evaluation of curable composition for photo-nanoimprint lithography >

Each of the compositions obtained in Examples 1 to 25 and Comparative Examples 1 to 20 was measured and evaluated according to the following evaluation method.

Tables 1, 2 and 4 show the polymerizable unsaturated monomers (Examples and Comparative Examples) used in the composition, respectively.

Table 2 and Table 5 show the compounding ratios of the polymerizable unsaturated monomers used in the composition (Examples).

Tables 3 and 6 show the results of the present invention (Examples and Comparative Examples), respectively.

<Viscosity Measurement>

The viscosity was measured at 25 占 0.2 占 using RE-80L type rotary clay system manufactured by Toki Sangyo Co., Ltd.

The rotational speed at the time of measurement is not less than 0.5 mPa · s but less than 5 mPa · s at 100 rpm, at least 5 mPa · s at less than 10 mPa · s at 50 rpm, at less than 30 mPa · s at less than 30 mPa · s at 20 rpm, s or more, 10 rpm or less for 60 mPa s or less, 5 rpm for 60 mPa s or more and less than 120 mPa · s, and 1 rpm or 0.5 rpm for 120 mPa · s or more.

&Lt; Measurement of photocuring speed &

The measurement of photo-curability was performed by using a high-pressure mercury lamp as a light source and changing the absorption of the monomer at 810 cm ^-1 in real time using a Fourier transform infrared spectrometer (FT-IR) . A represents the case where the curing reaction rate is 0.2 / sec or more, and B represents the case where the curing reaction rate is less than 0.2 / sec.

&Lt; Adhesion >

When the adhesive tape was peeled off from the surface of the photocured resist pattern by photocuring, whether the photocured resist pattern adhered to the tape side was attached or not was visually observed and evaluated.

A: There is no pattern attachment on the tape side.

B: Appearance of the pattern is confirmed although it is very thin on the tape side

C: Apparent attachment of the pattern is confirmed on the tape side

<Peelability>

When the mold was peeled off after the photo-curing, whether or not unrecorded materials remained in the mold was observed with an optical microscope and evaluated as follows.

A: No residue

B: With residue

&Lt; Observation of residual film property and pattern shape >

The shape of the pattern after transfer and the residue of the transfer pattern were observed by a scanning electron microscope, and the residual film property and the pattern shape were evaluated as follows.

(Residual film)

A: Residues are not observed

B: Residues are slightly observed.

C: Many residues are observed

(Pattern shape)

A: Almost the same as the pattern of the original plate on which the pattern shape of the mold is based

B: There is a portion (a range of less than 20% of the pattern of the original plate) different from the pattern shape of the original plate which is the basis of the pattern shape of the mold

C: Obviously different from the pattern of the original plate which is the basis of the pattern shape of the mold, or the film thickness of the pattern is different by 20% or more from the pattern of the original plate

&Lt; Spin application suitability &

* Coating property (I)

The composition of the present invention was spin-coated on a 4-inch-thick 0.7 mm-thick glass substrate having an aluminum (Al) coating film having a thickness of 4000 angstroms so as to have a thickness of 5.0 탆, Observations were made and evaluated as follows.

A: Appearance and coating line (striation) are not observed.

B: The application line was slightly observed

C: Appearance or application line was strongly observed

&Lt; Slit application suitability &

* Coating property (II)

The composition of the present invention was applied to a 4-inch-thick 0.7 mm-thick glass (Al) film having a film thickness of 4000 angstroms formed using a slit coater resist coating apparatus (Head Coater System, manufactured by Hirata Kiko Co., Ltd.) Coated on a substrate (550 mm x 650 mm) to form a resist film having a film thickness of 3.0 mu m, and the presence or absence of deviation in the shape of a stripe formed laterally and longitudinally was observed and evaluated as follows.

A: No deviation of line shape was observed

B: Deviation of line shape was weakly observed

C: Deviation of line shape was strongly observed, or appearance was observed on the resist film

<Etching Properties>

The composition of the present invention was formed into a pattern on the aluminum (Al) formed on a glass substrate, and after curing, the aluminum thin film was etched with phosphoric acid etchant to observe a line / space of 10 mu m with eyes, And evaluated as follows.

A: A line of aluminum having a line width of 10 ± 2.0 μm was obtained

B: The line width of the line exceeded ± 2.0 μm.

C: There is a missing part of the line or there is a connection between the lines

<Overall evaluation>

The comprehensive evaluation was conducted based on the following criteria. It is very practical above the real B rank.

A: B rank is within 2 items.

B: B rank is 3 items.

C: When B rank is 4 or more, or C rank is 1 item.

D: When D rank is also one item.

- Example 1-

19.496 g of gamma-butyrolactone acrylate monomer (R-01), 68.24 g of tripropylene glycol diacrylate monomer (R-29), and ethylene oxide-modified trimethylolpropane triacrylate monomer (R-30) as polymerizable unsaturated monomers ), 2.50 g of 2,4,6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (Lucirin TPO-L manufactured by BASF) (P-1) as a photopolymerization initiator, EFTOP EF-122A , W-1) were weighed and mixed at room temperature for 24 hours to obtain a homogeneous solution. Table 1 shows the composition ratios of the polymerizable unsaturated monomers used, and Table 2 shows the composition ratios.

The thus adjusted composition was spin-coated on a glass substrate having a thickness of 4 inches and a thickness of 0.7 mm to form an aluminum (Al) coating having a thickness of 4000 angstroms so as to have a thickness of 5.0 占 퐉. The spin coat coated film was set in a nanoimprint apparatus using a high-pressure mercury lamp (lamp power: 2000 mW / cm2) manufactured by ORC as a light source, and a mold pressing force of 0.8 kN, a degree of vacuum during exposure of 10 Torr, And exposed at 100 mJ / cm 2 from the rear surface of a mold made of polydimethylsiloxane (SILPOT 184 made by Doray Dow Corning Co., Ltd., having a groove depth of 5.0 탆 and cured at 80 캜 for 60 minutes), and after the exposure, And a resist pattern was obtained. Subsequently, the aluminum (Al) portion not covered with the resist was removed by a phosphoric acid nitric acid etchant to form an electrode pattern made of aluminum (Al). The resist peeling was performed by immersing the substrate in a monoethanolamine / dimethyl sulfoxide mixed stripping solution at 80 캜 for 3 minutes. The results are shown in Table 2. From the results shown in Table 3, it was found that the composition of the present invention satisfied both photocurability, adhesion, releasability, retentivity, pattern shape, coatability (spin coatability, slit coatability) and etchability.

- Example 2-

38.97 g of? -Acryloxy-?,? - dimethyl-? -Butyrolactone monomer (R-2) as a polymerizable unsaturated monomer, 48.71 g of hydroxypivalic neopentyl glycol diacrylate monomer (S- 9.742 g of propylene oxide-modified trimethylolpropane triacrylate (S-6), 2,4,6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (Lucirin TPO-L, (W-3) as a surface active agent were mixed and kneaded at room temperature for 24 hours to obtain a homogeneous solution. The composition was exposed and patterned in the same manner as in Example 1 to investigate the characteristics of the composition. The results are shown in Table 3. From the results shown in Table 3, it was confirmed that the composition of the present invention can comprehensively satisfy the photocurability, adhesion, releasability, retentivity, pattern shape, applicability (spin coatability, slit coatability) and etchability.

- Examples 3 to 27-

In the same manner as in Example 1, the polymerizable unsaturated monomers shown in Table 1 were mixed in the ratios shown in Table 2 and the compositions shown in Table 2 were prepared. This adjusted composition was patterned in the same manner as in Example 1 to investigate the characteristics of the composition. The results are shown in Table 3. The compositions of Examples 3 to 27 were able to comprehensively satisfy the photocurability, adhesion, releasability, retentivity, pattern shape, coatability (spin coatability, slit coatability) and etchability.

- Comparative Example 1-

The composition described in Comparative Example 4 of an ultraviolet curing coating for an optical disk protective film disclosed in Japanese Patent Application Laid-Open No. 7-70472 was prepared in the same manner as in Example 1 of the present invention by using the polymerizable unsaturated monomers shown in Table 4 , And the compositions shown in Table 5 were prepared. This adjusted composition was patterned in the same manner as in Example 1 to investigate the characteristics of the composition. The results are shown in Table 6.

As shown in Table 5, the composition of Comparative Example 1 was not able to satisfy the releasability, coatability (spin coatability, slit coatability).

- Comparative Example 2-

The composition described in the examples of the optical disk overcoat composition disclosed in Japanese Patent Application Laid-Open No. 4-149280 was used in the same manner as in Example 1 of the present invention and the polymerizable unsaturated monomers shown in Table 4 were dispersed in the proportion shown in Table 5 The composition was adjusted by mixing. This adjusted composition was patterned by the same method as in Example 1 to investigate the characteristics of the composition. The results are shown in Table 6.

As shown in Table 6, the composition of Comparative Example 2 was not able to satisfy the adhesiveness, residual film property, coating property (spin coatability, slit coatability) and etching property.

- Comparative Example 3-

The composition described in Example 1 of the protective coat composition disclosed in Japanese Patent Application Laid-Open No. 7-62043 was used in the same manner as in Example 1 of the present invention and the polymerizable unsaturated monomers shown in Table 4 were dispersed in the proportion shown in Table 5 The composition was adjusted by mixing. This adjusted composition was patterned by the same method as in Example 1 to investigate the characteristics of the composition. The results are shown in Table 6.

As shown in Table 6, the composition of Comparative Example 3 was not able to satisfy the residual film property, the pattern shape, the coatability (slit coatability), and the etching property.

- Comparative Example 4-

The composition described in Comparative Example 2 of the protective coat composition disclosed in JP-A-2001-93192 was mixed with the polymerizable unsaturated monomer shown in Table 4 in the ratio shown in Table 5 by the same method as in Example 1 of the present invention To adjust the composition. This adjusted composition was patterned by the same method as in Example 1 to investigate the characteristics of the composition. The results are shown in Table 6.

As shown in Table 6, the composition of Comparative Example 4 could not satisfy the adhesion and the etching property.

- Comparative Example 5-

The composition described in Example 2 of the ultraviolet ray and electron beam curable composition disclosed in Japanese Patent Application Laid-Open No. 2001-270973 was used in the same manner as in Example 1 of the present invention and the polymerizable unsaturated monomer shown in Table 4 To prepare a composition. This adjusted composition was patterned by the same method as in Example 1 to investigate the characteristics of the composition. The results are shown in Table 6.

As shown in Table 6, the composition of Comparative Example 5 did not satisfy the photocurability, retentivity, pattern shape, coatability (spin coatability, slit coatability) and etchability.

- Comparative Example 6-

The composition described in Example 1 of the protective coat composition disclosed in JP-A-7-53895 was mixed with the polymerizable unsaturated monomers shown in Table 4 in the proportions shown in Table 5 in the same manner as in Example 1 of the present invention To adjust the composition. This adjusted composition was patterned by the same method as in Example 1 to investigate the characteristics of the composition. The results are shown in Table 6.

As shown in Table 6, the composition of Comparative Example 6 was not satisfactory in releasability, applicability (slit coatability), and etching property.

- Comparative Example 7-

The composition described in Example 1 of the painting composition disclosed in Japanese Patent Application Laid-Open No. 2003-165930 was mixed with the polymerizable unsaturated monomers shown in Table 4 in the proportions shown in Table 5 in the same manner as in Example 1 of the present invention The composition was adjusted. This adjusted composition was patterned by the same method as in Example 1 to investigate the characteristics of the composition. The results are shown in Table 6.

As shown in Table 6, the composition of Comparative Example 7 was not able to satisfy the adhesiveness, residual film property, pattern shape, coatability (spin coatability) and etching property.

- Comparative Example 8-

A composition containing NVP (N-vinylpyrrolidone) described in "Industrial Chemistry Society, 2005," First page of "Beginner's Book 38 First Nanoimprint Technology" was patterned in the same manner as in Example 1 to investigate the composition characteristics. The results are shown in Table 6.

As shown in Table 6, the composition of Comparative Example 8 did not satisfy the requirements of photo-curability, releasability, pattern shape, and etching property.

The composition of the present invention can be used in various applications such as semiconductor integrated circuits, flat screens, microelectromechanical systems (MEMS), sensor devices, optical disks, magnetic recording media such as high density memory disks, optical parts such as diffraction gratings and relief holograms, , An optical film or a polarizing element for producing a flat panel display, a thin film transistor of a liquid crystal display, an organic transistor, a color filter, an overcoat layer, a column material, a rib material for liquid crystal alignment, a micro lens array, Can be used as a photo-nanoimprint resist composition for forming a fine pattern at the time of manufacturing a reactor, a nanobio device, an optical waveguide, an optical filter, a photonic liquid crystal, and the like.

Particularly, in the present invention, in the light transmitting nano stamping method (also referred to as optical nanoimprint lithography), a step of forming a liquid curable composition for uncured light nanoimprint lithography on a substrate, a step of pressing a light- A step of curing the photocurable composition layer by irradiating light from the back surface of the mold or the back surface of the substrate to form a pattern to be fitted to a desired pattern, a step of releasing the light-transmitting mold from the coating film, And can be suitably used for forming fine patterns used in the method.

Further, the composition of the present invention makes it possible to manufacture a microstructure of an electronic part which is substantially more economical than the conventional photolithographic method.

Claims (15)

Wherein the polymerizable unsaturated monomer comprises 88 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 11% by mass of a photopolymerization initiator, and 0.001 to 5% by mass of a fluorinated surfactant, A monofunctional polymerizable unsaturated monomer containing a site having an ethylenic unsaturated bond in the molecule and a site having at least one heteroatom in a molecule is contained in an amount of from 10% by mass to 80% by mass of the polymerizable unsaturated monomer, And at least one of 1,9-nonanediol di (meth) acrylate and polyethylene glycol di (meth) acrylate. The curable composition for photo-nanoimprint lithography according to claim 1, wherein the monofunctional polymerizable unsaturated monomer contains at least one compound selected from the following (a), (b) and (c). (a) a polymerizable unsaturated monomer having an aliphatic cyclic moiety containing a hetero atom and a moiety having an ethylenic unsaturated bond in one molecule (b) a polymerizable unsaturated monomer having an ethylenic unsaturated bond in one molecule and a moiety having -C (= O) - bond and NR bond (R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) (c) a monofunctional polymerizable unsaturated monomer containing a moiety having an ethylenic unsaturated bond in the molecule and a moiety having at least one heteroatom, wherein the moiety has an ethylenically unsaturated bond in one molecule and a moiety having 6 to 12 carbon atoms The polymerizable unsaturated monomer having an aliphatic cyclic moiety The positive resist composition according to claim 1, wherein the monofunctional polymerizable unsaturated monomer (a) contains at least one polymerizable unsaturated monomer having a site having an ethylenic unsaturated bond in one molecule and an alicyclic site containing a heteroatom, And the heteroatom of the monofunctional polymerizable unsaturated monomer of (a) is in the form of any one of O, N, and S. The curable composition for light nanoimprint lithography according to claim 1, Wherein the polymerizable unsaturated monomer comprises 88 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 11% by mass of a photopolymerization initiator, and 0.001 to 5% by mass of a fluorinated surfactant, (1) to (VIII) as monomers in an amount of 10% by mass to 80% by mass of the polymerizable unsaturated monomer, and further contains 1,9-nonanediol monomer (Meth) acrylate, and polyethylene glycol di (meth) acrylate. The curable composition for light nanoimprint lithography according to claim 1, &Lt; General Formula (I) >

(In the general formula (I), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring); R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each represent a hydrogen atom, Or an alkoxy group having 1 to 6 carbon atoms, n1 is 1 or 2, m1 is 0, 1 or 2. Z ¹¹ is an alkylene group having 1 to 6 carbon atoms, . represents an oxygen atom or -NH-, 2 of Z ¹¹ are different and W ¹¹ is -C (= O) - or -SO ₂ -. R ¹³ represents an R ¹² and and R ¹⁴ and R ¹⁵ are each to each other It may be combined to form a ring.) &Lt; General Formula (II) >

(In the general formula (II), R ²¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring), and R ²² , R ²³ , R ²⁴ and R ²⁵ each represent a hydrogen atom, A halogen atom and an alkoxy group having 1 to 6 carbon atoms, R ²² and R ^23, and R ²⁴ and R ²⁵ may be bonded to each other to form a ring, n 2 is 1 or 2 , And m is any one of 0, 1, and 2. Y ²¹ represents an alkylene group having 1 to 6 carbon atoms or an oxygen atom. &Lt; General Formula (III) >

(In the general formula (III), R ³² , R ³³ , R ³⁴ and R ³⁵ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (may form a ring), a halogen atom or an alkoxy group having 1 to 6 carbon atoms. n3 is any one of 1, 2, 3, m3 represents 0, 1, any one of 2 X ³¹ is -C (= O) -., represents an alkylene group having 1 to 6 carbon atoms, 2 X ³¹ Y ³² represents an alkylene group having 1 to 6 carbon atoms or an oxygen atom. &Lt; General Formula (IV) >

(In the general formula (IV), R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring). R ⁴² and R ⁴³ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and being optionally), a halogen atom, an alkoxy group having a carbon number of 1 ~ 6 W ⁴¹ represents a single bond or -C (= O) -.. represents the n4 is 2, 3, 4 represents any one of X ⁴² is - C (= O) - or an alkylene group having 1 to 6 carbon atoms, and each X ⁴² may be the same or different, and M ⁴¹ represents a hydrocarbon group having 1 to 4 carbon atoms, an oxygen atom or a nitrogen atom, M ⁴¹ may be the same or different.) &Lt; General Formula (V) >

(In the general formula (V), R ⁵¹ represents a bond, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (which may form a ring), Z ⁵² represents an oxygen atom, -CH = N-, represents an alkylene group. W ⁵² is (as may form a ring), an alkyl group having 1 to 6 carbon atoms represents a alkylene group or an oxygen atom. R ⁵⁴ and R ⁵⁵ are each a hydrogen atom, a group having 1 to 6 carbon atoms, a halogen atom, And R ⁵⁴ and R ⁵⁵ may be bonded to each other to form a ring, and when X ⁵¹ represents a single bond or a non-bond and R ⁵¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms X ⁵¹ represents a single bond, R ⁵¹ if the non-bond X ⁵¹ represents a non-bonded. m5 is 0, 1, is any one of ^{2. W 52, Z 52,} R 54, R 55 1 out of more than Containing an oxygen atom or a nitrogen atom. &Lt; General Formula (VI) >

(Wherein R ⁶¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ⁶² and R ⁶³ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a (CH ₃ ) _{2 N- (CH 2) m6 -} (m6 is 1, 2 or _{3), CH 3 CO- (CR} 64 R 65) p6 - (R 64 and R ⁶⁵ each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (F represents a search may form), p6 is either of 1, 2 or _{3), (CH 3) 2} -N- (CH 2) p6 -. (p6 is either of 1, 2 or 3). = CO group, and R ⁶² and R ⁶³ are not simultaneously hydrogen atoms, and X ⁶ represents -CO-, -COCH ₂ -, -COCH ₂ CH ₂ -, -COCH ₂ CH ₂ CH ₂ -, -COOCH ₂ CH ₂ -). &Lt; General Formula (VII) >

(In the general formula (VII), R ⁷¹ and R ⁷² are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring), and R ⁷³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms ). &Lt; General Formula (VIII) >

(In the general formula (VIII), R ⁸¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (may form a ring), or a hydroxyalkyl group having 1 to 6 carbon atoms. R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ are each a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms (may form a ring) or a hydroxyalkyl group having 1 to 6 carbon atoms, W ⁸¹ is an alkylene group having 1 to 6 carbon atoms, -NH- group, -N-CH ₂ - group or -NC ₂ H ₄ - group W ⁸² is a single bond or -C (= O) - When W ⁸² is a single bond, R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ are not all hydrogen atoms, and n 7 represents an integer of 0 to 8. Wherein the polymerizable unsaturated monomer comprises 88 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 11% by mass of a photopolymerization initiator, and 0.001 to 5% by mass of a fluorinated surfactant, A curable composition for a photo-nanoimprint lithography characterized by containing a monofunctional polymerizable unsaturated monomer represented by the following general formula (I) as a monomer. &Lt; General Formula (I) >

(In the general formula (I), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring); R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each represent a hydrogen atom, Or an alkoxy group having 1 to 6 carbon atoms, n1 is 1 or 2, m1 is 0 or 1. Z ¹¹ is an alkylene group having 1 to 6 carbon atoms, an oxygen atom or -NH - denotes a group, the two Z ¹¹ are different from each other, at least one of Z ¹¹ is oxygen atom W ¹¹ is -C (= O) -.. a is R ¹² and R ¹³ and R ¹⁴ and R ¹⁵ respectively each other It may be combined to form a ring.) Wherein the polymerizable unsaturated monomer comprises 88 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 11% by mass of a photopolymerization initiator, and 0.001 to 5% by mass of a fluorinated surfactant, A curable composition for a photo-nanoimprint lithography characterized by containing a monofunctional polymerizable unsaturated monomer represented by the following formula (II) as a monomer. &Lt; General Formula (II) >

(In the general formula (II), R ²¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring), and R ²² , R ²³ , R ²⁴ and R ²⁵ each represent a hydrogen atom, A halogen atom and an alkoxy group having 1 to 6 carbon atoms, R ²² and R ^23, and R ²⁴ and R ²⁵ may be bonded to each other to form a ring, n 2 is 1 or 2 , And m is 0 or 1. Y ²¹ represents an alkylene group having 1 to 6 carbon atoms or an oxygen atom. Wherein the polymerizable unsaturated monomer comprises 88 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 11% by mass of a photopolymerization initiator, and 0.001 to 5% by mass of a fluorinated surfactant, A curable composition for light-nanoimprint lithography characterized by containing a monofunctional polymerizable unsaturated monomer represented by the following formula (III) as a monomer. &Lt; General Formula (III) >

(In the general formula (III), R ³² , R ³³ , R ³⁴ and R ³⁵ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (may form a ring), a halogen atom or an alkoxy group having 1 to 6 carbon atoms. n3 is any one of 1, 2, 3, m3 represents 0, 1, any one of 2 X ³¹ is -C (= O) -., represents an alkylene group having 1 to 6 carbon atoms, 2 X ³¹ Y ³² represents an alkylene group having 1 to 6 carbon atoms or an oxygen atom. Wherein the polymerizable unsaturated monomer comprises 88 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 11% by mass of a photopolymerization initiator, and 0.001 to 5% by mass of a fluorinated surfactant, Wherein the monofunctional polymerizable unsaturated monomer represented by the following general formula (IV) is contained in an amount of 10% by mass to 80% by mass of the polymerizable unsaturated monomer as the monomer, and further contains 1,9-nonanediol di (meth) acrylate and polyethylene glycol (Meth) acrylate, and di (meth) acrylate. The curable composition for optical nanoimprint lithography according to claim 1, &Lt; General Formula (IV) >

(In the general formula (IV), R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring), R ⁴² and R ⁴³ each represent a hydrogen atom, W ⁴¹ represents a single bond or -C (= O) -, n4 represents any one of 2, 3 and 4. X ⁴² represents -C (= O) - or an alkylene group having 1 to 6 carbon atoms, and each X ⁴² is the same or different M ⁴¹ represents a hydrocarbon group having 1 to 4 carbon atoms, an oxygen atom or a nitrogen atom, and each M ⁴¹ may be the same or different.) Wherein the polymerizable unsaturated monomer comprises 88 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 11% by mass of a photopolymerization initiator, and 0.001 to 5% by mass of a fluorinated surfactant, A curable composition for a photo-nanoimprint lithography characterized by containing a monofunctional polymerizable unsaturated monomer represented by the following general formula (V) as a monomer. &Lt; General Formula (V) >

(In the general formula (V), R ⁵¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring). Z ⁵² represents an oxygen atom, -CH = N- or an alkylene group having 1 to 6 carbon atoms , W ⁵² represents an alkylene group having 1 to 6 carbon atoms or an oxygen atom, R ⁵⁴ and R ⁵⁵ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (may form a ring), a halogen atom, of an alkoxy group, it may be R ⁵⁴ and R ⁵⁵ may be bonded to each other to form a ring. X ⁵¹ represents a single bond. m5 is 0, 1, is any one of ^{2. W 52, Z 52,} R 54, R 55 And at least one of them contains an oxygen atom or a nitrogen atom. Wherein the polymerizable unsaturated monomer comprises from 88 to 99% by mass of a polymerizable unsaturated monomer, from 0.1 to 11% by mass of a photopolymerization initiator, and from 0.001 to 5% by mass of at least one of a fluorinated surfactant, a silicone surfactant and a fluorinated silicone surfactant, Wherein the monofunctional polymerizable unsaturated monomer represented by the following general formula (VI) is contained in the polymerizable unsaturated monomer in an amount of 10% by mass to 80% by mass as a monomer, and further contains 1,9-nonanediol di (meth) acrylate and polyethylene glycol (Meth) acrylate, and di (meth) acrylate. The curable composition for optical nanoimprint lithography according to claim 1, &Lt; General Formula (VI) >

(Wherein R ⁶¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ⁶² and R ⁶³ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a (CH ₃ ) _{2 N- (CH 2) m6 -} (m6 is 1, 2 or _{3), CH 3 CO- (CR} 64 R 65) p6 - (R 64 and R ⁶⁵ each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (F represents a search may form), p6 is either of 1, 2 or _{3), (CH 3) 2} -N- (CH 2) p6 -. (p6 is either of 1, 2 or 3). = CO group, and R ⁶² and R ⁶³ are not simultaneously hydrogen atoms, and X ⁶ represents -CO-, -COCH ₂ -, -COCH ₂ CH ₂ -, -COCH ₂ CH ₂ CH ₂ -, -COOCH ₂ CH ₂ -). Wherein the polymerizable unsaturated monomer comprises 88 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 11% by mass of a photopolymerization initiator, and 0.001 to 5% by mass of a fluorinated surfactant, A curable composition for optical nanoimprint lithography characterized by containing a monofunctional polymerizable unsaturated monomer represented by the following formula (VII) as a monomer. &Lt; General Formula (VII) >

(In the general formula (VII), R ⁷¹ and R ⁷² are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (may form a ring), and R ⁷³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms ). Wherein the polymerizable unsaturated monomer comprises 88 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 11% by mass of a photopolymerization initiator, and 0.001 to 5% by mass of a fluorinated surfactant, A curable composition for a photo-nanoimprint lithography characterized by containing a monofunctional polymerizable unsaturated monomer represented by the following formula (VIII) as a monomer. &Lt; General Formula (VIII) >

(In the general formula (VIII), R ⁸¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (may form a ring) or a hydroxyalkyl group having 1 to 6 carbon atoms, R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ (which may form a ring) alkyl group each represent a hydrogen atom, a hydroxyl group, having 1 to 6 carbon atoms, represents a hydroxyalkyl group having 1 to 6 carbon atoms, R ^82, R ^83, R ⁸⁴ and R of two or more of ⁸⁵ the W ⁸¹ is an alkylene group having 1 to 6 carbon atoms, -NH- group, -N-CH ₂ - group or -NC ₂ H ₄ - group, W ⁸² is a single bond or -C (= O) - When W ⁸² is a single bond, R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ are not all hydrogen atoms, and n 7 represents an integer of 0 to 8. The positive resist composition according to claim 1, which further comprises a second polymerizable unsaturated monomer containing at least one ethylenic unsaturated bond and a silicon atom and / or phosphorus atom, And 0.1% by mass to 10% by mass with respect to the compound. The positive resist composition according to claim 3, further comprising a second polymerizable unsaturated monomer containing at least one ethylenic unsaturated bond and a silicon atom and / or phosphorus atom, wherein the second polymerizable unsaturated monomer is a polymerizable And 0.1% by mass to 10% by mass with respect to the compound. 14. A method for manufacturing a photo-nanoimprint lithography system, comprising the steps of: applying the curable composition for optical nanoimprint lithography according to any one of claims 1 to 14; Pressing a light-transmissive mold onto a resist layer on the substrate to modify the curable composition for light-nanoimprint lithography; A step of irradiating light from the back side of the mold or the back side of the substrate to form a resist pattern for curing the coating film to fit the desired pattern; and a step of detaching the light-transmitting mold from the coating film.