JP2009206196A - Curable composition for nanoimprint, cured body using the same and manufacturing method thereof, and member for liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition for nanoimprint which has superior pattern transfer precision, strength of a cured film, and peelability from a mold, a cured body using the same and a manufacturing method thereof, and a member for a liquid crystal display. <P>SOLUTION: The curable composition for nanoimprint contains aromatic alkenyl ester carboxylate expressed by general formula (1), the viscosity of the composition being 3 to 18 mPa s. In formula (1), R<SP>1</SP>represents an alkenyl group with 2-6C, R<SP>2</SP>represents an alkenyl group with 2-6C or an alkenyloxy group with 2-6C, and Ar represents aromatic hydrocarbon. Here, (n) is an integer not less than 1, (m) is an integer not less than 0, and n+m is an integer not less than 2. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a curable composition for nanoimprint, a cured product using the same, a method for producing the same, and a member for a liquid crystal display device using the cured product. More specifically, a curable composition for nanoimprint, which is suitable for producing a so-called permanent film such as a thin film transistor for a liquid crystal display, a protective film for a liquid crystal color filter, a spacer, and other fine processing applications for liquid crystal display device members. The present invention relates to a cured product using, a manufacturing method thereof, and a liquid crystal display device member using the cured product.

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

  There are two types of nanoimprint methods: a thermal nanoimprint method using a thermoplastic resin as a material to be processed (for example, see Non-Patent Document 1) and an optical nanoimprint using a photocurable composition (for example, see Non-Patent Document 2). The technology has been proposed. In the case of the thermal nanoimprint method, the mold is pressed on a polymer resin heated to a temperature higher than the glass transition temperature, and the mold is released after cooling to transfer the fine structure to the resin on the substrate. Since this method can be applied to various resin materials and glass materials, it is expected to be applied to various fields. For example, Patent Documents 1 and 2 below disclose thermal nanoimprinting methods that form a nanopattern at low cost using a thermoplastic resin.

  On the other hand, in the optical nanoimprint method that irradiates light through a transparent mold or a transparent substrate and photocures the photocurable composition, it is not necessary to heat the material for transferring the pattern when the mold is pressed, and imprinting at room temperature is possible. It becomes possible. Recently, new developments such as a nanocasting method combining the advantages of both and a reversal imprint method for producing a three-dimensional laminated structure have been reported.

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

  As an application example of the nanoimprint method, first, an application example for manufacturing a high-density semiconductor integrated circuit will be described. 2. Description of the Related Art In recent years, semiconductor integrated circuits have been miniaturized and integrated, and photolithography apparatuses have been improved in accuracy as a pattern transfer technique for realizing the fine processing. However, according to the demand for further miniaturization, the processing method approaches the wavelength of the light source for light exposure, and the conventional lithography technique is approaching the limit. Therefore, an electron beam drawing apparatus, which is a kind of charged particle beam apparatus, is used in place of lithography technology in order to further refine the pattern and increase the accuracy. Pattern formation using an electron beam by an electron beam drawing apparatus or the like uses a method of drawing a mask pattern unlike a batch exposure method in pattern formation using a light source such as i-line or excimer laser. For this reason, the more patterns to be drawn, the longer the exposure (drawing) time, and the longer time it takes to form the pattern. For this reason, as the degree of integration of the semiconductor integrated circuit is dramatically increased to 256 mega, 1 giga, and 4 giga, the pattern formation time is correspondingly increased, and there is a concern that the throughput is remarkably deteriorated. Therefore, in order to increase the speed of pattern formation by an electron beam lithography system, development of a collective figure irradiation method that combines various shapes of masks and collectively irradiates them with electron beams to form complex shapes of electron beams is progressing. It has been. However, while miniaturization of the pattern is promoted, the electron beam drawing apparatus needs to be enlarged, and a mechanism for controlling the mask position with higher accuracy is required. It was happening.

On the other hand, using a nanoimprint lithography technique (optical nanoimprint method) as a technique for forming a fine pattern at a low cost has been studied. For example, Patent Document 1 and Patent Document 3 below disclose a nanoimprint technique in which a silicon wafer is used as a stamper and a fine structure of 25 nanometers or less is formed by pattern transfer. Patent Document 4 below discloses a composite composition using nanoimprints that is applied to the field of semiconductor microlithography.
Along with this trend, nanoimprint lithography has been applied to the fabrication of semiconductor integrated circuits such as fine mold fabrication technology, mold durability, mold fabrication cost, mold-resin detachability, imprint uniformity, alignment accuracy, and inspection technology. Considerations for application are starting to increase.

Next, an application example of the optical nanoimprint method to a flat display such as a liquid crystal display (LCD) or a plasma display (PDP) will be described.
With the trend toward larger and higher-definition LCD and PDP substrates, optical nanoimprint lithography has recently attracted attention as an inexpensive alternative to conventional photolithography methods used in the manufacture of thin film transistors (TFTs) and electrode plates. Therefore, it has become necessary to develop a photo-curable resist that replaces the etching photoresist used in the conventional photolithography method.

  In addition, application of optical nanoimprint lithography has been started for transparent protective film materials used as structural members such as LCDs and spacers that define cell gaps in liquid crystal displays (see, for example, Patent Documents 5 and 6). . Unlike the above-described etching resist, such a resist for a structural member is finally left in a display such as a flat display panel, and is therefore sometimes referred to as “permanent resist” or “permanent film”.

  As a permanent film to which a conventional photolithography technique is applied, for example, a protective film provided on a TFT substrate of a liquid crystal panel, or a high temperature process during sputtering of an ITO film by reducing a step between R, G and B layers. For example, a protective film provided on the color filter in order to impart resistance. Conventionally, photo-curing resins and thermosetting resins such as siloxane polymers, silicone polyimides, epoxy resins, and acrylic resins have been used for transparent permanent films for color filters (see Patent Documents 7 and 8 below). In the formation of these protective films (permanent films), the uniformity of the coating film, adhesion to the substrate, high light transmittance after heat treatment exceeding 200 ° C., planarization characteristics, solvent resistance, scratch resistance Various characteristics such as these are required.

  Also, in the field of spacers used in liquid crystal displays, photocurable compositions comprising a resin, a photopolymerizable monomer and an initiator have generally been widely used in conventional photolithography methods (for example, patents). Reference 9). The spacer generally forms a pattern having a size of about 10 μm to 20 μm by photolithography using a photocurable composition on the color filter substrate after forming the color filter or after forming the color filter protective film. Further, it is formed by heat curing by post-baking. The spacer used in such a liquid crystal display is required to have high mechanical properties against external pressure, such as hardness, developability, pattern accuracy, and adhesion.

  For this reason, development of the photocurable composition suitable for formation of permanent films (permanent resist), such as the said transparent protective film and spacer using a nanoimprint method, is calculated | required.

  As for the coating uniformity of the photocurable composition, the coating film thickness uniformity at the center and periphery of the substrate, dimensional uniformity due to higher resolution, film thickness, shape, etc., as the substrate becomes larger The demands are getting severe in various parts.

  Conventionally, in the field of manufacturing liquid crystal display devices using a small glass substrate, a method of spinning after dropping in the center has been used as a resist coating method (see, for example, Non-Patent Document 3). However, in the method of spinning after the central dropping, it is difficult to meet demands other than coating uniformity. For this reason, as an alternative technique, a new resist coating method using a discharge nozzle type that can be applied to a large substrate after the fourth generation substrate, particularly after the fifth generation substrate has been proposed. The resist application method by the discharge nozzle method is a method of applying a photoresist composition to the entire coating surface of the substrate by relatively moving the discharge nozzle and the substrate. For example, a plurality of nozzle holes are arranged in a line. A method of using a discharge nozzle that can discharge the photoresist composition in a strip shape, or after applying the photoresist composition to the entire coated surface of the substrate and then spinning the substrate. A method of adjusting the film thickness has been proposed. Therefore, in order to apply to these liquid crystal display element manufacturing fields, the coating uniformity on the substrate is required for the curable composition for nanoimprint.

  Further, as a technique for improving the coating property of a protective film such as a positive photoresist, a pigment-dispersed photoresist for producing a color filter or a magneto-optical disk, a technique of adding various surfactants or the like is known (for example, Patent Documents 10 to 17), and an example of using a photocurable resin containing a fluorosurfactant as an optical nanoimprint etching resist for manufacturing a semiconductor integrated circuit is disclosed (for example, refer to Patent Document 18). However, a method for improving the substrate coating property of a curable composition for nanoimprinting that does not contain pigments, dyes, and organic solvents used for the permanent film has not been known so far.

  Furthermore, in the optical nanoimprint method, it is necessary to improve the fluidity of the photocurable composition in the cavity of the concave portion of the mold surface where the pattern is formed. In addition, it is necessary to improve the adhesion between the resist and the base material (substrate, support) while improving the peelability between the mold and the resist. However, it has been difficult to simultaneously satisfy all of the fluidity in the cavity, the releasability from the mold, and the adhesion to the base material of the curable composition for optical nanoimprint.

  Photocurable resins applied to nanoimprints are roughly classified into radical polymerization types and ion polymerization types based on the difference in reaction mechanism, and these hybrid types are added. Any type of curable composition can be used for nanoimprint applications, but since a wide range of materials can be selected, a radical polymerization type curable composition is generally used (for example, non-patent literature). 4). As the radical polymerization type curable composition, a composition containing a monomer (monomer) or oligomer having a vinyl group or (meth) acryl group capable of radical polymerization and a photopolymerization initiator is generally used. It is done. When the radically polymerizable curable composition is irradiated with light, the radical generated by the photopolymerization initiator attacks the vinyl group and chain polymerization proceeds to form a polymer. Moreover, when a bifunctional or higher polyfunctional group monomer or oligomer is used, a crosslinked structure can be obtained. Non-Patent Document 5 below discloses a composition that can be imprinted at low pressure and room temperature by using a low-viscosity and UV-curable monomer.

Although the required characteristics of materials used for optical nanoimprint lithography are often different depending on the application to which they are applied, the demands on process characteristics are common regardless of the application. For example, the main requirement items shown in Non-Patent Document 6 below are applicability, substrate adhesion, low viscosity (<5 mPa · s), peelability, low cure shrinkage, fast curability, and the like. In particular, there is a strong demand for a low-viscosity material in applications that require imprinting at a low pressure or a reduction in the remaining film ratio. On the other hand, when a required characteristic is mentioned according to a use, about the optical member, the refractive index of light, light transmittance, etc. are mentioned, for example. As for the etching resist, etching resistance, reduction of remaining film thickness and the like can be mentioned. The key to material design is how to control these required characteristics and balance them. For this reason, at least the process material and the permanent film have greatly different required characteristics, so the material must be developed according to the process and application. Non-Patent Document 6 below discloses a photocurable material having a viscosity of about 60 mPa · s (25 ° C.) as a material applied to such optical nanoimprint lithography. Similarly, Non-Patent Document 7 below discloses a fluorine-containing photosensitive resin having a viscosity of 14.4 mPa · s whose main component is monomethacrylate and improved peelability.
However, with respect to the composition used in optical nanoimprinting, there has been no report on a design guideline for a material to be adapted to each application although there is a description of a demand for viscosity.

  Patent Documents 19 and 20 below disclose examples in which a photocurable resin containing a polymer having an isocyanate group is used for embossing to produce a relief hologram or a diffraction grating. Patent Document 21 below discloses a curable composition for optical nanoimprinting for imprinting that contains a polymer, a photopolymerization initiator, and a viscosity modifier.

Further, the following Non-Patent Document 8 includes (1) a functional acrylic monomer, (2) a functional acrylic monomer, and (3) a photocurable radical polymerizable composition in which a functional acrylic monomer and a photopolymerization initiator are combined. In addition, there is disclosed an example in which a photocationically polymerizable composition containing a photocurable epoxy compound and a photoacid generator is applied to nanoimprint lithography to examine thermal stability and mold releasability.
Non-Patent Document 9 below discloses a technique for improving problems such as peelability between a photocurable resin and a mold, film shrinkage after curing, and reduction in sensitivity due to photopolymerization inhibition in the presence of oxygen (1). There is disclosed a curable composition for optical nanoimprint, which comprises a) a functional acrylic monomer, (2) a functional acrylic monomer, a silicone-containing monofunctional acrylic monomer, and a photopolymerization initiator.

Non-Patent Document 10 below uses a surface-treated mold by applying a curable composition for optical nanoimprinting containing a monofunctional acrylic monomer, a silicone-containing monofunctional monomer, and a photopolymerization initiator on a silicone substrate. Thus, it is disclosed that pattern defects after molding are reduced. Further, in the following Non-Patent Document 11, a curable composition for optical nanoimprint including a silicone monomer, a trifunctional acrylic monomer, and a photopolymerization initiator is applied on a silicone substrate, and high resolution is achieved by using an SiO ₂ mold. A composition having excellent coating uniformity is disclosed. Furthermore, Non-Patent Document 12 discloses an example in which a 50 nm pattern size is formed by a cationic polymerizable composition in which a specific vinyl ether compound and a photoacid generator are combined. This composition is characterized by low viscosity and high curing speed, but it is stated that template peelability is an issue.

  However, as shown in Non-Patent Documents 8 to 12, although various photocurable resins in which an acrylic monomer, an acrylic polymer, and a vinyl ether compound having different functional groups are applied to optical nanoimprint lithography are disclosed, a curable composition is disclosed. Guidelines regarding material design such as preferred types, optimum monomer types, monomer combinations, optimum monomer or resist viscosity, preferred resist solution properties, and improved resist coatability are not fully disclosed. For this reason, a combination of preferable materials for widely applying the curable composition to optical nanoimprint lithography applications is not known, and curable compositions for optical nanoimprint capable of exhibiting satisfactory performance in various applications have been heretofore The actual situation was not proposed.

  In addition, some of the compositions disclosed in Non-Patent Documents 11 and 12 have low viscosity, but when both are photocured to form a pattern and subsequently subjected to heat treatment, the transmittance of the finished cured film is obtained. Is low (colored), and the hardness is insufficient, so that practical performance as a permanent film is not sufficient.

  Non-Patent Documents 13 and 14 below propose inorganic / organic hybrid materials composed of a mixture of silica sol treated with a photofunctional cross-linking material, (meth) acrylic monomer, and photopolymerization initiator. Application has been reported. Further, Non-Patent Documents 13 and 14 report that a 200 nm line pattern formation example of an imprint material and a patterning up to a line width of 600 nm as a molding material are reported. However, this material also has problems such as insufficient releasability from the mold and insufficient hardness of the cured film, and is not always satisfactory. In the compositions of Non-Patent Documents 13 and 14, low-viscosity materials are also disclosed, but both have low transmittance of the cured film after photocuring to form a pattern and subsequent heat treatment. (In other words, the cured film is colored) and the hardness is insufficient.

  In addition, Patent Document 22 discloses a pattern forming method using a fluorine-containing curable material in order to improve the releasability from the mold, as well as colloidal silica subjected to surface treatment, and a specific ( A composition for a hard coat containing a (meth) acrylic monomer, a leveling agent, and a photopolymerization initiator is disclosed, and its application to an optical disk having both film hardness and low curing shrinkage has been reported. However, these compositions have insufficient mold releasability and substrate coatability, and are difficult to apply to optical nanoimprint lithography. Further, when heat treatment is performed after photocuring, the pattern is colored, and it is difficult to apply as a permanent film requiring low transmittance and light transmittance.

  The following Patent Document 23 discloses a photocurable composition for nano-imprint using a (meth) acrylate monomer containing a cyclic structure in order to impart dry etching properties. However, in these compositions, even when heat treatment is performed after photocuring, transmittance due to coloring is seen, and it is difficult to use as a permanent film that requires light transmittance, the hardness of the cured film, solvent resistance The sex is also insufficient.

  Patent Document 24 below discloses a curable resin composition using a monofunctional aromatic alkenyl ester. Further, in Patent Document 25 below, a composition for nanoimprinting containing a polymeric silicon compound is reported, and diallyl phthalate is exemplified as one of the coexisting monomers.

  As described above, the main technical problems as a permanent film include pattern accuracy, adhesion, transparency after heat treatment exceeding 200 ° C., high mechanical properties (strength against external pressure), scratch resistance, and flattening properties. There are many problems such as solvent resistance and reduction of outgas during heat treatment. Even when the curable composition for optical nanoimprint is applied as a permanent film, (1) uniformity of the coating film, (2) transparency after heat treatment, as in the case of a resist using a conventional acrylic resin, ( 3) It is important to provide scratch resistance.

  At the same time, in addition to the above points (1) to (3), (4) ensuring the fluidity of the resist to the recesses of the mold, no solvent or a small amount It is necessary to consider that it is necessary to reduce the viscosity under the use of a solvent, and (5) that it is easily peeled off from the mold after photocuring and does not adhere to the mold. Technical difficulty is further increased.

In addition, compositions that have been known for use in inkjet compositions and protective films for magneto-optical disks, and curable compositions for optical nanoimprints that are used as etching resists are optical nanoimprints that are used in the production of permanent films. Although there is a common part between the curable composition for use and the material, the required characteristics are greatly different from the viewpoint of high-temperature heat treatment and mechanical strength. For this reason, if a photo-curable resin applied for inkjet, magneto-optical disk protective film or etching resist application is applied as it is as a permanent film resist, it is quite practical in terms of transparency, mechanical strength, solvent resistance, etc. No one can withstand. As described above, although various materials are disclosed for the curable composition for optical nanoimprint, there is no sufficient design guideline for the curable composition suitable for producing a permanent film. It is.
US Pat. No. 5,772,905 US Pat. No. 5,956,216 US Pat. No. 5,259,926 JP 2005-527110 Gazette JP 2005-197699 A Japanese Patent Laying-Open No. 2005-301289 JP 2000-39713 A JP-A-6-43643 Japanese Patent Laid-Open No. 2004-240241 Japanese Patent Laid-Open No. 7-230165 JP 2000-181055 A JP 2004-94241 A JP-A-4-149280 JP-A-7-62043 JP 2001-93192 A JP 2005-8759 A JP 2003-165930 A JP 2007-84625 A JP 2004-59820 A JP 2004-59822 A JP 2006-114882 A JP 2000-143924 A JP 2007-186570 A JP-A-10-251473 JP 2007-72374 A S.Chou et al.:Appl.Phys.Lett.Vol.67,3114 (1995) M.Colbun et al,: Proc.SPIE, Vol. 3676,379 (1999) Electronic Journal 121-123 No.8 (2002) F.Xu et al.:SPIE Microlithography Conference, 5374,232 (2004) DJResnick et al .: J.Vac.Sci.Technol.B, Vol.21, No.6,2624 (2003) Latest resist material handbook, P1, 103-104 (2005, published by the Information Organization) CM Publishing: Nanoimprint Development and Applications P159-160 (2006) N.Sakai et al.:J.Photopolymer Sci.Technol.Vol.18, No.4,531 (2005) M. Stewart et al .: MRS Buletin, Vol. 30, No. 12, 947 (2005) T.Beiley et al .: J.Vac.Sci.Technol.B18 (6), 3572 (2000) B. Vratzov et al .: J. Vac. Sci. Technol. B21 (6), 2760 (2003) EKKim et al .: J. Vac. Sci. Technol, B22 (1), 131 (2004) Proc.SPIE Int.Soc.Opt.Eng., Vol.6151, No.Pt2,61512F （2006） Science and Industry, Vol.80, No.7,322 (2006)

  The hardness and mechanical strength of the pattern (cured film) formed from the curable composition for nanoimprinting can be improved by using a polyfunctional monomer that gives a high crosslinking density. However, polyfunctional monomers are high-viscosity compounds, and it is difficult to obtain satisfactory cured film properties under low-viscosity constraints. Furthermore, since the polymerization of the polyfunctional monomer proceeds at a time when irradiated with light, the residue when the resin mold is used is also a problem.

Therefore, as a result of intensive studies, the present inventor has paid attention to the fact that aromatic alkenyl esters and allyl groups have low polymerizability during light irradiation, but can react by baking (heating) to form a crosslinking point. . That is, it can be estimated that the aromatic alkenyl ester and the allyl group can reduce the residue when the resin mold is used because the crosslinking (polymerization) reaction can be controlled.
In addition, the alkenyl ester group and the allyl group can lower the viscosity of the compound than the (meth) acrylate group. For this reason, it has been difficult to design a low viscosity / multifunctional product with (meth) acrylate, but a low viscosity / multifunctionalization can be achieved by using an alkenyl ester group or an allyl group. Furthermore, the low viscosity of alkenyl ester groups and allyl groups contributes to the improvement of the strength of the cured film, but the merit of being able to use aromatic rings (benzene rings, naphthalene rings) that cause an increase in viscosity as the mother nucleus Have

  However, as described above, in the following Patent Document 24, a curable resin composition using an aromatic alkenyl ester is reported. However, this composition uses a monofunctional alkenyl ester and improves the hardness of the cured film. I can't let you. In addition, nothing is disclosed regarding measures for improving the hardness of the cured film.

  Further, as described above, in Patent Document 25, diallyl phthalate is described as one of the monomers coexisting in the composition in the text. However, in this patent document, there is no description regarding the viscosity restriction of the composition when the mold pattern is transferred to the composition, and it is difficult to transfer the pattern when the mold pressing pressure is several atmospheres or less when referring to the examples. It is. Further, when diallyl phthalate is used as a reactive diluent, it is difficult to increase the polymerization degree of the polymerizable compound only by light irradiation, and the strength of the pattern (cured film) cannot be improved. In addition, Patent Document 25 does not disclose any measures for improving the hardness of the cured film by baking (heating) or the like.

  As described above, as a result of intensive studies by the present inventors, the use of an aromatic carboxylic acid alkenyl ester as a polymerizable compound can solve the above-mentioned problems such as pattern transfer accuracy, strength of a cured film, and transparency after heat curing. The knowledge that the adhesion (residue) of the curable composition to the mold when using a resin mold can be improved was obtained.

  In order to solve the above problems, the present invention provides a curable composition for nanoimprints excellent in pattern transfer accuracy, cured film strength, and mold releasability, a cured product using the same, and a method for producing the same, and Another object is to provide a member for a liquid crystal display device.

[1] A curable composition for nanoimprints, comprising an aromatic carboxylic acid alkenyl ester represented by the following general formula (1), wherein the composition has a viscosity of 3 to 18 mPa · s.

（式中、Ｒ¹は炭素数２〜６のアルケニル基を表し、Ｒ²は炭素数２〜６のアルケニル基もしくは炭素数２〜６のアルケニルオキシ基を表し、Ａｒは芳香族炭化水素を表す。ｎは１以上の整数を表し、ｍは０以上の整数を表す。ｎ＋ｍは２以上の整数である。）

(In the formula, R ¹ represents an alkenyl group having 2 to 6 carbon atoms, R ² represents an alkenyl group having 2 to 6 carbon atoms or an alkenyloxy group having 2 to 6 carbon atoms, and Ar represents an aromatic hydrocarbon. N represents an integer of 1 or more, m represents an integer of 0 or more, and n + m is an integer of 2 or more.)

[2] The curable composition for nanoimprints according to [1], wherein the aromatic carboxylic acid alkenyl ester is represented by the following general formula (2) or the following general formula (3).

（各式中、Ｒ²は炭素数２〜６のアルケニル基もしくは炭素数２〜６のアルケニルオキシ基を表す。ｎは１以上の整数を表し、ｍは０以上の整数を表す。ｎ＋ｍは２以上の整数である。）

(In each formula, R ² represents an alkenyl group having 2 to 6 carbon atoms or an alkenyloxy group having 2 to 6 carbon atoms. N represents an integer of 1 or more, m represents an integer of 0 or more, and n + m is 2. (It is an integer above.)

[3] The curable composition for nanoimprints according to [1] or [2], further comprising another polymerizable monomer different from the aromatic carboxylic acid alkenyl ester.

[4] The curable composition for nanoimprints according to [3], wherein the other polymerizable monomer is a (meth) acrylate monomer.

[5] The curable composition for nanoimprints according to any one of [1] to [4], further comprising a photopolymerization initiator.

[6] The curable composition for nanoimprints according to any one of [1] to [5], further comprising a surfactant.

[7] The curable composition for nano-imprints according to any one of [1] to [6], further comprising an antioxidant.

[8] The curable composition for nanoimprints according to any one of [1] to [7], which is substantially a solvent-free composition.

[9] The curable composition for nanoimprints according to any one of [1] to [8], wherein the content of the organic solvent is 3% by mass or less in the entire composition.

[10] A cured product obtained by curing the curable composition for nanoimprints according to any one of [1] to [9].

[11] A liquid crystal display member comprising the cured product according to [10].

[12] A step of applying the curable composition for nanoimprints according to any one of [1] to [9] onto a substrate to form a pattern forming layer;
Pressing the mold against the surface of the pattern forming layer;
Irradiating the pattern forming layer with light;
The manufacturing method of the hardened | cured material characterized by including.

[13] The method for producing a cured product according to [12], further comprising a step of heating the pattern forming layer irradiated with light.

  ADVANTAGE OF THE INVENTION According to this invention, the curable composition for nanoimprints excellent in pattern transfer precision, the strength of a cured film, and peelability from a mold, a cured product using the same, a method for producing the same, and a member for a liquid crystal display device Can be provided.

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

Further, in the present specification, “meth (acrylate)” represents “acrylate” and “methacrylate”, “meth (acryl)” represents “acryl” and “methacryl”, and “meth (acryloyl)” represents “ Represents “acryloyl” and “methacryloyl”. Further, in the present specification, “monomer” and “monomer” are synonymous. The monomer in the present invention is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 1,000 or less. In the present specification, “functional group” refers to a group involved in a polymerization reaction.
In addition, the nanoimprint referred to in the present invention means pattern transfer having a size of about several tens of nm to several μm, and it is needless to say that the nanoimprint is not limited to the nano order.
In addition, in the description of group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

[Curable composition for nanoimprint]
The curable composition for nanoimprinting of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) contains an aromatic carboxylic acid alkenyl ester represented by the following general formula (1), and the viscosity of the composition: Is 3 to 18 mPa · s.

（式中、Ｒ¹は炭素数２〜６のアルケニル基を表し、Ｒ²は炭素数２〜６のアルケニル基もしくは炭素数２〜６のアルケニルオキシ基を表し、Ａｒは芳香族炭化水素を表す。ｎは１以上の整数を表し、ｍは０以上の整数を表す。ｎ＋ｍは２以上の整数である。）

(In the formula, R ¹ represents an alkenyl group having 2 to 6 carbon atoms, R ² represents an alkenyl group having 2 to 6 carbon atoms or an alkenyloxy group having 2 to 6 carbon atoms, and Ar represents an aromatic hydrocarbon. N represents an integer of 1 or more, m represents an integer of 0 or more, and n + m is an integer of 2 or more.)

  Usually, the curable composition used for the photo-nanoimprint method is a photopolymerization initiator that initiates a polymerization reaction of the polymerizable monomer by light irradiation, if necessary, with a polymerizable monomer having a polymerizable functional group. Agent, surfactant or antioxidant. The curable composition for nanoimprinting of the present invention has, as the polymerizable monomer, an aromatic carboxylic acid alkenyl ester represented by the general formula (1) (hereinafter referred to as “aromatic carboxylic acid alkenyl ester in the present invention”). Therefore, the cured product formed using the composition of the present invention has the ability to form a fine concavo-convex pattern (pattern transfer accuracy), light transmittance, and peelability from the mold (to the mold). The adhesion residue is small, and the pattern curability after the composition is cured is also high. Moreover, the hardened | cured material (pattern) formed using the curable composition for nanoimprints of this invention has favorable light transmittance even after hardening (for example, after the heat-hardening process in 200 degreeC or more). The composition of the present invention can have excellent coating film properties in other respects such as coating suitability and other processability. For this reason, the curable composition for nanoimprinting of the present invention can be widely applied to fields where optical nanoimprint lithography can be applied.

That is, the curable composition for nanoimprinting of the present invention can have the following characteristics.
(1) Since the solution fluidity at room temperature is excellent, the composition easily flows into the cavity of the mold recess, and the atmosphere is difficult to be taken in. Residues hardly remain after curing.
(2) The cured film after curing is excellent in mechanical properties, adhesion between the coating film and the substrate, and peelability between the coating film and the mold. A good pattern can be formed without causing surface roughness due to stringing (good pattern transfer accuracy).
(3) Since it is excellent in coating uniformity, it is suitable for the field of coating / microfabrication on large substrates.
(4) Since it has high mechanical properties such as light transmittance, residual film property, scratch resistance (curability) and solvent resistance, it can be suitably used as various permanent films.

  For this reason, the curable composition for nanoimprints of the present invention is, for example, a member for semiconductor integrated circuits and liquid crystal display devices that have been difficult to develop (particularly, thin film transistors for liquid crystal displays, protective films for liquid crystal color filters, spacers, etc. And other applications such as partition materials for plasma display panels, flat screens, micro electromechanical systems (MEMS), sensor elements, optical disks, and high-density memories. Magnetic recording media such as discs, optical parts such as diffraction grating relief holograms, nanodevices, optical devices, optical films and polarizing elements, organic transistors, color filters, overcoat layers, column materials, liquid crystal alignment rib materials, microlenses Array, immunoassay chip, DNA separation chip Microreactor nanobio devices, optical waveguides, can also be widely applied to manufacturing, such as an optical filter, photonic crystal.

  Among the above fields, the cured product obtained by curing the curable composition for nanoimprinting of the present invention is light transmissive even after being cured by heat treatment (post-baking) at 200 ° C. or higher after light irradiation. In particular, it can be suitably used as a permanent film that requires light transmittance (for example, a color filter protective film for liquid crystal display devices, a spacer, etc.).

-Viscosity of the composition-
First, the viscosity of the curable composition for nanoimprints of the present invention will be described. The viscosity in the present invention means a viscosity at 25 ° C. unless otherwise specified. The curable composition for nanoimprinting of the present invention has a viscosity at 25 ° C. of 3 to 18 mPa · s. By setting such a viscosity, it is possible to impart the ability to form a fine concavo-convex pattern before curing, coating suitability and other processing suitability. After curing, resolution, line edge roughness, residual film properties, substrate adhesion Alternatively, excellent coating film properties can be imparted in other respects. The viscosity of the curable composition for nanoimprinting is not simply low, but only if it has a specific viscosity range, that is, a specific viscosity range of 3 to 18 mPa · s, the object of the present invention can be achieved. I found it. That is, when the viscosity of the photocurable composition of the present invention is less than 3 mPa · s, a problem of substrate coating suitability and a decrease in mechanical strength of the film occur. Specifically, it is not preferable to make the viscosity too low because unevenness on the surface occurs during application of the composition or the composition flows out of the substrate during application. On the other hand, when the viscosity of the photocurable composition of the present invention exceeds 18 mPa · s, when the mold having a fine concavo-convex pattern is brought into close contact with the photocurable composition, the composition hardly flows into the cavity of the concave portion of the mold. Therefore, since air is easily taken in, bubble defects are likely to occur, and a residue tends to remain after photocuring in the mold convex portion. In addition, since the viscosity of the optical nanoimprint composition disclosed so far in the resist material handbook, P1, 103-104 (2005, published by the Information Organization) has a viscosity of about 50 mPa · s, after bubble defects or photocuring There is a problem that residue is likely to remain in the concave portion of the mold, and it can be applied only to limited applications. The viscosity of the curable composition for nanoimprinting of the present invention is preferably 5 to 15 mPa · s, more preferably 7 to 12 mPa · s.

  Generally, in order to adjust the viscosity of the composition, it is possible to blend various monomers, oligomers and polymers having different viscosities. In order to design the viscosity of the curable composition for nanoimprints of the present invention within the above range, the monomer is diluted with a compound having a monomer viscosity of 10 mPa · s or less to adjust the viscosity of the composition. It is preferable.

  The curable composition for nanoimprinting of the present invention contains (A) an aromatic carboxylic acid alkenyl ester (polymerizable monomer in the present invention) in the present invention, and (B) other polymerizability described later as other components. You may contain a monomer, (C) photoinitiator (D) surfactant, and (E) antioxidant.

-(A) Aromatic carboxylic acid alkenyl ester in the present invention-
The aromatic carboxylic acid alkenyl ester contained in the curable composition for nanoimprinting of the present invention may be only one type, or two or more types may be used in combination. In addition, the content of the aromatic carboxylic acid alkenyl ester in the composition of the present invention is 5 to 95 with respect to the total amount of the composition from the viewpoint of adjusting the composition viscosity, providing mold releasability, and imparting mechanical strength. % By mass is preferable, 10 to 80% by mass is more preferable, and 15 to 60% by mass is particularly preferable.

  An alkenyl ester group or an allyl group can lower the viscosity of the compound than a (meth) acrylate group. As a result, it was difficult to design a low-viscosity and multifunctional product with (meth) acrylate, but according to the curable composition for nanoimprinting of the present invention, two or more alkenyl ester groups were used as the polymerizable monomer. By using an aromatic carbonyl acid alkenyl ester containing an alkenyl group such as or allyl group, it is possible to satisfy the low viscosity of the composition and achieve polyfunctionalization of the polymerizable monomer. Furthermore, the aromatic carboxylic acid alkenyl ester in the present invention realizes a low viscosity due to the alkenyl group, thereby preventing aromatic rings (benzene ring, naphthalene ring) contributing to improving the strength of the cured film while suppressing an increase in viscosity. It has the merit that it can be used for a nucleus.

  The curable composition for nanoimprinting in the present invention is a compound represented by the following general formula (1).

（式中、Ｒ¹は炭素数２〜６のアルケニル基を表し、Ｒ²は炭素数２〜６のアルケニル基もしくは炭素数２〜６のアルケニルオキシ基を表し、Ａｒは芳香族炭化水素を表す。ｎは１以上の整数を表し、ｍは０以上の整数を表す。ｎ＋ｍは２以上の整数である。）

(In the formula, R ¹ represents an alkenyl group having 2 to 6 carbon atoms, R ² represents an alkenyl group having 2 to 6 carbon atoms or an alkenyloxy group having 2 to 6 carbon atoms, and Ar represents an aromatic hydrocarbon. N represents an integer of 1 or more, m represents an integer of 0 or more, and n + m is an integer of 2 or more.)

In the general formula (1), the alkenyl group having 2 to 6 carbon atoms represented by R ¹ and R ² is preferably an alkenyl group having 2 to 3 carbon atoms from the viewpoint of suppressing increase in the compound viscosity. Examples of the alkenyl group include a vinyl group, a propenyl group (—CH═CH—CH ₃ ), an allyl group (—CH ₂ —CH═CH ₂ ), and a 6-hexenyl group.
Further, in the general formula (1), the alkenyloxy group having 2 to 6 carbon atoms represented by R ^2, from the viewpoint of suppressing an increase of the compound viscosity, preferably an alkenyloxy group having 2 to 3 carbon atoms. Examples of the alkenyloxy group include a vinyloxy group (—O—CH═CH ₂ ), a propenyloxy group (—O—CH═CH—CH ₃ ), and an allyloxy group (—O—CH ₂ —CH═CH ₂ ). A 6-hexenyloxy group is mentioned.

In general formula (1), Ar represents an aromatic hydrocarbon. The aromatic hydrocarbon may be either a monocyclic structure or a polycyclic structure, and in the polycyclic structure, a condensed polycyclic structure such as naphthalene, or two or more single aromatic hydrocarbons such as bisphenol is a single bond or It may be a ring assembly structure connected by an organic linking group. When Ar has a condensed polycyclic structure, the number of ring structures is preferably 2 or less from the viewpoint of viscosity. As said aromatic hydrocarbon, a C6-C10 aromatic hydrocarbon is preferable from a raise viewpoint of a compound viscosity and a compatible viewpoint with another compound. Examples of the aromatic hydrocarbon include a benzene ring, a naphthalene ring, and a pyridine ring. From the viewpoint of compatibility with other compounds, benzene and naphthalene are preferable.
In general formula (1), n represents an integer of 1 or more, and m represents an integer of 0 or more. Since the aromatic carboxylic acid alkenyl ester in the present invention is n + m of 2 or more, that is, a polyfunctional compound, the strength of the cured film can be secured.
The upper limit of n and m is not particularly limited, but n + m is preferably 6 or less, and more preferably 4 or less, from the viewpoints of the viscosity of the composition and polymerization reactivity. Said n becomes like this. Preferably it is 1-6, More preferably, it is 1-3. m is preferably 0 to 3, and more preferably 0 to 1. That is, from the viewpoint of suppressing increase in the compound viscosity and imparting mechanical strength of the cured film, n + m is preferably 2 to 6, and more preferably 2 to 4.

The total carbon number of the aromatic carboxylic acid alkenyl ester in the present invention is preferably 12 to 26 and more preferably 14 to 20 from the viewpoint of suppressing increase in the compound viscosity. In addition, the molecular weight of the aromatic carboxylic acid alkenyl ester in the present invention is preferably 150 to 700, and more preferably 180 to 500, from the viewpoint of suppressing increase in the compound viscosity.
Furthermore, in the general formula (1), R ¹ , R ² and Ar may have a substituent such as an alkyl group or a halogen atom, if necessary.

（各式中、Ｒ²は炭素数２〜６のアルケニル基もしくは炭素数２〜６のアルケニルオキシ基を表す。ｎは１以上の整数を表し、ｍは０以上の整数を表す。ｎ＋ｍは２以上の整数である。） The aromatic carboxylic acid alkenyl ester in the present invention is preferably a compound represented by the following general formula (2) or (3).

(In each formula, R ² represents an alkenyl group having 2 to 6 carbon atoms or an alkenyloxy group having 2 to 6 carbon atoms. N represents an integer of 1 or more, m represents an integer of 0 or more, and n + m is 2. (It is an integer above.)

  Specific examples (compounds A-1 to A-10) of the aromatic carboxylic acid alkenyl ester in the present invention are listed below. However, the aromatic carboxylic acid alkenyl ester in the present invention is not limited thereto.

-(B) Other polymerizable monomer-
As described above, the curable composition for nanoimprinting of the present invention may further contain other polymerizable monomers for the purpose of improving the composition viscosity, film hardness, flexibility and the like. Examples of the other polymerizable monomer include a polymerizable unsaturated monomer having 1 to 6 ethylenically unsaturated bond-containing groups; a compound having an oxirane ring (epoxy compound); a vinyl ether compound; a styrene derivative; A compound having a fluorine atom; a propenyl ether or a butenyl ether can be exemplified, and a polymerizable unsaturated monomer having 1 to 6 ethylenically unsaturated bond-containing groups from the viewpoint of promoting curability during light irradiation Is preferred.

The polymerizable unsaturated monomer having 1 to 6 ethylenically unsaturated bond-containing groups will be described.
First, specific examples of the polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group (monofunctional polymerizable unsaturated monomer) include 2-acryloyloxyethyl phthalate and 2-acryloyloxy. 2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meta ) Acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4- Hydroxybutyl ( Acrylate), acrylic acid dimer, benzyl (meth) acrylate, butanediol mono (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, ethylene oxide modified (hereinafter referred to as “EO”). ) Cresol (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) ) Acrylate, isobornyl (meth) acrylate, dicyclohentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isomyristyl ( Acrylate), lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate , Neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, trimethoxysilylpropyl acrylate, Ethyl oxetanyl methyl acrylate, ethyl isocyanate (meth) acrylate , Epichlorohydrin (hereinafter referred to as “ECH”) modified phenoxy acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, Polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, tert-butyl (meth) acrylate, tribromophenyl (Meth) acrylate, EO-modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate, p- Examples are isopropenylphenol, styrene, α-methylstyrene, acrylonitrile and vinylcarbazole.
Among these, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethoxypropyl acrylate, and ethyl oxetanylmethyl acrylate are particularly preferably used in the present invention.

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

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

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

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

  Examples of the compound having an oxirane ring (epoxy compound) include polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycol, and polyglycidyl ethers of aromatic polyols. Examples include teters, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds, and epoxidized polybutadienes. These compounds can be used alone or in combination of two or more thereof.

  Examples of the compound having an oxirane ring (epoxy compound) that can be preferably used in the present invention include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, and brominated. Bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycid Ethers, polypropylene glycol diglycidyl ethers; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin; fats Diglycidyl esters of long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol or alkylene oxide to these; glycidyl of higher fatty acids Examples thereof include esters.

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

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

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

As other polymerizable monomer used in the present invention, a vinyl ether compound may be used in combination.
As the vinyl ether compound, known compounds can be appropriately selected. For example, 2-ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, diethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether. 1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, tri Methylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, tet Ethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene vinyl ether , Trimethylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether, pentaerythritol triethylene vinyl ether, pentaerythritol tetraethylene vinyl ether, 1,1,1- Squirrel [4- (2-vinyloxy ethoxy) phenyl] ethane, bisphenol A divinyloxyethyl carboxyethyl ether.
Among these, trimethylolpropane trivinyl ether and bisphenol A divinyloxyethyl ether are preferably used in the present invention.

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

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

  Other styrene derivatives that can be used in combination with the aromatic carboxylic acid alkenyl ester of the present invention include, for example, styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methyl. Styrene, p-methoxy-β-methylstyrene, p-hydroxystyrene, and the like can be mentioned. Examples of vinyl naphthalene derivatives include 1-vinylnaphthalene, α-methyl-1-vinylnaphthalene, β-methyl-1 -Vinylnaphthalene, 4-methyl-1-vinylnaphthalene, 4-methoxy-1-vinylnaphthalene, etc. can be mentioned.

  In addition, for the purpose of improving the peelability and applicability from the mold, trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, perfluorobutyl-hydroxypropyl ( Use in combination with compounds having fluorine atoms such as (meth) acrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, etc. Can do.

  As another polymerizable monomer used in the present invention, propenyl ether and butenyl ether can also be used. Examples of the propenyl ether or butenyl ether include 1-dodecyl-1-propenyl ether, 1-dodecyl-1-butenyl ether, 1-butenoxymethyl-2-norbornene, 1-4-di (1-butenoxy) butane, 1,10-di (1-butenoxy) decane, 1,4-di (1-butenoxymethyl) cyclohexane, diethylene glycol di (1-butenyl) ether, 1,2,3-tri (1-butenoxy) propane, propenyl ether propylene Carbonate or the like can be suitably applied.

  The preferred content of the other polymerizable monomer described above varies depending on the content of the polymerizable compound in the present invention in the composition. For example, in the composition of the present invention, the range is from 10 to 90% by mass. Preferably, it is contained in the range of 20-80 mass%.

  Next, a preferred blend form of the aromatic carboxylic acid alkenyl ester and other polymerizable monomer in the present invention (hereinafter, these may be collectively referred to as “polymerizable unsaturated monomer”) will be described. As described above, the content of the aromatic carboxylic acid alkenyl ester in the composition of the present invention is preferably 5 to 95% by mass, more preferably 10 to 80% by mass, and still more preferably 15 to 60% by mass. When another polymerizable monomer is used in combination, the content thereof is preferably included in the range of 10 to 90% by mass, and more preferably in the range of 20 to 80% by mass. The total content of polymerizable unsaturated monomers in the composition of the present invention is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, more preferably 30 to 70% from the viewpoint of promoting curability during light irradiation. Mass% is particularly preferred. In the present invention, the mass mixing ratio of the aromatic carboxylic acid alkenyl ester and the other polymerizable monomer in the present invention is preferably in the range of 1 to 10 to 10 to 1. From the viewpoints of copolymerization and co-reaction, among the other polymerizable monomers described above, the polymerizable monomer used in combination with the aromatic carboxylic acid alkenyl ester in the present invention is preferably a (meth) acrylate monomer.

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

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

  As the radical photopolymerization initiator used in the present invention, for example, a commercially available initiator can be used. Examples of these include Irgacure® 2959 available from Ciba (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, Irgacure ( (Registered trademark) 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure (registered trademark) 500 (1-hydroxycyclohexyl phenyl ketone, benzophenone), Irgacure (registered trademark) 651 (2,2-dimethoxy-1,2-diphenylethane- 1-one), Irgacure® 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1), Irgacure® 907 (2-methyl-1 [4- Methylthiophenyl] -2-morpholino Lopan-1-one, Irgacure® 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2,4 , 4-trimethyl-pentylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone), Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide) , 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Irgacure® OXE01 (1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- ( O-benzoyloxime), Darocur 1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Darocur® 1116, 1398, 1174 and 1020, CGI242 (ethanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide), Lucirin TPO available from BASF -L (2,4,6-trimethylbenzoylethoxyphenylphosphine oxide), ESACURE 1001M (1- [4-benzoylphenylsulfanyl] phenyl] -2-methyl-2- (4-methyl), available from ESACUR Nippon Siber Hegner Phenyl Ruphonyl) propan-1-one, Adeka optomer (registered trademark) N-1414 (carbazole phenone), Adeka optomer (registered trademark) N-1717 (acridine) available from Asahi Denka Co., Ltd. (Registered trademark) N-1606 (triazine series), TFE-triazine (2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3, manufactured by Sanwa Chemical Co., Ltd.) 5-triazine), TME-triazine (2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine) manufactured by Sanwa Chemical Co., Ltd. MP-triazine (2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine) manufactured by Sanwa Chemical, TAZ-1 manufactured by Midori Chemical 13 (2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), TAZ-108 manufactured by Midori Chemical (2- (3,4) -Dimethoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine), benzophenone, 4,4'-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzoyl-4'-methyldiphenyl Sulfide, 4-phenylbenzophenone, ethyl Michler's ketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2- Methyl thioxanthone, thioxanthone Nium salt, benzoin, 4,4′-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetophenone, diethoxyacetophenone and dibenzosuberone, o-Benzoyl methyl benzoate, 2-benzoylnaphthalene, 4-benzoyl biphenyl, 4-benzoyl diphenyl ether, 1,4-benzoylbenzene, benzyl, 10-butyl-2-chloroacridone, [4- (methylphenylthio) phenyl ] Phenylmethane), 2-ethylanthraquinone, 2,2-bis (2-chlorophenyl) 4,5,4 ', 5'-tetrakis (3,4,5-trimethoxyphenyl) 1,2'- Imidazole, 2,2-bis (o-chlorophenyl) 4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, tris (4-dimethylaminophenyl) methane, ethyl-4- (dimethylamino) ) Benzoate, 2- (dimethylamino) ethyl benzoate, butoxyethyl-4- (dimethylamino) benzoate, and the like.

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

-(D) Surfactant-
The curable composition for nanoimprinting of the present invention may contain a surfactant. The surfactant used in the present invention contains, for example, 0.001 to 5% by mass, preferably 0.002 to 4% by mass, and more preferably 0.005 to 3% by mass in the entire composition. It is. When using 2 or more types of surfactant, the total amount becomes the said range. The total amount is within the above range. When the surfactant is in the range of 0.001 to 5% by mass in the composition, the effect of coating uniformity is good, and deterioration of mold transfer characteristics due to excessive surfactant is unlikely to occur.
The surfactant preferably includes at least one of a fluorine-based surfactant, a silicone-based surfactant, and a fluorine / silicone-based surfactant, and includes both a fluorine-based surfactant and a silicone-based surfactant. Alternatively, it preferably contains a fluorine / silicone surfactant, and most preferably contains a fluorine / silicone surfactant. The fluorine-based surfactant and the silicone-based surfactant are preferably nonionic surfactants.
Here, the “fluorine / silicone surfactant” refers to one having both requirements of a fluorine surfactant and a silicone surfactant.
By using such a surfactant, a silicon wafer for manufacturing a semiconductor element, a glass square substrate for manufacturing a liquid crystal element, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, a tantalum alloy film, a silicon nitride film, Striation that occurs when the nanoimprint curable composition of the present invention is applied to a substrate on which various films are formed, such as an amorphous silicone film, an indium oxide (ITO) film doped with tin oxide, and a tin oxide film, It becomes possible to solve the problem of poor coating such as a scale-like pattern (unevenness of drying of the resist film). In addition, the fluidity of the composition of the present invention into the cavity of the mold recess is improved, the peelability between the mold and the resist is improved, the adhesion between the resist and the substrate is improved, the viscosity of the composition is decreased, etc. Is possible. In particular, the nanoimprint composition of the present invention can significantly improve the coating uniformity by adding the surfactant, and in a coating using a spin coater or a slit scan coater, good coating suitability regardless of the substrate size. Is obtained.

Examples of nonionic fluorosurfactants that can be used in the present invention include trade names Fluorard FC-430 and FC-431 (manufactured by Sumitomo 3M Co., Ltd.), trade names Surflon S-382 (Asahi Glass ( EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 (manufactured by Tochem Products), trade names PF-636, PF-6320, PF -656, PF-6520 (both OMNOVA Solutions, Inc.), trade names FT250, FT251, DFX18 (both manufactured by Neos Co., Ltd.), trade names Unidyne DS-401, DS-403, DS-451 ( All are made by Daikin Industries, Ltd.) and trade names Megafuk 171, 172, 173, 178K, 178A (all are Dainichi) Ink and Chemicals Co., Ltd.) and the like.
Examples of the nonionic silicone surfactant include trade name SI-10 series (manufactured by Takemoto Yushi Co., Ltd.), MegaFac Paintad 31 (manufactured by Dainippon Ink & Chemicals, Inc.), KP -341 (manufactured by Shin-Etsu Chemical Co., Ltd.).
Examples of the fluorine / silicone surfactant include trade names X-70-090, X-70-091, X-70-092, X-70-093 (all Shin-Etsu Chemical Co., Ltd. )), And trade names Megafuk R-08 and XRB-4 (both manufactured by Dainippon Ink & Chemicals, Inc.).

-(E) Antioxidant-
Furthermore, it is preferable that the curable composition for nanoimprints of the present invention contains an antioxidant. Content of the antioxidant used for this invention is 0.01-10 mass% in the whole composition, for example, Preferably it is 0.2-5 mass%. When using 2 or more types of antioxidant, the total amount becomes the said range.
The antioxidant suppresses fading caused by heat or light irradiation and fading caused by various oxidizing gases such as ozone, active oxygen, NO _x , SO _x (X is an integer). In particular, in the present invention, by adding an antioxidant, there is an advantage that coloring of a cured film can be prevented and a reduction in film thickness due to decomposition can be reduced. Examples of such antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates, Examples include thiourea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like. Among these, hindered phenol antioxidants and thioether antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness.

  Commercially available products of the antioxidant include trade names Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Geigy Co., Ltd.), trade names Antigene P, 3C, FR, Sumilyzer S, Sumilyzer GA80 (Sumitomo Chemical Co., Ltd.) Product name) ADK STAB AO70, AO80, AO503 (manufactured by ADEKA Corporation) and the like. These may be used alone or in combination.

-Other ingredients-
In addition to the above-described components, the composition of the present invention includes a polymer component, a release agent, an organometallic coupling agent, a polymerization inhibitor, an ultraviolet absorber, a light stabilizer, an anti-aging agent, a plasticizer, and an adhesive. Accelerators, thermal polymerization initiators, photobase generators, colorants, elastomer particles, photoacid multipliers, basic compounds, and other flow regulators, antifoaming agents, dispersants, and the like may be added.

In the composition of the present invention, for the purpose of further increasing the crosslinking density, a polyfunctional oligomer having a molecular weight higher than that of the other polyfunctional polymerizable monomer may be blended within a range that achieves the object of the present invention. it can. Examples of the polyfunctional oligomer having photoradical polymerizability include various acrylate oligomers such as polyester acrylate, urethane acrylate, polyether acrylate, and epoxy acrylate, and hydrolysis condensates of trimethoxysilylpropyl acrylate.
The curable composition for nanoimprinting of the present invention may further contain a polymer component from the viewpoint of improving imprintability and curability. The polymer component is preferably a polymer having a polymerizable functional group in the side chain. The weight average molecular weight of the polymer component is preferably 5,000 to 50,000, more preferably 10,000 to 30,000 from the viewpoint of improving the crosslinking density. The addition amount of the polymer component is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, still more preferably 0 to 10% by mass, and most preferably 2% by mass or less, relative to the component excluding the solvent of the composition. It is. When the content of the polymer component having a molecular weight of 2000 or more in the components excluding the solvent in the composition of the present invention is 30% by mass or less, the pattern forming property is improved. Further, from the viewpoint of pattern formability, it is preferable that the resin component is as few as possible, and it is preferable that the resin component is not included except for surfactants and trace amounts of additives.

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

  The silicone-based release agent has particularly good releasability from the mold when combined with the photo-curable resin used in the present invention, and the phenomenon that the plate is taken off hardly occurs. The silicone release agent is a release agent having an organopolysiloxane structure as a basic structure, and examples thereof include unmodified or modified silicone oil, polysiloxane containing trimethylsiloxysilicate, and silicone acrylic resin. Further, it is possible to apply a silicone leveling agent generally used in a hard coat composition.

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

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

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

  When a release agent is added to the curable composition for nanoimprints of the present invention, it is preferably added in a proportion of 0.001 to 10% by mass in the total amount of the composition, and added in a range of 0.01 to 5% by mass. More preferably. When the content of the release agent is in the range of 0.01 to 5% by mass, the effect of improving the peelability between the mold and the curable composition layer for nanoimprinting is improved, and further due to the repelling at the time of coating the composition. The problem of surface roughness of the coating film occurs, the adhesion of the substrate itself or the adjacent layer, for example, the deposited layer in the product, or the destruction of the film during transfer (film strength becomes too weak) occurs. Can be suppressed.

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

  Examples of the silane coupling agent that can be used in the composition of the present invention include vinyl silanes such as vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane; γ-methacryloxypropyl Trimethoxysilane; epoxy silane such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane; N-β- (amino Aminosilanes such as ethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane ;and, Examples of other silane coupling agents include γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, and γ-chloropropylmethyldiethoxysilane.

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

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

  Examples of the aluminum coupling agent include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, ethylacetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), alkyl Examples thereof include acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetoacetate) and the like.

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

  In order to improve storage stability etc., you may mix | blend a polymerization inhibitor with the curable composition for nanoimprint of this invention. Examples of the polymerization inhibitor include phenols such as hydroquinone, tert-butylhydroquinone, catechol, and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines; copper and the like. The polymerization inhibitor is preferably blended arbitrarily in a proportion of 0.001 to 10% by mass with respect to the total amount of the composition of the present invention.

  An ultraviolet absorber can also be used for the curable composition for nanoimprints of the present invention. Commercially available UV absorbers include Tinuvin P, 234, 320, 326, 327, 328, 213 (above, manufactured by Ciba Geigy Co., Ltd.), Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350, 400 (manufactured by Sumitomo Chemical Co., Ltd.) and the like. It is preferable to mix | blend an ultraviolet absorber arbitrarily in the ratio of 0.01-10 mass% with respect to the whole quantity of the curable composition for optical nanoimprints.

  A light stabilizer can also be used in the curable composition for nanoimprinting of the present invention. Commercially available products of the light stabilizer include Tinuvin 292, 144, 622LD (manufactured by Ciba Geigy Corp.), Sanol LS-770, 765, 292, 2626, 1114, 744 (manufactured by Sankyo Kasei Kogyo Co., Ltd.). ) And the like. The light stabilizer is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the composition.

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

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

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

  When hardening the composition of this invention, a thermal-polymerization initiator can also be added as needed. Preferred examples of the thermal polymerization initiator include peroxides and azo compounds. Specific examples include benzoyl peroxide, tert-butyl-peroxybenzoate, azobisisobutyronitrile, and the like. The thermal polymerization initiator in the composition is preferably 5% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less. The addition of the thermal polymerization initiator is preferably 0.1% by mass or more in order to obtain the effect.

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

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

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

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

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

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

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

  In addition, the moisture content at the time of preparation of the curable composition for nanoimprint of the present invention is preferably 2.0% by mass or less, more preferably 1.5% by mass, and further preferably 1.0% by mass or less. By making the water content at the time of preparation 2.0% by mass or less, the storage stability of the composition of the present invention can be made more stable.

  Moreover, although a solvent can also be used for the curable composition for nanoimprints of the present invention, it is preferably a substantially solvent-free composition. Here, “substantially solvent-free composition” means a composition that does not substantially contain an organic solvent in the composition, specifically, the organic solvent in the composition. It is preferable that content is 3 mass% or less in all the compositions. That is, since the composition of the present invention preferably contains other monofunctional and / or bifunctional monomers as described above as reactive diluents, the organic solvent for dissolving the components of the composition of the present invention is It is not always necessary to contain. In addition, if an organic solvent is not included, a baking process for the purpose of volatilization of the solvent is not necessary, so that there is a great merit that it is effective for simplifying the process. Therefore, in the composition of the present invention, the content of the organic solvent is preferably 3% by mass or less, more preferably 2% by mass or less, and it is particularly preferable not to contain it. As described above, the composition of the present invention does not necessarily contain an organic solvent. However, in the case of dissolving a compound that does not dissolve in the reactive diluent as the composition of the present invention, or when finely adjusting the viscosity. Any of these may be added. The organic solvent that can be preferably used in the composition of the present invention is a solvent generally used in curable compositions for optical nanoimprints and photoresists, which dissolves and uniformly disperses the compound used in the present invention. There is no particular limitation as long as it does not react with these components.

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

  Further, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. A high boiling point solvent can also be added. These may be used alone or in combination of two or more.

  Among these, methoxypropylene glycol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, methyl isobutyl ketone, 2-heptanone and the like are particularly preferable.

[Method for producing cured product]
Next, the manufacturing method of the hardened | cured material (especially fine uneven | corrugated pattern) using the curable composition for nanoimprints of this invention is demonstrated. In the method for producing a cured product of the present invention, a step of forming a pattern forming layer by applying the curable composition for nanoimprinting of the present invention on a substrate or a support (base material), and a mold on the surface of the pattern forming layer. A fine concavo-convex pattern can be formed by curing the composition of the present invention through the step of pressing and the step of irradiating the pattern forming layer with light. In particular, in the present invention, in order to improve the degree of curing of the cured product, it is preferable to further include a step of heating the pattern forming layer after light irradiation.
The cured product obtained by the method for producing a cured product of the present invention is excellent in pattern precision, curability, and light transmittance, and is particularly suitable as a protective film for liquid crystal color filters, spacers, and other liquid crystal display device members. Can be used.
Specifically, a layer (pattern forming layer) consisting of the composition of the present invention is applied on a base material (substrate or support) by applying at least a pattern forming layer consisting of the composition of the present invention and drying as necessary. To form a pattern receptor (with a pattern-forming layer provided on the substrate), press the mold against the surface of the pattern-receiving layer of the pattern receptor, and transfer the mold pattern. The concavo-convex pattern forming layer is cured by light irradiation and heating. Light irradiation and heating may be performed a plurality of times. The optical imprint lithography according to the pattern forming method (a method for producing a cured product) of the present invention can be laminated and multiple patterned, and can be used in combination with ordinary thermal imprint.

  The curable composition for nanoimprinting of the present invention can form a fine pattern with low cost and high accuracy by an optical nanoimprinting method. For this reason, what was formed using the conventional photolithographic technique can be formed with further high precision and low cost. For example, the composition of the present invention is applied on a substrate or a support, and a layer made of the composition is exposed, cured, and dried (baked) as necessary to be used for a liquid crystal display (LCD). It can also be applied as a permanent film such as an overcoat layer or an insulating film, an etching resist for a semiconductor integrated circuit, a recording material, or a flat panel display. In particular, the pattern formed using the curable composition for nanoimprinting of the present invention is excellent in etching property and can be preferably used as an etching resist for dry etching using fluorocarbon or the like. Since the curable composition for nanoimprinting of the present invention is excellent in light transmittance after curing, it is particularly suitable for producing a permanent film such as an overcoat layer or an insulating film.

  In permanent films (resist for structural members) used in liquid crystal displays (LCDs) and resists used in substrate processing of electronic materials, ions of metals or organic substances in the resist are used so as not to hinder the operation of the product. It is desirable to avoid contamination with sexual impurities as much as possible. For this reason, the concentration of the ionic impurities of the metal or organic matter in the curable composition for nanoimprints of the present invention is preferably 1000 ppm or less, desirably 10 ppm or less, more preferably 100 ppb or less.

Below, the manufacturing method (pattern formation method (pattern transfer method)) of the hardened | cured material using the curable composition for nanoimprints of this invention is described concretely.
In the manufacturing method of the hardened | cured material of this invention, first, the composition of this invention is apply | coated on a base material, and a pattern formation layer is formed.
As a coating method when the curable composition for nanoimprinting of the present invention is coated on a substrate, generally known coating methods such as a dip coating method, an air knife coating method, a curtain coating method, and a wire bar coating method are used. , Gravure coating method, extrusion coating method, spin coating method, slit scanning method, ink jet method and the like. Moreover, although the film thickness of the pattern formation layer which consists of a composition of this invention changes with uses to be used, it is about 0.05 micrometer-30 micrometers. Further, the composition of the present invention may be applied by multiple coating. In addition, you may form other organic layers, such as a planarization layer and an adhesive bond layer, for example between a base material and the pattern formation layer which consists of a composition of this invention. As a result, the pattern forming layer and the base material are not in direct contact with each other, so that adhesion of dust to the base material, damage to the base material, etc. can be prevented, or the adhesion between the pattern forming layer and the base material can be improved. Can do. In addition, the pattern formed with the composition of this invention is excellent in adhesiveness with an organic layer, even when it is a case where an organic layer is provided on a base material.

  The substrate (substrate or support) on which the curable composition for nanoimprinting of the present invention is applied can be selected depending on various applications, such as quartz, glass, optical film, ceramic material, vapor deposition film, and magnetic film. , Reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, polymer substrate such as SOG (Spin On Glass), polyester film, polycarbonate film, polyimide film, TFT array substrate, PDP electrode plate, glass and transparent There are no particular restrictions on plastic substrates, conductive substrates such as ITO and metals, insulating substrates, semiconductor fabrication substrates such as silicone, silicone nitride, polysilicon, silicone oxide, and amorphous silicone. Further, the shape of the substrate is not particularly limited, and may be a plate shape or a roll shape. In addition, as described later, a light transmissive or non-light transmissive material can be selected as the base material depending on the combination with the mold.

Subsequently, in the manufacturing method of the hardened | cured material of this invention, in order to transcribe | transfer a pattern to a pattern formation layer, a mold is pressed (pressed) on the pattern formation layer surface. Thereby, the fine pattern previously formed on the pressing surface of the mold can be transferred to the pattern forming layer.
The molding material that can be used in the present invention will be described. In optical nanoimprint lithography using the composition of the present invention, a light transmissive material is selected as at least one of a molding material and / or a base material. In optical imprint lithography applied to the present invention, a curable composition for nanoimprinting of the present invention is applied on a substrate to form a pattern forming layer, and a light-transmitting mold is pressed on this surface, The pattern forming layer is cured by irradiating light from the back surface. Moreover, the curable composition for optical nanoimprint can be apply | coated on a transparent base material, a mold can be pressed, light can be irradiated from the back surface of a base material, and the curable composition for optical nanoimprint can also be hardened.
The light irradiation may be performed with the mold attached or after the mold is peeled off. In the present invention, the light irradiation is preferably performed with the mold in close contact.

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

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

  The mold used in the method for producing a cured product of the present invention may be a mold subjected to a release treatment in order to improve the peelability between the curable composition for optical nanoimprint and the mold surface. Examples of such molds include those that have been treated with a silane coupling agent such as silicone or fluorine, such as Optool DSX manufactured by Daikin Industries, Ltd. or Novec EGC-1720 manufactured by Sumitomo 3M Co., Ltd. Commercially available release agents can also be suitably used.

  When photoimprint lithography is performed using the composition of the present invention, it is usually preferable to perform the mold pressure at 10 atm or less in the method for producing a cured product of the present invention. By setting the mold pressure to 10 atm or less, the mold and the substrate are hardly deformed and the pattern accuracy tends to be improved. Further, it is preferable from the viewpoint that the apparatus can be reduced because the pressure is low. As the mold pressure, it is preferable to select a region in which the uniformity of mold transfer can be ensured within a range in which the remaining film of the curable composition for optical nanoimprinting on the mold convex portion is reduced.

In the method for producing a cured product of the present invention, the irradiation amount of light irradiation in the step of irradiating the pattern forming layer with light may be sufficiently larger than the irradiation amount necessary for curing. The irradiation amount necessary for curing is appropriately determined by examining the consumption of unsaturated bonds of the curable composition for optical nanoimprint and the tackiness of the cured film.
In the photoimprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually room temperature, but the light irradiation may be performed while heating in order to increase the reactivity. As a pre-stage of light irradiation, if it is in a vacuum state, it is effective in preventing bubble mixing, suppressing the decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the curable composition for optical nanoimprinting. It may be irradiated with light. Moreover, the preferable vacuum degree at the time of light irradiation in the manufacturing method of the hardened | cured material of this invention is the range of 10 ^<-1 > Pa to normal pressure.

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

During exposure is preferably in the range of exposure intensity of ^{1mW / cm 2 ~50mW / cm 2} . By making the exposure time 1 mW / cm ² or more, the exposure time can be shortened so that productivity is improved, and by making the exposure time 50 mW / cm ² or less, deterioration of the properties of the permanent film due to side reactions can be suppressed. It tends to be preferable. The exposure dose is desirably in the range of 5 mJ / cm ^{2 to} 1000 mJ / cm ² . If it is less than 5 mJ / cm ² , the exposure margin becomes narrow, photocuring becomes insufficient, and problems such as adhesion of unreacted substances to the mold tend to occur. On the other hand, if it exceeds 1000 mJ / cm ² , the permanent film may be deteriorated due to decomposition of the composition.

  Further, during exposure, in order to prevent inhibition of radical polymerization by oxygen, an inert gas such as nitrogen or argon may be flowed to control the oxygen concentration to less than 100 mg / L.

  In the manufacturing method of the hardened | cured material of this invention, after making a pattern formation layer harden | cure by light irradiation, it is preferable to include the process (post-baking process) which adds and heats the hardened pattern. The heating may be performed either before or after the mold is peeled from the pattern forming layer after light irradiation, but it is preferable to heat the pattern forming layer after the mold is peeled off. As heat which heat-hardens the composition of this invention after light irradiation, 150-280 degreeC is preferable and 200-250 degreeC is more preferable. In addition, the time for applying heat is preferably 5 to 60 minutes, and more preferably 15 to 45 minutes.

Moreover, the pattern formed by the manufacturing method of the hardened | cured material of this invention is useful also as an etching resist. When using the nanoimprinting composition of the present invention as an etching resist, first, a method for producing a cured product of the present invention on a substrate using, for example, a silicon wafer on which a thin film such as SiO ₂ is formed as a substrate. To form a nano-order fine pattern. Thereafter, a desired pattern can be formed on the substrate by etching using an etching gas such as hydrogen fluoride in the case of wet etching or CF _{4 in} the case of dry etching. The curable composition for nanoimprinting of the present invention has particularly good etching resistance against dry etching.

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

  As described above, the cured product formed by the method for producing a cured product of the present invention can be used as a permanent film (resist for a structural member) or an etching resist used in a liquid crystal display (LCD) or the like. In addition, after manufacturing, bottled in containers such as gallon bottles and coated bottles, transported and stored. In this case, in order to prevent deterioration, the inside of the container is replaced with inert nitrogen or argon. Also good. Further, at the time of transportation and storage, the temperature may be normal temperature, but the temperature may be controlled in the range of −20 ° C. to 0 ° C. in order to prevent the permanent film from being altered. Of course, it is preferable to shield from light so that the reaction does not proceed.

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

[Preparation of curable composition for nanoimprint]
As shown in the following Tables 1 to 3, in addition to the above-mentioned aromatic carboxylic acid alkenyl ester and the following polymerizable compound (functional monomer) in the present invention, the following polymerization initiator P-1 and the following surfactant W- 1 and W-2, and the following antioxidants Ac-1 and Ac-2 were added to prepare a curable composition for nanoimprinting.

<Other monofunctional monomers>
R-1: benzyl acrylate (Biscoat # 160: manufactured by Osaka Organic Chemical Co., Ltd.)
R-2: Trimethoxysilylpropyl acrylate (KBM-5103: manufactured by Shin-Etsu Chemical Co., Ltd.)
R-3: Ethyl oxetanyl methyl acrylate (OXE-10: manufactured by Osaka Organic Chemical Co., Ltd.)

<Other bifunctional monomers>
S-01: Neopentyl glycol diacrylate <other trifunctional or higher monomer>
S-10: Trimethylolpropane triacrylate (Aronix M-309: manufactured by Toagosei Co., Ltd.)
S-11: High molecular silicon compound (Ac-SQ: manufactured by Toagosei Co., Ltd.)

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

<Surfactant>
W-1: Fluorosurfactant (manufactured by Tochem Products Co., Ltd .: Fluorosurfactant)
W-2: Silicone surfactant (manufactured by Dainippon Ink and Chemicals, Inc .: MegaFuck Paint 31)

<Antioxidant>
Ac-1: Sumilizer GA80 (manufactured by Sumitomo Chemical Co., Ltd.)
Ac-2: ADK STAB AO503 (manufactured by ADEKA Corporation)

表３中、比較例１における化合物Ｘ−１は特開平１０―２５１４７３号公報に記載の安息香酸アリルエステルである。また、比較例２は特開２００７―７２３７４号公報に記載の高分子ケイ素化合物とフタル酸ジアリルとからなる組成物である。

In Table 3, Compound X-1 in Comparative Example 1 is benzoic acid allyl ester described in JP-A-10-251473. Comparative Example 2 is a composition comprising a polymeric silicon compound and diallyl phthalate described in JP-A-2007-72374.

[Evaluation of curable composition for nanoimprint]
About the composition of each Example and the comparative example, it measured and evaluated according to the following evaluation method about the viscosity, pattern precision, peelability, hardness, and transmittance | permeability. The results are shown in Table 4.

<Viscosity measurement>
The viscosity was measured at 25 ± 0.2 ° C. using a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd. The rotational speed during measurement is 0.5 mPa · s to less than 5 mPa · s at 100 rpm, 5 mPa · s to less than 10 mPa · s at 50 rpm, 10 mPa · s to less than 30 mPa · s at 20 rpm, 30 mPa · s. -More than s and less than 60 mPa * s were performed at 10 rpm, more than 60 mPa * s and less than 120 mPa * s were performed at 5 rpm, and more than 120 mPa * s were performed at 1 rpm or 0.5 rpm.

<Observation of pattern transfer accuracy>
The compositions of each Example and Comparative Example were spin-coated on a glass substrate so as to have a film thickness of 3.0 μm. The mold was pressure-bonded to the spin-coated coated base film in a vacuum chamber, and then returned to atmospheric pressure with nitrogen gas. The substrate to which the mold was attached was transferred to an exposure box, and exposed under the condition of 240 mJ / cm ² from the mold side with an exposure machine using a high-pressure mercury lamp (lamp power 2000 mW / cm ² ) manufactured by ORC under a nitrogen atmosphere. After the exposure, the mold was released to obtain a resist pattern. The obtained resist pattern was completely cured by heating in an oven at 230 ° C. for 30 minutes. The mold has a line / space pattern of 10 μm and is made of polydimethylsiloxane having a groove depth of 4.0 μm (manufactured by Dow Corning Toray Co., Ltd., SILPOT 184 cured at 80 ° C. for 60 minutes).
The pattern shape after the transfer was observed with a scanning electron microscope or an optical microscope, and the pattern shape was evaluated according to the following guidelines.
A: It is almost the same as the pattern of the original plate from which the pattern shape of the mold is based.
B: There is a part (a range of less than 10% of the pattern of the original plate) that is partly different from the original pattern shape of the mold pattern.
C: There is a part (a range of 10% or more and less than 20% of the pattern of the original plate) that is partly different from the original pattern shape of the mold pattern shape.
D: The pattern of the original plate that is the basis of the pattern shape of the mold is clearly different, or the film thickness of the pattern is 20% or more different from the pattern of the original plate.

<Evaluation of mold peelability (residue)>
The same operation as the pattern transfer accuracy evaluation was repeated 10 times using the same mold, and whether or not the composition component was adhered to the mold was observed with a scanning electron microscope and an optical microscope, and the peelability was evaluated as follows. did.
A: Adhesion of the curable composition to the mold was not recognized at all.
B: Slight adhesion of the curable composition was observed on the mold.
C: Adhesion of the curable composition of the mold was clearly recognized.

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

<Evaluation of light transmittance>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm, the mold was not pressure-bonded, and was exposed at an exposure amount of 240 mJ / cm ² in a nitrogen atmosphere, and then heated in an oven at 230 ° C. for 30 minutes. The film was cured. The cured film was measured for light transmittance at 400 nm with UV-2400PC manufactured by Shimadzu Corporation. The light transmittances of Examples 1 to 8 were all 97% or more, and were more transparent than the other samples. Moreover, all of Comparative Examples 1-4 were less than 90%.

  As can be seen from Table 4, the compositions of the examples containing the aromatic carboxylic acid alkenyl ester in the present invention and having a viscosity in the range of 3 to 18 mPa · S were obtained. The hardness was good. On the other hand, although the viscosity of the composition falls within 3 to 18 mPa · s, Comparative Example 1 using the benzoic acid allyl ester described in JP-A-10-251473 without using the aromatic carboxylic acid alkenyl ester in the present invention. The composition obtained was inferior in hardness and light transmittance of the obtained cured product. Further, Comparative Example 2 using diallyl phthalate and the polymeric silicon compound described in JP-A-2007-72374 exceeded the viscosity of 1000 Pa · s, and was inferior in pattern accuracy, peelability and light transmittance. It was. Although the viscosity of the composition falls within 3 to 18 mPa · s, the composition of Comparative Example 3 using an acrylate-based polymerizable monomer without using the aromatic carboxylic acid alkenyl ester in the present invention is peelable and light. The transmittance was inferior. Moreover, although the aromatic carboxylic acid alkenyl ester of the present invention was used, the composition of Comparative Example 4 having a viscosity exceeding 18 mPa · s was inferior in pattern accuracy and transmittance.

Claims (13)

A curable composition for nanoimprints, comprising an aromatic carboxylic acid alkenyl ester represented by the following general formula (1), wherein the composition has a viscosity of 3 to 18 mPa · s.

(In the formula, R ¹ represents an alkenyl group having 2 to 6 carbon atoms, R ² represents an alkenyl group having 2 to 6 carbon atoms or an alkenyloxy group having 2 to 6 carbon atoms, and Ar represents an aromatic hydrocarbon. N represents an integer of 1 or more, m represents an integer of 0 or more, and n + m is an integer of 2 or more.) The curable composition for nanoimprints according to claim 1, wherein the aromatic carboxylic acid alkenyl ester is represented by the following general formula (2) or the following general formula (3).

(In each formula, R ² represents an alkenyl group having 2 to 6 carbon atoms or an alkenyloxy group having 2 to 6 carbon atoms. N represents an integer of 1 or more, m represents an integer of 0 or more, and n + m is 2. (It is an integer above.)   The curable composition for nanoimprints according to claim 1, further comprising another polymerizable monomer different from the aromatic carboxylic acid alkenyl ester.   The curable composition for nanoimprints according to claim 3, wherein the other polymerizable monomer is a (meth) acrylate monomer.   Furthermore, a photoinitiator is included, The curable composition for nanoimprints of any one of Claims 1-4 characterized by the above-mentioned.   Furthermore, surfactant is included, The curable composition for nanoimprints of any one of Claims 1-5 characterized by the above-mentioned.   Furthermore, antioxidant is included, The curable composition for nanoimprints of any one of Claims 1-6 characterized by the above-mentioned.   The curable composition for nanoimprints according to any one of claims 1 to 7, which is a substantially solvent-free composition.   Content of an organic solvent is 3 mass% or less in all the compositions, The curable composition for nanoimprints of any one of Claims 1-8 characterized by the above-mentioned.   Hardened | cured material characterized by hardening the curable composition for nanoimprints of any one of Claims 1-9.   A member for a liquid crystal display device, comprising the cured product according to claim 10. Applying the curable composition for nanoimprints according to any one of claims 1 to 9 on a substrate to form a pattern forming layer;
Pressing the mold against the surface of the pattern forming layer;
Irradiating the pattern forming layer with light;
The manufacturing method of the hardened | cured material characterized by including.   Furthermore, the process of heating the said pattern formation layer irradiated with light is included, The manufacturing method of the hardened | cured material of Claim 12 characterized by the above-mentioned.