WO2009110536A1

WO2009110536A1 - Curable composition for nanoimprint, cured product using the same, method for producing the cured product, and member for liquid crystal display device

Info

Publication number: WO2009110536A1
Application number: PCT/JP2009/054134
Authority: WO
Inventors: 裕之米澤; 丘高柳
Original assignee: 富士フイルム株式会社
Priority date: 2008-03-06
Filing date: 2009-03-05
Publication date: 2009-09-11
Also published as: KR20100126728A; CN101959932A; JP2009209337A

Abstract

Disclosed is a curable composition for nanoimprint, which is characterized by containing a compound having an oxethane ring, a functional acid anhydride, a radically photopolymerizable monomer and a radical photopolymerization initiator. The curable composition for nanoimprint is also characterized in that the total content of compounds having a radically polymerizable functional group in the composition is 50-99.5% by mass. The composition excels in pattern precision, surface hardness, light transmittance and heat resistance after thermal curing.

Description

Curable composition for nanoimprint, cured product using the same, method for producing the same, and member for liquid crystal display device

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.

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 an uneven pattern on a resist. This is a technology that precisely deforms and transfers fine patterns. Once a mold is made, it is economical because it can be easily and repeatedly formed with fine structures such as nanostructures. In addition, it is a nano-processing technology with few harmful wastes and emissions, so it can be applied to various fields in recent years. 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 onto a polymer resin heated to a temperature higher than the glass transition temperature, and after cooling, the mold is released 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 laminated 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, an application example for manufacturing a high-density semiconductor integrated circuit will be described first. 2. Description of the Related Art In recent years, semiconductor integrated circuits have been miniaturized and integrated, and the photolithography apparatus has 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 a color filter substrate after forming a 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 a photocurable composition suitable for the formation of a permanent film (permanent resist) such as the transparent protective film or spacer using the nanoimprint method is demanded.

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 elements 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 are 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. Moreover, it is necessary to improve the adhesiveness between a resist and a base material (a board | substrate, a support body), improving the peelability between a mold and a 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.

In optical nanoimprint lithography, a liquid curable composition for optical nanoimprint is dropped onto a substrate such as a silicon wafer, quartz, glass, film, or other material such as a ceramic material, a metal, or a polymer, and approximately several tens nm to several It is applied with a film thickness of μm, a mold having fine irregularities with a pattern size of about several tens of nm to several tens of μm is pressed and pressurized, and the composition is cured by irradiating with light in the pressurized state. In general, a mold is released from the film to obtain a transferred pattern. Thus, when performing light irradiation in the state which pressurized the mold to the coating film, at least one of a base material or a mold needs to be transparent. Usually, light irradiation is generally performed from the mold side. In this case, an inorganic material such as quartz or sapphire that transmits UV light, a light-transmitting resin, or the like is often used as the mold material.

The optical nanoimprint method is (1) no heating / cooling process is required and high throughput is expected compared to the thermal nanoimprint method, and (2) imprinting at a low pressure is possible because a liquid composition is used. Major advantages include (3) no dimensional change due to thermal expansion, (4) the mold is transparent and easy to align, and (5) a robust three-dimensional crosslinked body is obtained after curing. It is done. It is particularly suitable for semiconductor micromachining applications where alignment accuracy is required and for micromachining applications in the field of flat panel displays.

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

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

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

The photo-curable resin applied to nanoimprint is roughly classified into radical polymerization type and ion polymerization type due to 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.

Further, Patent Documents 20 and 21 below disclose examples in which a photocurable resin containing a polymer having an isocyanate group is used for embossing for producing a relief hologram or a diffraction grating. Patent Document 22 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 photo-cationic 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 nanoimprinting containing a silicone monomer, a trifunctional acrylic monomer, and a photopolymerization initiator is applied on a silicone substrate, and high resolution is achieved by using a 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 23 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.

Non-patent literature 15 and patent literature 24 have reported the curable composition containing polysiloxane for nanoimprint applications. In addition, as a curable composition containing polysiloxane, Patent Document 25 reports a composition for producing an optical article by a stamper method.

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, flattening properties, There are many problems such as solvent resistance and reduction of outgas during heat treatment. When the nanoimprint curable composition is applied as a permanent film, the uniformity of the coating film, (2) transparency after heat treatment, and (3) scratch resistance, as in the case of a resist using a conventional acrylic resin, etc. Gender is important.

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 JP 2005-301289 A JP 2000-39713 A JP-A-6-43643 Japanese Patent Laid-Open No. 2004-240241 Japanese Patent Laid-Open No. 7-230165 JP 2000-181055 A JP 2004-94241 A JP-A-4-149280 JP-A-7-62043 JP 2001-93192 A JP 2005-8759 A JP 2003-165930 A JP 2007-84625 A International Publication WO99 / 22849 Pamphlet JP 2004-59820 A JP 2004-59822 A JP 2006-114882 A JP 2000-143924 A JP 2007-72374 A JP 2005-92099 A

As problems specific to the curable composition for optical nanoimprint, in addition to the performances (1) to (3), it is important to provide (4) a high elastic recovery rate as one of the mechanical properties. Further, when designing the composition of the curable composition for nanoimprint, in addition to the above points (1) to (4), at the same time, (5) ensuring the fluidity of the resist to the concave portion of the mold, It is necessary to consider that it is necessary to reduce the viscosity under the use of a small amount of solvent, and (6) that it can be easily peeled off from the mold after photocuring and does not adhere to the mold. The technical difficulty of product design is further increased.
As a result of investigation by the present inventors, it has been found that (4) a composition capable of obtaining a high elastic recovery rate can be designed by including polysiloxane in the composition.

As described above, curable compositions containing polysiloxane are reported in Non-Patent Document 15 and Patent Document 25 for nanoimprint applications. However, the compositions reported in these documents are both highly viscous. For this reason, when forming a structure by a nanoimprint method using a large-sized substrate, the pattern accuracy decreases due to a decrease in the fluidity of the resist (composition) in the concave portion of the mold, and further within the substrate (that is, Thickness variation (at the center and end of the substrate) becomes a problem. However, this problem is not disclosed in Non-Patent Document 15 and Patent Document 25.

Also, as described above, a composition for producing optical articles by a stamper method is reported in Patent Document 26 regarding a curable composition containing polysiloxane. In the stamper method, it is generally possible to form a structure using a composition having a high stamper pressure and a high viscosity. However, in the optical nanoimprint application, there arises a problem that the pattern accuracy is lowered and a thickness unevenness in the substrate surface.

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.

In order to solve the above-mentioned problems, the present invention is to provide a curable composition for nanoimprinting that is excellent in photocurability, and particularly suitable for a transparent protective film such as a flat panel display or a permanent film such as a spacer, Specifically, a curable composition for nanoimprints excellent in pattern accuracy, surface hardness, light transmittance and heat resistance after heat curing, a cured product using the same, a method for producing the same, and a member for a liquid crystal display device The purpose is to provide.

Based on the above problems, the inventors of the present invention have conducted extensive studies and found that the above problems can be solved by the following means.

[1] A compound containing a compound having an oxetane ring, a functional acid anhydride, a photoradical polymerizable monomer, and a photoradical polymerization initiator, and having a radical polymerizable functional group in the composition A curable composition for nanoimprints, wherein the total content is 50 to 99.5% by mass.

[2] The curable composition for nanoimprints according to [1], wherein the composition has a viscosity of 3 to 18 mPa · s at 25 ° C.

[3] The curable composition for nanoimprints according to [1] or [2], wherein the compound having an oxetane ring has a photoradically polymerizable functional group.

[4] The curable composition for nanoimprints according to any one of [1] to [3], wherein the functional acid anhydride has a radically polymerizable functional group.

[5] The curable composition for nanoimprints according to any one of [1] to [4], further comprising an antioxidant.

[6] The curable composition for nanoimprints according to any one of [1] to [5], wherein the content of the monomer containing a nitrogen atom in the composition is 5.0% by mass or less .

[7] As described in any one of [1] to [6], a light transmittance of 400 nm is 95% or more when a thin film having a thickness of 3.0 μm is formed by exposure and heating. A curable composition for nanoimprint.

[8] A cured product obtained by curing the curable composition for nanoimprints according to any one of [1] to [7].

[9] The cured product according to [8], wherein a light transmittance of 400 nm at a thickness of 3.0 μm is 95% or more.

[10] A liquid crystal display device member comprising the cured product according to [8].

[11] A step of applying the curable composition for nanoimprints according to any one of [1] to [7] 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.

[12] The method for producing a cured product according to [11], 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 nanoimprint excellent in the pattern accuracy after heat-curing, surface hardness, light transmittance, and heat resistance, the hardened | cured material using this, its manufacturing method, and the member for liquid crystal display devices 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.

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 this specification, “functional group” refers to a group involved in polymerization.
In addition, the nanoimprint referred to in the present invention refers to pattern transfer having a size of about several tens of nanometers to several tens of micrometers, and is not limited to nano-order ones.

[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”) includes a compound having an oxetane ring, a functional acid anhydride, a photoradical polymerizable monomer, a photo A radical polymerization initiator, and the total content of molecules having radical polymerizable functional groups in the composition is 50 to 99.5% by mass.
The composition of the present invention contains a compound having an oxetane ring and a functional acid anhydride that is a curing agent in addition to the photoradical polymerizable monomer and the photoradical polymerization initiator, so that it is photocurable. In addition, it has thermosetting properties. Thereby, after hardening a composition by light irradiation, the composition of this invention can raise surface hardness etc. more by heating by a heating process further.

Moreover, the curable composition for nanoimprints of the present invention can be widely used for optical nanoimprint lithography, and can have the following characteristics.
(1) Since the composition of the present invention is excellent in solution fluidity at room temperature, the composition easily flows into the cavity of the mold recess, and the atmosphere is difficult to be taken in. In any of the recesses, it is difficult for residues to remain after photocuring.
(2) The cured film after curing the composition of the present invention has excellent mechanical properties, excellent adhesion between the coating film and the substrate, and excellent peelability between the coating film and the mold. A good pattern can be formed because the pattern is not broken when the film is peeled off, and the surface of the coating film is not threaded to cause surface roughening (good pattern 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, 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 , Microreactors, nanobio devices, optical waveguides, can also be widely applied to manufacturing, such as an optical filter, photonic crystal.

(Content of compound having radical polymerizable functional group)
In the curable composition for nanoimprinting of the present invention, the total content of compounds having radically polymerizable functional groups in the composition is 50 to 99.5% by mass. The “compound having a radically polymerizable functional group” is a compound having a radically polymerizable functional group having an ethylenically unsaturated bond such as a (meth) acryl group, a vinyl group, or an allyl group. For example, when the compound having an oxetane ring in the present invention described later is oxetane (meth) acrylate, since the (meth) acryl group is a radical polymerizable functional group, it corresponds to the compound having the radical polymerizable functional group. To do.

When the total content of the compound having a radical polymerizable functional group in the composition of the present invention is less than 50% by mass, it cannot be sufficiently cured even by light irradiation, and the mold pattern cannot be accurately transferred. In addition, physical properties such as hardness of the cured film are insufficient. Further, when the total content of the compound having a radical polymerizable functional group in the composition of the present invention exceeds 95.5% by mass, additives such as a photo radical polymerization initiator and a surfactant do not function sufficiently. The pattern accuracy and the physical properties of the cured film are deteriorated. From the viewpoint of pattern accuracy and cured film physical properties, the total content of the compound having a radical polymerizable functional group in the composition of the present invention is preferably 60 to 99% by mass, and more preferably 70 to 98% by mass.

(Compound having oxetane ring)
The curable composition for nanoimprinting of the present invention contains a compound having an oxetane ring (hereinafter sometimes simply referred to as “oxetane compound”). Since the composition of the present invention contains a compound having an oxetane ring, excellent hardness can be obtained by heating.
The number of oxetane ring structures (oxetanyl groups) contained in the compound having an oxetane ring in the present invention is preferably 1 to 4, and more preferably 1 to 3, from the viewpoint of curing speed and cured film properties.
In the present invention, the total number of carbon atoms of the compound having an oxetane ring is preferably 5 to 50, and more preferably 5 to 20 from the viewpoint of reducing the viscosity of the composition.
The molecular weight of the compound having an oxetane ring in the present invention is preferably from 100 to 1,000, and more preferably from 100 to 400, from the viewpoint of reducing the viscosity of the composition.
In addition, the compound having an oxetane ring in the present invention preferably has a photoradically polymerizable functional group. Examples of the radical photopolymerizable functional group include a functional group having an ethylenically unsaturated bond, and a (meth) acryl group, a vinyl group, an allyl group, and a styryl group are preferable. The number of radically polymerizable groups contained in the compound having an oxetane ring in the present invention is preferably 1 to 4, more preferably 1 to 2, from the viewpoint of pattern accuracy during light irradiation and adhesion to the substrate. The compound having an oxetane ring contained in the composition of the present invention may be one type or two or more types. In the composition of the present invention, an oxetane compound having a photoradically polymerizable functional group and an oxetane compound not having this may be used in combination. When using together the compound (x) which has a photoradically polymerizable functional group, and the oxetane compound (y) which does not have this, as the content ratio (x: y, x reference | standard), pattern accuracy after light irradiation and From the viewpoint of suppressing volatilization of unreacted components during heating, 1/2 to 5/1 is preferable, and 1/1 to 2/1 is more preferable.

In the curable composition for nanoimprints of the present invention, the content of the compound having an oxetane ring in the entire composition is preferably 5 to 50% by mass from the viewpoint of pattern accuracy after light irradiation, and is 10 to 30% by mass. Further preferred. However, when the compound having an oxetane ring in the present invention has a photo-radical polymerizable functional group, the content thereof, as described above, considers the content of the compound having a radical polymerizable functional group in the composition of the present invention. Can be determined. At this time, the content of the oxetane compound having a photoradically polymerizable functional group is related to the content of the compound having another radical polymerizable functional group or the content of the oxetane compound having no photoradically polymerizable functional group. It is determined appropriately from the relationship.

Examples of the compound having an oxetanyl group in the present invention include 3-ethyl-3-hydroxymethyloxetane (trade name: OXT-101, manufactured by Toagosei Co., Ltd.), 1,4-bis [[(3-ethyl- 3-Oxetanyl) methoxy] methyl] benzene (trade name: OXT-121, manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (phenoxymethyl) oxetane (trade name: OXT-211, manufactured by Toagosei Co., Ltd.) ), Di [1-ethyl (3-oxetanyl)] methyl ether (trade name: OXT-221, manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (trade name: OXT-212, manufactured by Toagosei Co., Ltd.), 4,4′-bis [3-ethyl- (3-oxetanyl) methoxymethyl] biphenyl (trade name: ETERRNACOLL) XBP, manufactured by Ube Industries, Ltd.), silsesquioxane modified oxetane (trade name: OX-SQ, manufactured by Toagosei Co., Ltd.), oxetane (meth) acrylate (trade name: OXE-10, 30, Osaka Organic) Chemical Co., Ltd.).

(Functional acid anhydride)
The curable composition for nanoimprinting of the present invention contains a functional acid anhydride. The acid anhydride compound in the present invention functions as a curing agent for the compound having an oxetane ring. Since the composition of the present invention contains a functional acid anhydride, a high surface hardness can be obtained after heat curing.
In the present invention, the “functional acid anhydride” means a compound obtained by dehydration condensation of two molecules of oxo acid and chemically bonded to other functional groups by heating or the like.
Examples of the functional acid anhydride in the present invention include phthalic anhydrides, citraconic anhydrides, succinic anhydrides, propionic anhydrides, maleic anhydrides, acetic anhydrides, and the like, from the viewpoint of viscosity reduction and composition stability. Therefore, phthalic anhydrides and maleic anhydrides are preferable.

The total number of carbon atoms of the functional acid anhydride in the present invention is preferably 10 to 100, more preferably 10 to 50, from the viewpoint of reducing the viscosity of the composition.
The molecular weight of the functional acid anhydride in the present invention is preferably from 100 to 1,000, more preferably from 100 to 500, from the viewpoint of reducing the viscosity of the composition.

In addition, the functional acid anhydride in the present invention preferably has a radically polymerizable functional group. Examples of the photoradical polymerizable functional group include a functional group having an ethylenically unsaturated bond, and a (meth) acryl group, a vinyl group, an allyl group, and a styryl group are preferable. The number of radical photopolymerizable groups contained in the functional acid anhydride in the present invention is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of pattern accuracy during light irradiation and adhesion to the substrate. 1 type may be sufficient as the functional acid anhydride contained in the composition of this invention, and 2 or more types may be sufficient as it. Moreover, the composition of this invention may use together the functional acid anhydride which has a photoradically polymerizable functional group, and the functional acid anhydride which does not have this. When using together the compound (q) which has a radical photopolymerizable functional group, and the functional acid anhydride (w) which does not have this, as the content ratio (q: w, q reference | standard), after light irradiation From the viewpoint of pattern accuracy and suppression of volatilization of unreacted components during heating, 1/2 to 5/1 is preferable, and 1/1 to 2/1 is more preferable.

In the curable composition for nanoimprints of the present invention, the content of the functional acid anhydride in the entire composition is preferably 5 to 50% by mass, and preferably 10 to 30% by mass from the viewpoint of pattern accuracy after light irradiation. Further preferred. However, when the functional acid anhydride in the present invention has a photo-radical polymerizable functional group, the content thereof, as described above, considers the content of the compound having a radical polymerizable functional group in the composition of the present invention. Can be determined. At this time, the content of the functional acid anhydride having a photoradically polymerizable functional group is related to the content of a compound having another radical polymerizable functional group or a functional acid having no photoradically polymerizable functional group. It is determined appropriately from the relationship with the anhydride content.

In the curable composition for nanoimprints of the present invention, the content ratio (a: b, a basis) of the compound (a) having a oxetane ring and the functional acid anhydride (b) in the present invention is unreacted. From the viewpoint of minimizing the amount of functional groups, 3/1 to 1/3 is preferable, and 2/1 to 1/2 is more preferable.

Examples of the functional acid anhydride in the present invention include methyl-1,2,3,6-tetrahydrophthalic anhydride (trade name: Epicron B570, manufactured by Dainippon Ink and Chemicals), methyl-hexahydrophthalic anhydride. Acid (trade name: Epicron B650, manufactured by Dainippon Ink and Chemicals), methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride (trade name: MHAC-P, Hitachi Chemical) Kogyo Co., Ltd.), 4-methylhexahydrophthalic anhydride (trade name: Ricacid M H-700, manufactured by Shin Nippon Rika Co., Ltd.), citraconic anhydride, dodecene succinic anhydride (trade name: Ricacid DDSA, Shin Nippon Rika Co., Ltd.), glycerol bis (anhydrous trimellitate) monoacetate (trade name: Ricacid MTA-10, Shin Nippon Rika Co., Ltd.), Japan Quinhard-200 (trade name) manufactured by ON Co., Ltd., EpiCure YH-306 (trade name) manufactured by Japan Epoxy Resin Co., Ltd., Aldrich Reagent (P25205, 294152, B9750, B4600, 41287, N818, N1607, 3307376 ) And the like.

(Photoradical polymerizable monomer)
The curable composition for nanoimprinting of the present invention contains a photoradical polymerizable monomer. Since the composition of the present invention contains a photo-radically polymerizable monomer, good pattern accuracy can be obtained after light irradiation. In the present invention, the “photo radical polymerizable monomer” means a monomer capable of causing a polymerization reaction by light irradiation to form a high molecular weight product.

The main function of the photoradically polymerizable monomer used in the present invention is appropriately selected for the purpose of adjusting the viscosity of the composition and the mechanical properties of the cured film. From the viewpoint of adjusting the viscosity of the composition, it is preferable to use a low-viscosity photo-radically polymerizable monomer. In order to improve the pattern accuracy of the cured product, the viscosity of the composition is usually preferably 18 mPa · s or less, and for that purpose, a polymerizable monomer having a viscosity as low as possible is used. preferable. Since the viscosity of photoradical polymerizable monomers is related to molecular weight, intermolecular interaction, etc., the reduction in viscosity of photoradical polymerizable monomers can be achieved by taking low molecular weight and low molecular interactions into consideration. Can be achieved.

The radical photopolymerizable monomer used in the present invention is preferably a compound having a viscosity of 100 mPa · s or less, more preferably 50 mPa · s or less, particularly preferably 10 mPa · s or less, from the viewpoint of adjusting the viscosity of the composition. preferable.
The weight average molecular weight of the photoradically polymerizable monomer in the present invention is preferably 500 or less, more preferably 100 to 400, and particularly preferably 100 to 300, from the viewpoint of adjusting the viscosity of the composition.

Examples of the photoradically polymerizable functional group possessed by the photoradically polymerizable monomer in the present invention include a functional group having an ethylenically unsaturated bond, such as (meth) acryl group, vinyl group, allyl group, styryl. Groups are preferred. 1 type may be sufficient as the radical photopolymerizable monomer contained in the composition of this invention, and 2 or more types may be sufficient as it. Further, the composition of the present invention comprises a photoradical polymerizable monomer having a photoradically polymerizable functional group and a photoradical polymerizable monomer having no photoradical polymerizable functional group (for example, a polymerizable monomer having a cationic polymerizable group). (Mer) may be used in combination.

Also, from the viewpoint of imparting mechanical properties to the cured film, it is preferable to use a bifunctional or higher polyfunctional monomer. Such a polyfunctional monomer inevitably has a high molecular weight and thus has a high viscosity, and the pattern accuracy may be lowered by increasing the viscosity of the composition. Therefore, the polymerizable monomer used in the present invention is a combination of a low-viscosity monomer for adjusting viscosity and a polyfunctional monomer for imparting mechanical properties of a cured film, or an oxetane compound or a functional acid anhydride in the present invention. It is selected comprehensively considering the combination of objects.

In the curable composition for nanoimprints of the present invention, the content of the photoradically polymerizable monomer in the entire composition is preferably 20 to 90% by mass, and preferably 30 to 70% by mass from the viewpoint of pattern accuracy after light irradiation. % Is more preferable. However, the content of the photoradical polymerizable monomer in the present invention is determined in consideration of the content of the compound having a radical polymerizable functional group in the composition of the present invention as described above.

In the present invention, only one kind of silsesquioxane compound may be contained, or two or more kinds thereof may be contained. In the composition of the present invention, the silsesquioxane compound is preferably contained in a proportion of 1 to 40% by mass, more preferably 1 to 20% by mass. By setting it as such a range, the composition viscosity and the mechanical characteristic of a cured film can be made compatible.

Examples of the photoradical polymerizable monomer in the present invention include a polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group (monofunctional polymerizable unsaturated monomer). Specifically, 2-acryloyloxyethyl phthalate, 2-acryloyloxy 2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (Meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acrylic acid dimer, benzyl (meth) acrylate, butanediol mono (meth) acrylate Rate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, ethylene oxide modified (hereinafter referred to as “EO”) cresol (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) ) Acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclohentanyl (meth) acrylate, dicyclo Pentanyloxyethyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate Methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, Nonylphenoxy polypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, epichlorohydrin (hereinafter referred to as “ECH”) modified phenoxy acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol ( (Meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene Glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, tert-butyl (meta ) Acrylate, tribromophenyl (meth) acrylate, EO-modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate, p-isopropenylphenol, styrene, α-methylstyrene, acrylonitrile, vinylcarbazole, ethyl oxetanylmethyl acrylate Illustrated.
Among these, acrylate monomers are particularly preferably used in the present invention.

In addition, as the photoradical polymerizable monomer in the present invention, a bifunctional polymerizable unsaturated monomer having two ethylenically unsaturated bond-containing groups can also be preferably used. Examples of the bifunctional polymerizable unsaturated monomer include diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di (meth) 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 bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) Acrylate, ECH-modified hexahydrophthalic acid diacrylate, hydroxypivalate 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 (meta ) Acrylate, poly (propylene glycol-tetramethylene glycol) di (meth) acrylate, polyester (di) acrylate, poly Tylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ECH-modified propylene glycol di (meth) acrylate, silicone di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate , Tricyclodecane dimethanol (di) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, EO modified tripropylene glycol di (meth) acrylate, triglycerol di (meth) Acrylate, dipropylene glycol di (meth) acrylate, divinylethyleneurea, divinylpropyleneurea, dicyclopentenyl (meth) acrylate, di Black pentenyl oxyethyl (meth) acrylate, dicyclopentanyl di (meth) acrylate, 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, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl di (meth) acrylate and the like are preferably used in the present invention. It is done.

As the radical photopolymerizable monomer in the present invention, a polyfunctional polymerizable unsaturated monomer having three or more ethylenically unsaturated bond-containing groups can also be preferably used. Examples of the polyfunctional polymerizable unsaturated monomer include ECH-modified glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, pentaerythritol triacrylate, and EO-modified phosphorus. Acid triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, tris (acryloxy) Ethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol Roxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol ethoxytetra (Meth) acrylate, pentaerythritol tetra (meth) acrylate, etc. are mentioned.

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.

As the radical photopolymerizable monomer used in the present invention, a vinyl ether compound may be used.
The vinyl ether compound can be appropriately selected from known ones such as 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, Raethylene 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 Tris [4- (2-vinyloxy ethoxy) phenyl] ethane, bisphenol A divinyloxyethyl carboxyethyl ether.

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

In addition, as the radical photopolymerizable monomer used in the present invention, a styrene derivative can also be employed. Examples of the styrene derivative include p-methoxystyrene, p-methoxy-β-methylstyrene, p-hydroxystyrene, and the like.

Other styrene derivatives that can be used in combination with the monofunctional polymer of the present invention include, for example, styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, Examples include p-methoxy-β-methylstyrene, p-hydroxystyrene, and the like. Furthermore, in the present invention, vinyl naphthalene derivatives can also be used. For example, 1-vinylnaphthalene, α-methyl-1-vinylnaphthalene, β-methyl-1-vinylnaphthalene, 4-methyl-1-vinylnaphthalene 4-methoxy-1-vinylnaphthalene and the like.

In addition, for the purpose of improving the mold release and coating properties, trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, perfluorobutyl-hydroxypropyl ( Compounds having a fluorine atom such as (meth) acrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate and tetrafluoropropyl (meth) acrylate are also used in the present invention. It can be used as a photoradical polymerizable monomer or used in combination with the photoradical polymerizable monomer in the present invention.

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

Next, in the present invention, a compound having a radical polymerizable group and an oxetane ring, a polymerizable acid anhydride, a photo radical polymerizable monomer (hereinafter, these are collectively referred to as “polymerizable unsaturated monomer”). A preferable blend form of (some) will be described.
The monofunctional polymerizable unsaturated monomer is usually used as a reactive diluent and is effective in reducing the viscosity of the composition of the present invention. Usually, 10 mass of the total polymerizable unsaturated monomer. % Or more is added. Preferably, it is added in the range of 20 to 80% by mass, more preferably 25 to 70% by mass, and particularly preferably 30 to 60% by mass.
Since the monofunctional polymerizable unsaturated monomer is better as a reactive diluent, it is preferable to add 10% by mass or more of the total polymerizable unsaturated monomer.
The monomer having two unsaturated bond-containing groups (bifunctional polymerizable unsaturated monomer) is preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 80% by mass or less of the total polymerizable unsaturated monomer. Preferably, it is added in a range of 70% by mass or less. The ratio of the monofunctional and bifunctional polymerizable unsaturated monomer is preferably 1 to 95% by mass, more preferably 3 to 95% by mass, and particularly preferably 5 to 90% by mass of the total polymerizable unsaturated monomer. It is added in the range of mass%. The ratio of the polyfunctional polymerizable unsaturated monomer having 3 or more unsaturated bond-containing groups is preferably 80% by mass or less, more preferably 70% by mass or less, and particularly preferably the total polymerizable unsaturated monomer. Is added in a range of 60% by mass or less. Since the viscosity of a composition can be lowered | hung by making the ratio of the polymerizable unsaturated monomer which has 3 or more of polymerizable unsaturated bond containing groups into 80 mass% or less, it is preferable.

(Photo radical polymerization initiator)
The curable composition for nanoimprints of the present invention contains a radical photopolymerization initiator. The composition of this invention can make the pattern precision after light irradiation favorable by including the radical photopolymerization initiator which starts radical polymerization reaction by light irradiation. Photoradical polymerization initiator The content of the photoradical polymerization initiator used in the present invention is, for example, preferably from 0.1 to 15 mass%, more preferably from 0.2 to 12 mass%, based on the entire composition. Particularly preferred is 0.3 to 10% by mass. When using 2 or more types of photoinitiators, the total amount becomes the said range.
When the ratio of the radical 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 ratio of the radical photopolymerization initiator is 15% by mass or less, the light transmittance, the colorability, the handleability and the like tend to be improved, which is preferable. Until now, various addition amounts of preferred photopolymerization initiators and / or photoacid generators have been studied for ink jet compositions and dye display / color pigment compositions for liquid crystal display color filters, but for nanoimprinting. A preferred photopolymerization initiator and / or photoacid generator addition amount for the curable composition for photo nanoimprint lithography is not reported. That is, in a system containing dyes and / or pigments, these may act as radical trapping agents, affecting the photopolymerizability and sensitivity. 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 radical photopolymerization initiator used in the present invention, a compound having activity with respect to the wavelength of the light source to be used is blended to generate an appropriate active species.

As the radical photopolymerization initiator used in the present invention, for example, a commercially available initiator can be used. As these examples, for example, those described in paragraph No. 0091 of JP-A No. 2008-105414 can be preferably used.

Furthermore, in addition to the radical photopolymerization initiator, a photosensitizer can 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 Polymers 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.

(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 in the total composition, preferably 0.002 to 4% by mass, and more preferably 0.005 to 3% by mass. It is. When using 2 or more types of surfactant, the total amount becomes the said range. The total amount is in 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 mold transfer characteristics are hardly deteriorated due to excessive surfactant.
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 (all OMNOVA Solutions, Inc.), trade names FT250, FT251, DFX18 (all manufactured by Neos), trade names Unidyne DS-401, DS-403, DS-451 (all 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.).

(Antioxidant)
Furthermore, it is preferable that the curable composition for nanoimprints of the present invention contains an antioxidant. The content of the antioxidant used in the present invention is, for example, 0.01 to 10% by mass, preferably 0.2 to 5% by mass in the total composition. 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. 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 antioxidants include trade names “Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Geigy Co., Ltd.), trade names“ Antigene P, 3C, FR, Sumilizer S, and Sumilizer GA80 (Sumitomo Chemical Industries, 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 photo-radical polymerizability include various acrylate oligomers such as ester acrylate, polyurethane acrylate, polyether acrylate, and epoxy acrylate, and hydrolysis condensation products of trimethoxysilylpropyl acrylate. The addition amount of the oligomer component is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, further preferably 0 to 10% by mass, and most preferably 0 to 5% by mass with respect to the component excluding the solvent of the composition. % By mass.
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 from 2,000 to 100,000, more preferably from 5,000 to 50,000, from the viewpoint of compatibility with the polymerizable compound. The addition amount of the polymer component is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, further 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. 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 releasability, 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 mold release agent has particularly good releasability from the mold when combined with the photo-curable resin used in the present invention, and the phenomenon of taking a plate 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.

The modified silicone oil preferably has an 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 blended 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 repellency when the composition is applied. 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, γ-chloropropylmethyldiethoxysilane, and the like.

Examples of the titanium coupling agent include isopropyl triisostearoyl titanate, isopropyl tridodecyl benzene sulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite). ) Titanate, tetra (2,2-diallyloxymethyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacryliso Stearoyl titanate, isopropyl isostearoyl diacryl titanate, Sopuropirutori (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, and 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 organometallic coupling agent can be arbitrarily blended at a ratio of 0.001 to 10% by mass in the total solid content of the curable composition for nanoimprinting of the present 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 the curable composition for nanoimprints of the present invention, a polymerization inhibitor may be blended in order to improve storage stability and the like. Examples of the polymerization inhibitor include phenols such as hydroquinone, tert-butylhydroquinone, catechol and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines; 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 nanoimprinting of the present invention. Commercially available products of the ultraviolet absorber include Tinuvin P, 234, 320, 326, 327, 328, 213 (manufactured by Ciba Geigy Co., Ltd.), Sumsorb 110, 130, 140, 220, 250, 300, 320, 340, 350, 400 (manufactured by Sumitomo Chemical Co., Ltd.) and the like. The ultraviolet absorber is preferably blended arbitrarily in a proportion of 0.01 to 10% by mass with respect to the total amount of the curable composition for optical nanoimprint.

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

In the curable composition for nanoimprints of the present invention, a plasticizer can be added 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 nanoimprints 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, organophosphorus 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.

In the case of curing the composition of the present invention, a thermal polymerization initiator can be added as necessary. 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 8.0% by mass or less, more preferably 6.0% by mass or less, and still more preferably 4.0% by mass or less. In order to obtain the effect, the addition of the thermal polymerization initiator is preferably 3.0% by mass or more.

In the curable composition for nanoimprints of the present invention, a photobase generator may be added as necessary for the purpose of adjusting the pattern shape, sensitivity, and the like. Examples of the photobase generator include 2-nitrobenzylcyclohexyl carbamate, 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. As the pigment that can be used in the present invention, for example, those described in paragraph No. 0121 of JP-A No. 2008-105414 can be preferably used. The colorant is preferably blended in a proportion 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 have an average particle size of preferably 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 Resin Chemical 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 cure 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).

The curable composition for nanoimprints of the present invention preferably has a water content of 2.0% by mass or less, more preferably 1.5% by mass, and even more preferably 1.0% by mass or less at the time of preparation. 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.

Also, a solvent can be used in the curable composition for nanoimprinting of the present invention. The content of the organic solvent is preferably 3% by mass or less in the entire composition. That is, since the composition of the present invention preferably contains other monofunctional and / or bifunctional monomers as described above as reactive diluents, the organic solvent for dissolving the components of the composition of the present invention is It is not always necessary to contain. In the composition of the present invention, the content of the organic solvent is preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably not contained. 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.

The surface tension of the curable composition for nanoimprinting of the present invention is preferably in the range of 18 to 30 mN / m, and more preferably in the range of 20 to 28 mN / m. By setting it as such a range, the effect of improving surface smoothness is acquired.
In addition, the moisture content at the time of preparation of the curable composition for nanoimprinting 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.

(Viscosity of curable composition for nanoimprinting of the present invention)
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 nanoimprints of the present invention preferably has a viscosity at 25 ° C. of 3 to 18 mPa · s, more preferably 5 to 15 mPa · s, and particularly preferably 7 to 12 mPa · s. By setting the viscosity of the composition of the present invention to 3 mPa · s or more, there is a tendency that problems of substrate coating suitability and a decrease in mechanical strength of the film hardly occur. Specifically, by setting the viscosity to 3 mPa · s or more, it is preferable that unevenness on the surface is generated during the application of the composition or the composition can be prevented from flowing out of the substrate during the application. A composition having a viscosity of 3 mPa · s or more is also easier to prepare than a composition having a viscosity of less than 3 mPa · s. On the other hand, by setting the viscosity of the composition of the present invention to 18 mPa · s or less, even when a mold having a fine concavo-convex pattern is adhered to the composition, the composition flows into the cavity of the concave portion of the mold, and the atmosphere Is less likely to be taken in, so that it is difficult to cause bubble defects, and it is difficult for residues to remain after photocuring in the mold convex portion. Further, when the viscosity of the composition of the present invention is 18 mPa · s or less, the viscosity hardly affects the formation of a fine pattern.
Generally, the viscosity of the composition can be adjusted by blending 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, it is preferable to adjust the viscosity by adding a composition having a single viscosity of 5.0 mPa · s or less.

(Light transmittance of cured product)
The nanoimprint curable composition of the present invention preferably has a 400 nm light transmittance of 95% or more when a thin film (cured product) having a thickness of 3.0 μm is formed by exposure and heating. Here, the light transmittance at 400 nm means the light transmittance at a wavelength of 400 nm. The 400 nm light transmittance is more preferably 97% or more.
The 400 nm light transmittance can be measured by, for example, “UV-2400PC” manufactured by Shimadzu Corporation.

From the viewpoint of improving the light transmittance (400 nm light transmittance) of the cured product (suppressing a decrease in light transmittance due to yellowing), the curable composition for nanoimprinting of the present invention contains nitrogen atoms in the composition. The content of the monomer to be contained is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less.

The light transmittance (400 nm light transmittance) can also be improved by adding the above-mentioned antioxidant to the composition of the present invention.

[Method for producing cured product]
Next, the formation method of the hardened | cured material (especially fine uneven | corrugated pattern) using the curable composition for nanoimprints of this invention is demonstrated. A step of applying the curable composition for nanoimprinting of the present invention on a substrate or a support (base material) to form a pattern forming layer, a step of pressing a mold against the surface of the pattern forming layer, and the pattern forming layer A fine uneven | corrugated pattern can be formed by hardening the composition of this invention through the process of irradiating light. Particularly 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. That is, the curable composition for nanoimprints of the present invention is preferably cured by light and heat.
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.

As an application of the curable composition for nanoimprints of the present invention, the composition of the present invention is applied on a substrate or a support, and a layer comprising the composition is exposed, cured, and dried (baked) as necessary. Thus, a permanent film such as an overcoat layer or an insulating film can be produced.

In permanent films (resist for structural members) used in liquid crystal displays (LCDs), it is desirable to avoid contamination of metal or organic ionic impurities in the resist as much as possible so as not to hinder the operation of the display. The concentration is 1000 ppm or less, preferably 100 ppm 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. It can be formed by coating by a gravure coating method, an extrusion coating method, a spin coating method, a slit scanning method or the like. In addition, the film thickness of the pattern forming layer comprising the composition of the present invention is about 0.05 to 30 μm, although it varies depending on the intended use. 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, for example between a base material and the pattern formation layer which consists of a composition of this invention. Thereby, since the pattern formation layer and the substrate are not in direct contact with each other, it is possible to prevent adhesion of dust to the substrate, damage to the substrate, and the like.

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, SOG (spin on glass glass), polymer film such as polyester film, polycarbonate film, polyimide film, TFT array substrate, PDP electrode plate, glass or 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. Furthermore, as described later, as the substrate, a light transmissive or non-light transmissive material can be selected according to the combination with the mold or the like.

Next, in the method for producing a cured product of the present invention, in order to transfer the pattern to the pattern forming layer, a mold is pressed against the surface of the pattern forming layer. Thereby, the fine pattern previously formed on the pressing surface of the mold can be transferred to the pattern forming layer.

In optical nanoimprint lithography using the curable composition for nanoimprinting of the present invention, a light-transmitting material is selected for at least one of a molding material and / or a substrate. 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.

The non-light transmissive mold material used in the case of using the transparent substrate of the present invention is not particularly limited as long as it has a predetermined strength. Specific examples include ceramic materials, deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicone, silicone nitride, polysilicon, silicone oxide, and amorphous silicone. There are no particular restrictions. 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 that has been subjected to a release treatment in order to improve the releasability 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. Moreover, it is also 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 manufacturing method of the hardened | cured material of this invention, the irradiation amount of the light irradiation in the process of irradiating light to the said pattern formation layer should just be sufficiently larger than the irradiation amount required for hardening. 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.
Moreover, in the photoimprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually room temperature, but 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. In the method for producing a cured product of the present invention, a preferable degree of vacuum at the time of light irradiation is in 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).

In the exposure, it is desirable that the exposure illuminance is in the range of 1 mW / cm ² to 50 mW / cm ² . By setting it to 1 mW / cm ² or more, the exposure time can be shortened, so that productivity is improved. By setting it to 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 . When it is 5 mJ / cm ² or more, the exposure margin becomes narrow, photocuring becomes insufficient, and problems such as adhesion of unreacted materials to the mold can be prevented. Also. When the exposure amount is 1000 mJ / cm ² or less, deterioration of the permanent film due to decomposition of the composition can be suppressed.
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 method for producing a cured product of the present invention, it is preferable to include a step (post-baking step) in which the pattern forming layer is cured by light irradiation and then further cured by applying heat to the cured 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. The heat for heat-curing the composition of the present invention after light irradiation is preferably 150 to 280 ° C, more preferably 200 to 250 ° C. The time for applying heat is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.

In the present invention, the light irradiation in the photoimprint lithography may be sufficiently larger than the irradiation amount necessary for curing. The amount of irradiation necessary for curing is determined by examining the consumption of unsaturated bonds of the curable composition for optical nanoimprint lithography and the tackiness of the cured film.

In the photoimprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually room temperature, but the light irradiation may be performed while heating 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 reactivity decrease due to oxygen mixing, and improving the adhesion between the mold and the curable composition for optical nanoimprint lithography. It may be irradiated with light. In the present invention, a preferable degree of vacuum is in the range of 10 ⁻¹ Pa to normal pressure.

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

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, the permanent film is bottled in a container such as a gallon bottle or a coated bottle after manufacture, and is transported and stored. In this case, in order to prevent deterioration, the container is filled with inert nitrogen or argon. It may be replaced. 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 at a level where the reaction does not proceed.

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

As shown in Tables 1 and 2 below, in addition to the oxetane compound, functional anhydride, and polymerizable monomer, the following photo radical polymerization initiator P-1, the following surfactants W-1 and W-2, The following antioxidants A-1 and A-2 were added to prepare a curable composition for nanoimprinting. In addition, the numerical value (except a viscosity) in a table | surface is the mass%.

<Oxetane compound>
O-1: 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Co., Ltd .: OXT-101)
O-2: Oxetane acrylate (Osaka Organic Chemical Co., Ltd .: OXE-10)

<Functional anhydride>
H-1: Methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride (manufactured by Hitachi Chemical Co., Ltd .: MHAC-P)
H-2: Anhydride acrylate (manufactured by Sigma-Aldrich Japan Co., Ltd .: Aldrich reagent 330736)

<Photoradical polymerizable monomer>
M-1: benzyl acrylate (Osaka Organic Chemical Co., Ltd .: Biscote # 160)
M-2: Neopentyl glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd .: KARAYAD NPGDA)
M-3: trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd .: Aronix M309)

<N atom-containing polymerizable monomer>
N-1: N-vinylformamide (Arakawa Chemical Industries, Ltd .: Beam Set 770)

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

<Surfactant>
W-1: Non-fluorinated surfactant (manufactured by Takemoto Yushi Co., Ltd .: Pionein D6315)
W-2: Fluorosurfactant (Dainippon Ink & Chemicals, Inc .: MegaFuck F780F)

<Antioxidant>
A-1: Sumilyzer GA80 (manufactured by Sumitomo Chemical Co., Ltd.)
A-2: ADK STAB AO503 (Adeka Japan Co., Ltd.)

Of the above compounds, 0-2, H-2, M-1, M-2, M-3, and N-1 correspond to compounds having a radical polymerizable functional group. “Amount” indicates the content of the compound having a radical polymerizable functional group in the entire composition.

[Evaluation of curable composition for nanoimprint]
About the composition of each Example and the comparative example, it measured and evaluated in accordance with the following evaluation method about the viscosity, pattern precision, peelability, film | membrane reduction, hardness, and the transmittance | permeability. The results are shown in Tables 3 and 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 rotation speed at the time of measurement is 100 rpm for 0.5 mPa · s or more and less than 5 mPa · s, 50 rpm for 5 mPa · s or more and less than 10 mPa · s, 20 rpm for 10 mPa · s or more and less than 30 mPa · s, and 30 mPa · s. More than s and less than 60 mPa · s was carried out at 10 rpm, more than 60 mPa · s and less than 120 mPa · s was carried out at 5 rpm, and more than 120 mPa · s was carried out at 1 rpm or 0.5 rpm.

<Observation of pattern accuracy>
About each composition. It spin-coated on the glass substrate so that it might become a film thickness of 3.0 micrometers. The spin-coated coated base film was set in a nanoimprint apparatus using a high pressure mercury lamp (lamp power: 2000 mW / cm ² ) manufactured by ORC as a light source. The mold pressure was 0.8 kN and the degree of vacuum during exposure was 10 Torr ((about 1. As a mold under the condition of 33 × 10 ⁴ Pa), polydimethylsiloxane having a line / space pattern of 10 μm and a groove depth of 4.0 μm (“SILPOT184” manufactured by Toray Dow Corning Co., Ltd.) is 80 ° C. The product was pressed using a material made of a material cured in 60 minutes, and further exposed from the surface of the mold under the condition of 240 mJ / cm ^2. 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 pattern shape after the transfer was observed with a scanning electron microscope and an optical microscope, and the pattern shape was evaluated according to the following criteria.
A: Almost the same as the pattern of the original plate that is the basis of the pattern shape of the mold.
◯: There is a part (a range of less than 10% from the original pattern) that is partly different from the original pattern shape of the mold pattern shape.
Δ: 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.
X: The pattern pattern of the mold is clearly different from the original pattern, or the film thickness of the pattern is 20% or more different from the original pattern.

<Evaluation of film reduction>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm, and the mold was not subjected to pressure bonding, and was exposed at an exposure amount of 240 mJ / cm ² in a nitrogen atmosphere. Thereafter, it was cured by heating in an oven at 230 ° C. for 30 minutes. The film thickness before and after baking in an oven was measured, the reduction rate was determined, and the reduction rate (film reduction) of the film due to heating was evaluated according to the following criteria.
◎: Reduction rate is less than 5% ○: Reduction rate is 5% or more and less than 10% △: Reduction rate is 10% or more, less than 15% ×: Reduction rate is 15% or more

<Evaluation of pencil hardness>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm, and the mold was not subjected to pressure bonding, and was exposed at an exposure amount of 240 mJ / cm ² in a nitrogen atmosphere. Thereafter, pencil hardness was evaluated by a method in accordance with “JIS K5600-5-4” using a film cured by heating at 230 ° C. for 30 minutes in an oven.
◎: 4H or more ○: 3H
Δ: 2H
X: Less than 2H

<Evaluation of light transmittance (colorability)>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm, and the mold was not subjected to pressure bonding, and was exposed at an exposure amount of 240 mJ / cm ² in a nitrogen atmosphere. Thereafter, the film cured by heating at 230 ° C. for 30 minutes in an oven was measured for transmittance at 400 nm using “UV-2400PC” manufactured by Shimadzu Corporation.
A: The transmittance was 97% or more.
○: The transmittance was 95% or more and less than 97%.
Δ: The transmittance was 90 or more and less than 95%.
X: The transmittance was less than 90.

As can be seen from Table 3, all the compositions of the examples had good pattern accuracy and light transmittance, and had a high residual film ratio (film reduction) and hardness due to heating. Moreover, it was found from comparison between Example 9 and Example 10 that the N atom-containing monomer is 5.0% by mass or less and is more excellent in light transmission (coloring). Moreover, it turned out that the direction which contains antioxidant is excellent in light transmittance (coloring) from the comparison with Example 11 and another Example.

Further, as can be seen from Table 4, it was found that Comparative Examples 1 and 2, which did not contain a functional acid anhydride or a compound having an oxetane ring, had a particularly high rate of film reduction after heating. Moreover, the comparative example 3 which does not contain photoradically polymerizable monomers other than the compound which has an oxetane ring, and an acid anhydride had various performance deteriorated. Similarly, in Comparative Example 4 and Comparative Example 5, it can be seen that various performances are deteriorated because the content of the compound containing a radical polymerizable functional group is too small. In particular, in Comparative Example 4, imprintability is deteriorated because the viscosity of the composition is too high. In Comparative Example 6, since no radical photopolymerization initiator is contained, curing is insufficient and various performances are deteriorated.

Claims

The total content of the compound having a radical polymerizable functional group in the composition containing a compound having an oxetane ring, a functional acid anhydride, a radical photopolymerizable monomer, and a radical photopolymerization initiator. Is a curable composition for nanoimprints, characterized in that is from 50 to 99.5% by mass.
The curable composition for nanoimprints according to claim 1, wherein the viscosity of the composition is 3 to 18 mPa · s at 25 ° C.
The curable composition for nanoimprints according to claim 1 or 2, wherein the compound having an oxetane ring has a photoradically polymerizable functional group.
The curable composition for nanoimprints according to any one of claims 1 to 3, wherein the functional acid anhydride has a photoradically polymerizable functional group.
The curable composition for nanoimprints according to any one of claims 1 to 4, further comprising an antioxidant.
The curable composition for nanoimprints according to any one of claims 1 to 5, wherein the content of the monomer containing a nitrogen atom in the composition is 5.0% by mass or less.
The curable composition for nanoimprints according to any one of claims 1 to 6, wherein when a thin film having a thickness of 3.0 µm is formed by exposure and heating, the light transmittance of 400 nm is 95% or more. object.
A cured product obtained by curing the curable composition for nanoimprints according to any one of claims 1 to 7.
The cured product according to claim 8, wherein the light transmittance at 400 nm at a thickness of 3.0 μm is 95% or more.
A member for a liquid crystal display device, comprising the cured product according to claim 8.
Applying a nanoimprint curable composition according to any one of claims 1 to 7 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 manufacturing method of the hardened | cured material of Claim 11 including the process of heating the said pattern formation layer irradiated with light.