KR20090027169A - Curable composition for optical nanoimprint, a cured article and a method for making the same - Google Patents

Abstract

A curable composition for optical nanoimprint is provided to ensure photo-urable property, optical transmission, strippability, and pattern precision and to be desirable in a permanent film including the flat panel display. A curable composition for optical nanoimprint comprises (A) a monomer having two kinds of curable functional groups having different reactivity in the same molecule, (B) surfactant, and (C) antioxidant. At least one of the curable functional groups is alpha,beta-unsaturated ester group. The viscosity of the curable composition for optical nanoimprint is in range of 3 ~ 18 mPa.s.

Description

Curable composition for nanoimprint, hardened | cured material, and its manufacturing method {CURABLE COMPOSITION FOR OPTICAL NANOIMPRINT, A CURED ARTICLE AND A METHOD FOR MAKING THE SAME}

This invention relates to the curable composition for nanoimprints, hardened | cured material, its manufacturing method, the member for liquid crystal display devices using this hardened | cured material, and its manufacturing method.

The nanoimprint method develops an embossing technique that is well known in optical disk manufacturing, presses a mold original (commonly referred to as a mold, a stamper, or a template) in which a pattern of irregularities is formed, and mechanically deforms the micro pattern by pressing it into a resist. It is the technique to transfer precisely. Once a mold has been manufactured, it is economical as it is possible to simply and repeatedly mold microstructures such as nanostructures, and is a nano-processing technology with less harmful wastes and discharges. have.

In the nanoimprint method, when a thermoplastic resin is used as a work material (S. Chou et al .: Appl. Phys. Lett. Vol. 67, 3114 (1995)) and when a curable composition for photo nanoimprint is used (M. Colbun et al, Proc. SPIE, Vol. 3676, 379 (1999)). In the case of thermal nanoimprint, the microstructure is transferred to the resin on the substrate by pressing a mold on a polymer resin heated to a glass transition temperature or higher and releasing the mold after cooling. Since it is applicable also to various resin materials and glass materials, application to various aspects is anticipated. For example, US Pat. No. 5,772,905 and US Pat. No. 5,956,216 disclose methods of nanoimprint in which nanopatterns are inexpensively formed using thermoplastic resins.

On the other hand, in the optical nanoimprint system in which light is irradiated through the transparent mold and the photocurable curable composition for optical nanoimprint is photocured, imprint at room temperature becomes possible. Recently, new developments such as a nanocasting method combining both of these advantages and a reversal imprint method for producing a three-dimensional laminated structure have also been reported. In such a nanoimprint method, the following applications are considered. Firstly, the molded shape itself has a function and can be applied as various nanotechnology element parts or structural members, and is applicable to various micro-nano optical elements, high-density recording media, optical films, and flat panel displays. Structural member etc. are mentioned. Secondly, it is intended to build a laminated structure by simultaneous integral molding of micro and nano structures or simple interlayer positioning, and to apply them to the production of μ-TAS or biochips. Third, it is intended to be applied to the manufacture of high density semiconductor integrated circuits, to liquid crystal display transistors, or the like instead of conventional lithography by high precision positioning and high integration. In recent years, there has been an active response to the practical use of the nanoimprint method for these applications.

As an application example of the nanoimprint method, first, an application example to the manufacture of high density semiconductor integrated circuits will be described. In recent years, semiconductor integrated circuits have progressed in miniaturization and integration, and high precision of photolithography apparatuses has been advanced as a pattern transfer technique for realizing the microfabrication. However, processing methods have approached the wavelength of light exposure light sources, and lithography techniques have also approached their limits. For this reason, instead of lithography technology, an electron beam drawing apparatus, which is one type of charged particle beam apparatus, has been used in order to advance further refinement and high precision. The pattern formation using the electron beam is different from the batch exposure method in pattern formation using a light source such as an i-ray, an excimer laser, and takes a method of drawing a mask pattern. Therefore, the more patterns to be drawn, the more exposure (drawing) It took time and the time taken for pattern formation became a fault. Therefore, as the integration degree is dramatically increased to 256 megabytes, one gigabyte, and four gigabytes, the pattern formation time is also significantly increased, and there is a concern that the throughput is considerably reduced. Therefore, in order to speed up the electron beam drawing apparatus, development of the batch figure irradiation method which combines the mask of various shapes, irradiates an electron beam collectively, and forms the electron beam of a complicated shape is advanced. However, while miniaturization of the pattern has progressed, there is a drawback that the cost of the device is high, for example, an electron beam drawing apparatus must be enlarged, and a mechanism for more precisely controlling the mask position is required.

On the other hand, the proposed nanoimprint has been proposed as a technique for performing fine pattern formation at low cost. For example, U.S. Patent No. 5,772,905 and U.S. Patent No. 5,259,926 disclose nanoimprint techniques that use a silicon wafer as a stamper and form microstructures of 25 nanometers or less by transfer.

In addition, Japanese Patent Application Laid-Open No. 2005-527110 discloses a composite composition using nanoimprint applied to the field of semiconductor microlithography. On the other hand, studies have been actively conducted to apply nanoimprint to semiconductor integrated circuit manufacturing such as micro mold manufacturing technology, mold durability, mold manufacturing cost, mold release from resin, imprint uniformity and alignment accuracy, and inspection technology. I started to lose.

Next, application examples of nanoimprint to flat displays such as liquid crystal displays (LCDs) and plasma displays (PDPs) will be described.

With the trend of LCD substrates and PDP substrates becoming larger and higher in precision, optical nanoimprint has recently attracted attention as an inexpensive lithography instead of the conventional photolithography method used in the manufacture of thin film transistors (TFTs) and electrode plates. Therefore, the development of the photocurable resist which replaces the etching photoresist used by the conventional photolithographic method was needed.

Moreover, as a structural member, such as LCD, optical nanoimprinted to the transparent protective film material of Unexamined-Japanese-Patent No. 2005-197699, 2005-301289, or the spacer of Unexamined-Japanese-Patent No. 2005-301289, etc. Is also beginning to be reviewed. The resist for such a structural member is different from the above etching resist and is finally referred to as a permanent resist or a permanent film because it remains in the display.

A permanent film to which conventional photolithography is applied will be described. The permanent film is an element that is different from the etching resist and is left in a flat display panel or the like as it is. Specifically, the permanent film used on the TFT substrate will be described. In the case of a liquid crystal panel, a thin film transistor is formed on a glass substrate, and a transparent protective film layer (permanent film) is formed thereon to protect the thin film transistor. Moreover, in order to voltage-drive a liquid crystal, ITO (indium tin oxide) which is a transparent electrode is formed by sputtering. In the protective film, a contact hole is formed by photolithography before the ITO sputtering so as to electrically connect the thin film transistor and ITO, and further cured by post-baking in order to secure heat resistance. As the material, a positive resist or the like is often used.

Next, the transparent permanent film for color filters is demonstrated. In general, in a liquid crystal display, a black matrix using chromium oxide or a carbon black-containing resist is formed on a glass substrate, and then color filter layers of R, G, and B are formed on the entire surface. Photocurable resin etc. are apply | coated on this color filter, an electrode lead-out part etc. are removed by photolithography, and a protective film (permanent film) is formed by the heat processing by postbaking. The permanent membrane for color filters reduces the level | step difference between color filter layers, and enables the improvement of the high temperature treatment tolerance at the time of sputter film manufacture of ITO which is a transparent electrode.

Conventionally, as a transparent permanent film for color filters, the transparent permanent film was formed using photocurable resins and thermosetting resins, such as a siloxane polymer, a silicone polyimide, an epoxy resin, and an acrylic resin (Unexamined-Japanese-Patent No. 2000-39713, Japanese Unexamined Patent Publication No. Hei 6-43643).

In the formation of a permanent film formed on a thin film transistor or on a color filter, characteristics such as uniformity of the coating film, substrate adhesion, high light transmittance after heat treatment exceeding at least 200 ° C, planarization properties, solvent resistance, scratch resistance and the like Required.

Moreover, the spacer which defines the cell gap in a liquid crystal display is also a permanent film | membrane, and in conventional photolithography, the photocurable composition which consists of resin, a photopolymerizable monomer, and an initiator is generally used widely (Japanese Unexamined Patent) Publication 2004-240241). The spacer is generally coated with a photocurable composition after forming a color filter on the color filter substrate or after forming the protective film for the color filter, and forming a pattern having a size of about 10 μm to 20 μm by photolithography. It is formed by heat-curing by post-baking.

Spacers require high mechanical properties, hardness, developability, pattern precision, adhesion, and the like against external pressure.

However, the preferable composition of the photocurable composition for transparent protective film or spacer formation used by the nanoimprint method so far has not been disclosed at all.

In addition, regarding the coating film uniformity, the demand for the coating film uniformity is increased in various parts such as the uniformity of the coating film thickness for the center portion and the peripheral portion of the substrate, the dimensional uniformity due to the high resolution, the film thickness, and the shape. Conventionally, in the field of liquid crystal display device manufacturing using a small glass substrate, a method of spin after center dropping has been used as a resist coating method (Electronic Journal 121-123 No. 8 (2002)). In the coating method which spins after center dropping, favorable coating uniformity is obtained, but, for example, in the case of a large substrate of 1m in width and width, the amount of resist scattered and discarded during rotation (spinning) becomes very large, and Problems such as cracking of the substrate due to high-speed rotation and securing the tact time occur. In addition, since the coating performance in the method of spin after the central dropping depends on the rotational speed during spin and the coating amount of the resist, there is no general-purpose motor that can obtain the required acceleration when it is applied to the fifth generation substrate which is further enlarged. There is a problem that special motors are ordered to increase component costs. Moreover, even if the board | substrate size and apparatus size become large, the required performance in an application | coating process, such as application | coating uniformity +/- 3% and a tact time 60-70 second / sheet | piece, hardly changes, for example, spins after center dropping. In the method, it has become difficult to meet the requirements other than the coating uniformity. From such a situation, a resist coating method by a discharge nozzle type has been proposed as a new resist coating method that can be applied to large-sized substrates after the fourth generation substrate, particularly after the fifth generation substrate. The resist coating method by a discharge nozzle type is a method of apply | coating a photoresist composition to the whole surface of the application | coating surface of a board | substrate by moving a discharge nozzle and a board | substrate relatively, For example, the discharge or slit in which the some nozzle hole was arranged in rows. A method using a discharge nozzle which has a discharge port of a phase and which can discharge a photoresist composition in strip shape, etc. is proposed. Moreover, after apply | coating a photoresist composition to the whole surface of the application | coating surface of a board | substrate by a discharge nozzle type, the method of adjusting the film thickness by making the board | substrate spin is also proposed. Therefore, in order to apply the resist by conventional photolithography to the nanoimprint composition and to manufacture these liquid crystal display elements, application uniformity to a board | substrate becomes important.

In positive type photoresists used in semiconductor integrated circuit manufacturing or liquid crystal display production, pigment dispersion photoresist for color filter production, and the like, fluorine-based and / or silicon-based surfactants are added, and coating properties, specifically, strips generated during application on a substrate It is known to solve problems of coating defects such as formation and scaly shape (dry unevenness of a resist film) (Japanese Patent Laid-Open No. 7-230165, Japanese Patent Laid-Open No. 2000-181055, Japanese Patent Laid-Open No. 2004) -94241). Moreover, in order to improve the abrasion property and applicability | paintability of protective films, such as a compact disk and a magneto-optical disk, adding a fluorine type surfactant and a silicone type surfactant to a solvent-free photocurable composition is disclosed (Japanese Patent Laid-Open No. 2004-94241) , Japanese Unexamined Patent Publication No. Hei 4-149280, Japanese Unexamined Patent Publication No. Hei 7-62043, Japanese Unexamined Patent Publication No. 2001-93192). Similarly, in Japanese Unexamined Patent Publication No. 2005-8759, it is known to add a nonionic fluorine-based surfactant in order to improve the ink ejection stability of the inkjet composition. In Japanese Unexamined Patent Publication No. 2003-165930, when embossing a painting composition coated with a brush, a brush, a bar coater, or the like with a mold for hologram processing, the polymerizable unsaturated double bond-containing surfactant is 1% or more, preferably 3% or more is added, and the example which improves the water swellability of a cured film is disclosed. As described above, a technique of adding a surfactant to a protective film such as a positive type photoresist, a pigment dispersion photoresist for producing a color filter, a magneto-optical disk or the like and improving the coating property is a known technique. In addition, as can be seen in the examples of the inkjet or painting composition, a technique of adding a surfactant to a solvent-free photocurable resin and adding a surfactant for improving characteristics in each use is also known. Japanese Laid-Open Patent Publication No. 2007-84625 discloses an example of using a photocurable resin containing a fluorine-based surfactant as an etching resist using a photo nanoimprint method for manufacturing a semiconductor integrated circuit.

However, the method for improving the substrate coating property of the photocurable nanoimprint resist composition which does not have the pigment, dye, and organic solvent which are used for a permanent film as an essential component was not known until now.

In addition, in the photo nanoimprint, it is necessary to improve the fluidity of the composition into the cavity of the mold recess, and also to improve the peelability of the mold, to improve the peelability between the mold and the resist, and the adhesion between the resist and the substrate. Need to be good. It was difficult to make this fluidity | liquidity, peelability, and adhesiveness compatible.

The prior art regarding optical nanoimprint is explained in more detail. The photo nanoimprint is a drop of a liquid curable composition for photo nanoimprint on a substrate such as a silicon wafer, quartz, glass, film or other material such as a ceramic material, a metal, or a polymer. After coating with a film thickness, pressing a mold having fine irregularities having a pattern size of about several tens of nm to several tens of micrometers, and curing the composition by light irradiation in a pressurized state, the mold is released from the coating film to obtain a transferred pattern. The method is common. Therefore, in the case of optical nanoimprint, since light irradiation should be performed, at least one of a board | substrate or a mold needs to be transparent. Usually, light irradiation is common from the mold side, and a lot of inorganic materials, such as quartz and sapphire, which transmit UV light, a light-transmissive resin, etc. are used for a mold material.

In particular, light irradiation from the mold side is effective when the substrate itself is light-shielding, and specifically, when constructing a structure by using the photo nanoimprint method on a color filter used for LCD.

The optical nanoimprint method is capable of imprinting at low pressure because (1) heating / cooling process is unnecessary, high throughput is expected, and (2) liquid composition is used for thermal nanoimprint method. 3) There are no dimensional changes due to thermal expansion, (4) the mold is transparent, alignment is easy, and (5) the main advantage is that a rigid three-dimensional crosslinked product is obtained after curing. It is particularly suitable for semiconductor micromachining applications where alignment accuracy is required or micromachining applications in the field of flat panel displays.

In addition, another feature of the optical nanoimprint method is that the resolution does not depend on the wavelength of the light source as compared with conventional optical lithography, and therefore requires expensive equipment such as a stepper or an electron beam drawing device even when the nanometer order is finely processed. It is characterized by not. On the other hand, the photo-nanoimprint method requires an equal magnification mold, and there is concern about the durability and cost of the mold because the mold and the resin contact each other.

As described above, in order to apply a thermal and / or optical nanoimprint method to imprint a micrometer or nanometer-sized pattern to a large area, not only the uniformity of the pressurization pressure and the flatness of the disk (mould) are required, but also the It is necessary to control the fluidity of the composition into the cavity of the mold recess described above, and the behavior of the composition which flows under pressure.

The mold used in the photo nanoimprint can be made of various materials, for example, metals, semiconductors, ceramics, spin on glass (SOG), or constant plastics. For example, a mold of a flexible polydimethylsiloxane having the desired microstructure described in pamphlet of WO 99/22849 has been proposed. In order to form a three-dimensional structure on one surface of this mold, various lithographic methods can be used depending on the size of the structure and the specifications for its resolution. Lithography of electron beams and X-rays is typically used for structural dimensions less than 300 nm. Direct laser exposure and UV lithography are used for larger structures.

Regarding the optical nanoimprint method, the peelability of the mold and the curable composition for optical nanoimprint is important, and the surface treatment of the mold and the mold, specifically, adhesion is carried out using a hydrogenated silsesquioxane or a fluorinated ethylene propylene copolymer mold. Attempts to solve problems have been made so far.

Here, the photocurable resin used for photo nanoimprint is demonstrated. Photocurable resins applied to nanoimprints are broadly classified into radical polymerization type and ion polymerization type or their hybrid type from the difference in reaction mechanism. Any composition can be imprinted, with radical polymerization of a wide selection of materials being generally used (F. Xu et al .: SPIE Microlithography Conference, 5374, 232 (2004)). As the radical polymerization type, a composition containing a monomer (monomer) or oligomer having a vinyl group or a (meth) acryl group capable of radical polymerization and a photopolymerization initiator is generally used. When irradiated with light, radicals generated from the photopolymerization initiator attack the vinyl group, and chain polymerization proceeds to form a polymer. When a bifunctional or more than polyfunctional monomer or oligomer is used as a component, a crosslinked structure is obtained. In D. J. Resnick et al. : J. Vac. Sci. Technol. B, Vol. 21, No. 6, 2624 (2003) discloses a composition which can be printed at low pressure and room temperature by using a monomer having a low viscosity UV curable.

The characteristic of the material used for an optical nanoimprint is demonstrated in detail. The required properties of the material vary depending on the application used, and the demands on the process properties do not depend on the application and have in common. For example, the main required items shown in the latest resist material handbook, P1, 103-104 (2005, published by Information Agency) include coating properties, substrate adhesion, low viscosity (<5 mPa · s), peelability, and low curing shrinkage. Fast curing. In particular, it is known that the use of low-viscosity materials is strong in applications requiring low pressure imprint and reduction of residual film ratio. On the other hand, the required characteristics for each application include, for example, refractive index, optical transmittance, and the like for the optical member, and etching resistance and residual film thickness reduction for the etching resist. How to control these required characteristics and achieve proper balance is key to material design. Since at least the required properties of the process material and the permanent film differ greatly, the material needs to be developed according to the process and the application. As a material to be applied to such optical nanoimprint applications, the latest resist material handbook, P1, 103-104 (2005, published by Information Agency) discloses a photocurable material having a viscosity of about 60 mPa · s (25 ° C.). It is known. Similarly, CMC Publications: Development and Application of Nanoimprint P159 to 160 (2006) disclose fluorine-containing photosensitive resins having a viscosity of 14.4 mPa · s having a monomethacrylate as the main component and improving the peelability.

As described above, there is a request for a viscosity regarding the composition used in the photo nanoimprint, but there has been no report on the design guide of the material for each application.

The example of the photocurable resin applied to the photo nanoimprint is demonstrated so far. Japanese Unexamined Patent Application Publication No. 2004-59820 and Japanese Unexamined Patent Application Publication No. 2004-59822 disclose examples of embossing using a photocurable resin containing a polymer having an isocyanate group for producing a relief hologram or a diffraction grating. In addition, JP 2006-114882 A discloses a curable composition for photo nanoimprint for imprint containing a polymer, a photopolymerization initiator, and a viscosity modifier.

Japanese Laid-Open Patent Publication No. 2000-143924 discloses a pattern forming method using a fluorine-containing curable material in order to improve peelability with a mold.

In addition, Japanese Laid-Open Patent Publication No. 2007-186570 discloses a photocurable composition for nanoimprint using a (meth) acrylate monomer containing a cyclic structure in order to impart dry etching properties.

N. Sakai et al. J. Photopolymer Sci. Technol. Vol. 18, No. 4,531 (2005) discloses a photocurable radical polymerizable composition or photocurable comprising a combination of (1) a functional acrylic monomer, (2) a functional acrylic monomer, and (3) a functional acrylic monomer and a photopolymerization initiator. An example is disclosed in which a photocationic polymerizable composition containing an epoxy compound and a photoacid generator is applied to a nanoimprint to investigate thermal stability and mold peelability.

M. Stewart et al. : MRS Buletin, Vol. 30, No. 12, 947 (2005) are studies for improving problems such as peelability of photocurable resins and molds, film shrinkage after curing, and reduction of sensitivity by inhibiting photopolymerization in the presence of oxygen. A curable composition for photo nanoimprints containing (1) a functional acrylic monomer, (2) a functional acrylic monomer, a silicone-containing monofunctional acrylic monomer and a photopolymerization initiator is disclosed.

T. Beiley et al. : J. Vac. Sci. Technol. In B18 (6) and 3572 (2000), a curable composition for photo nanoimprint containing a monofunctional acrylic monomer, a silicon-containing monofunctional monomer, and a photopolymerization initiator is formed on a silicon substrate, and the photo nanoimprint is performed using a surface-treated mold. It is disclosed that defects after the furnace mold are reduced.

In B. Vratzov et al. : J. Vac. Sci. Technol. In B21 (6) and 2760 (2003), a curable composition for photo nanoimprint containing a silicon monomer, a trifunctional acrylic monomer, and a photopolymerization initiator is formed on a silicon substrate, and high resolution and uniformity of coating are performed by a SiO ₂ mold. Excellent compositions are disclosed.

E.K.Kim et al. : J. Vac. Sci. Technol, B22 (1) and 131 (2004) disclose an example in which a 50 nm pattern size is formed by a cation polymerizable composition in which a specific vinyl ether compound and a photoacid generator are combined. Although it is a characteristic that it is low in viscosity and fast in hardening rate, it is described that template peelability is a subject.

However, N. Sakai et al. J. Photopolymer Sci. Technol. 18, No. 4,531 (2005), M. Stewart et al. MRS Buletin, Vol. 30, No. 12,947 (2005), T. Beiley et al. : J. Vac. Sci. Technol. B 18 (6), 3572 (2000), B. Vratzov et al. : J. Vac. Sci. Technol. B 21 (6), 2760 (2003), E. K. Kim et al. : J. Vac. Sci. As shown in Technol, B22 (1), 131 (2004), various photocurable resins in which an acrylic monomer, an acrylic polymer, and a vinyl ether compound having different functional groups are applied to the photo nanoimprint have been disclosed. There are no guidelines for designing materials such as monomer species, combinations of monomers, optimal viscosity of monomers or resists, preferred solution properties of resists, and improved applicability of resists. Therefore, a preferred composition for widely applying the composition to optical nanoimprint applications is unknown, and it is a situation that a photo nanoimprint resist composition which has never been satisfied has not been proposed until now.

B. Vratzov et al. : J. Vac. Sci. Technol. B 21 (6), 2760 (2003), E. K. Kim et al. : J. Vac. Sci. Some of the compositions of Technol, B22 (1) and 131 (2004) have low viscosity, but all of them have a photocuring pattern to form a pattern, and the transmittance of the cured film in the case of continuous heat treatment is low (colored) and insufficient hardness. This is not practical as a permanent film. The composition is unknown.

Proc. SPIE Int. Soc. Opt. Eng., Vol. 6171, No. Pt2, 61512F (2006), Science and Industry, Vol. 80, No. 7,322 (2006) include silica sol, (meth) acrylic monomers and photopolymerization initiators treated with optical functional crosslinker materials. Inorganic-organic hybrid materials consisting of mixtures have been proposed, and applications to optical nanoimprints have been reported. Proc. SPIE Int. Soc. Opt. Eng., Vol. 6171, No. Pt2, 61512F (2006), Science and Industry, Vol. 80, No. 7,322 (2006), examples of pattern formation of 200 nm lines of imprint material and line widths of 600 nm as mold materials. It is reported that it can be patterned. By the way, there existed a problem, such as peelability with a mold, or the hardness of a cured film not enough, and was not necessarily satisfactory.

In addition, Proc. SPIE Int. Soc. Opt. Eng., Vol. 6171, No. Pt2, 61512F (2006), Science and Industry, Vol. 80, No. 7,322 (2006), although some of them have low viscosity, they are all photocured to form patterns and continued heating. The transmittance | permeability of the cured film at the time of a process is low, ie, it becomes colored and its hardness is insufficient. In particular, the composition which is practical as a permanent film is unknown.

In addition, Japanese Laid-Open Patent Publication No. 2000-143924 discloses a composition for hard coat containing a surface-treated colloidal silica, a specific (meth) acrylic monomer, a leveling agent, and a photopolymerization initiator, and has a film hardness and low curing shrinkage. Application to compatible optical disks has been reported, but the application to optical nanoimprint has been difficult in these compositions due to insufficient peelability with a mold and substrate applicability. Moreover, the transmittance | permeability at the time of heat processing after photocuring is low, ie, it becomes colored and cannot be used as a permanent film.

In addition, Japanese Laid-Open Patent Publication No. 2007-186570 reports a composition for etching resists using a (meth) arc having a cyclic structure, but in these compositions, the transmittance at the time of heat treatment after photocuring is low, That is, the problem that it is colored and cannot be used as a permanent film, the hardness and solvent resistance of a cured film are inadequate, and cannot be practical.

As a means of increasing the hardness and mechanical strength of the cured film, it can be achieved by using a polyfunctional monomer which imparts a high crosslinking density. Such a polyfunctional monomer is a high viscosity compound, and under the low viscosity constraint, obtaining satisfactory cured film properties It was difficult. In addition, the polymerization of the polyfunctional monomer proceeds at a time during light irradiation, and there is a problem that a residue remains when a resin mold is used.

As a curable composition for inkjet using a monomer having a photopolymerization site and a thermal reaction site in the same molecule, an international publication WO2004 / 099272 pamphlet has been reported. In this invention, the viscosity of the composition is high and cannot be applied to an optical nanoimprint as it is. Moreover, since the coloring of a cured film is also large, using for the spacer protective film for liquid crystal color filters has a problem in terms of permeability, and the improvement method is not disclosed.

Moreover, JP 2005-255854 A report the curable composition of the acrylate monomer which has a vinyl ether group in the same molecule. Although this invention can be applied to optical nanoimprint with a low viscosity, since the hardness of a cured film is lacking, the improvement method is not disclosed.

As described above, a resist composition that is practical as a permanent film and to which the photo nanoimprint method can be applied has not been proposed until now.

The main technical problems as a permanent film are pattern accuracy, adhesiveness, permeability after heat treatment exceeding 200 ° C., high mechanical properties (strength against external pressure), scratch resistance, planarization property, solvent resistance, and outgas reduction during heat treatment. There are many challenges. When applying the curable composition for photo nanoimprint as a permanent film, it is the same as the resist which used the conventional acrylic resin etc.,

(1) Uniformity of coating film

(2) Permeability after heat treatment

(3) scratch resistance

The grant of is important.

At the same time, in addition to the above (1) to (3), it is necessary to consider the following aspects (4) and (5) as the curable composition for optical nanoimprint, and the technical difficulty of designing the composition is further increased.

(4) Securing the fluidity of the resist with respect to the recesses of the mold and requiring low viscosity under the use of a solvent-free or small amount of solvent

(5) After photocuring, it is easily peeled off from the mold so that adhesion to the mold does not occur.

Although various materials are disclosed about the curable composition for optical nanoimprint for nanoimprint, the curable for optical nanoimprint used as a composition known for the use of an inkjet composition, a protective film for a magneto-optical disk, or an etching resist so far. Although the composition has a part common in the curable composition and material for optical nanoimprint used for a permanent film, it differs greatly from a viewpoint of high temperature heat processing, a mechanical strength, etc., and is applied to an inkjet, a protective film for a magneto-optical disk, and an etching resist. If the photocurable resin is applied as a resist for a permanent film as it is, what is practical in permeability, mechanical strength, solvent resistance, etc. cannot be obtained. In particular, high permeability is required.

This invention was achieved in view of the said situation, Comprising: It aims at providing the curable composition for nanoimprint excellent in photocurability and excellent in permeability. Moreover, it aims at providing the curable composition for nanoimprint suitable for permanent films, such as a flat panel display. In particular, it aims at providing the composition excellent in all of the permeability, peelability, and pattern precision after heat-hardening.

As a result of earnestly examining about the international publication WO2004 / 099272 pamphlet, when two or more types of curable functional groups which differ in reactivity in the same molecule, for example, the monomer which has a photopolymerization site | part and a thermal reaction site | part are used, the viscosity which has nanoimprintability In addition, since it provides the cured film physical property which satisfy | fills, and is semi-cured at the time of photopolymerization, it turned out that the effect which hardly remains is used even if an inexpensive resin mold is used. From this point of view, it was found that the above problems can be solved by the following means.

(1) The curable composition for nanoimprints containing the monomer (A) which has at least 2 type of reactivity different curable functional group in the same molecule, and (C) antioxidant.

(2) Curable composition for nanoimprints as described in (1) whose at least 1 is an (alpha), (beta)-unsaturated ester group among the said curable functional groups.

(3) Furthermore, curable composition for nanoimprints as described in (1) or (2) containing (B) surfactant.

(4) The curable composition for nanoimprinting according to any one of (1) to (3), wherein the composition has a viscosity of 3 to 18 mPa · s.

(5) A monomer having (A) two or more kinds of curable functional groups having different reactivity in the same molecule, and at least one of the curable functional groups being an α, β-unsaturated ester group, (B) surfactant, and (C) antioxidant The curable composition for nanoimprints containing at least, the curable composition for nanoimprints whose viscosity is the range of 3-18 mPa * s.

(6) The curable composition for nanoimprinting according to any one of (1) to (5), in which the monomer is represented by the following General Formula (1).

(In general formula (1), R <^1> represents a hydrogen atom or a hydroxymethyl group, X represents an organic group. M shows the integer of 1-3, n shows the integer of 1-4. Y is A curable functional group having a carbon-carbon unsaturated bond, a curable functional group having a carbon-nitrogen unsaturated bond, a curable functional group having a cyclic group containing an oxygen atom, or a group represented by the following general formula (2).

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

(7) At least one of Y in General Formula (1) is a vinyl ether group, an allyl ether group, an allyl ester group, a cyclohexenyl group, a cyclopentenyl group, a dicyclopentenyl group, a styryl group, a methacryloyloxy group, a meta Curable composition for nanoimprints as described in (6) chosen from the group which consists of a kryloyl amide group, an acrylamide group, a vinylsilane group, an N-vinyl heterocyclic group, and a maleimide group.

(8) The curable composition for nanoimprinting according to (6), wherein at least one of Y in General Formula (1) is selected from an allyl ether group, a cyclohexenyl group, and a dicyclopentenyl group.

(9) The curable composition for nanoimprint according to (6), wherein at least one of Y in General Formula (1) is an allyl ether group, and the sum of n and m is 3 to 6.

(10) The curable composition for nanoimprint according to (6), wherein at least one of Y in General Formula (1) is an isocyanate group or a nitrile group.

(11) The curable composition for nanoimprinting according to (6), wherein at least one of Y in General Formula (1) is selected from the group consisting of an oxetane ring, an oxirane ring, and an ethylene carbonate group.

(12) The curable composition for nanoimprinting according to any one of (6) to (11), in which X represents an organic group having 3 to 9 carbon atoms in general formula (1).

(13) The curable composition for nanoimprinting according to (6), wherein the compound represented by the general formula (1) is any one or more of the following general formulas (3) to (5).

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

(14) Curable composition for nanoimprint in any one of (1)-(13) containing polymerizable monomers other than the said monomer (A), and a photoinitiator.

(15) The curable composition for nanoimprinting according to any one of (1) to (14), wherein the antioxidant is selected from at least a hindered phenol-based antioxidant or a hindered amine-based antioxidant.

(16) Curable composition for nanoimprints in any one of (1)-(15) whose content of the said antioxidant is 10 mass% or less.

(17) Curable composition for nanoimprints in any one of (1)-(16) which does not contain the compound whose molecular weight exceeds 1000.

(18) The curable composition for nanoimprinting according to any one of (1) to (17), wherein the surface tension of the composition is in the range of 18 to 30 mN / m.

(19) The curable composition for nanoimprinting according to any one of (1) to (18), which is cured by performing light irradiation and heating.

Hardened | cured material which hardened the curable composition for nanoimprints in any one of (20) (1)-(19).

(21) The manufacturing method of the hardened | cured material containing what hardens | cures the curable composition for nanoimprint in any one of (1)-(19) by performing light irradiation and heating multiple times.

The member for liquid crystal display devices using the hardened | cured material of (22) and (20).

(23) The manufacturing method of the member for liquid crystal display devices containing hardening | curing the composition of any one of (1)-(19) by performing light irradiation and heating multiple times.

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

EMBODIMENT OF THE INVENTION Below, the content of this invention is demonstrated in detail. In addition, in this specification, "-" is used by the meaning which includes the numerical value described before and after that as a lower limit and an upper limit.

Hereinafter, the present invention will be described in detail. In addition, in this specification, meta (acrylate) represents an acrylate and a methacrylate, meta (acryl) represents an acryl and methacryl, and meta (acryloyl) represents acryloyl and methacryloyl. . In addition, in this specification, a monomer and a monomer are the same. The monomer in this invention is distinguished from an oligomer and a polymer, and the compound of the mass mean molecular weight says 1,000 or less. In this specification, a functional group means the group which participates in superposition | polymerization.

Incidentally, the nanoimprint referred to in the present invention refers to pattern transfer having a size of about several micrometers to several tens of nm, and needless to say, it is not limited to nano orders.

The curable composition for an optical nanoimprint of the present invention (hereinafter may be simply referred to as the "composition of the present invention") has high transmittance before curing, and is excellent in the ability to form a fine concavo-convex pattern, and is suitable for coating suitability and others. It can be made excellent in workability. Moreover, after hardening, it is excellent in hardness, Furthermore, it can be set as the coating film physical property outstanding comprehensively in various other aspects. Therefore, the composition of this invention can be used widely for optical nanoimprint.

That is, when the composition of this invention is used for optical nanoimprint, it can be set as having the following characteristics.

(1) Since the fluidity of the solution at room temperature is excellent, the composition easily flows into the cavity of the mold recessed portion, and since air is hard to enter, no bubble defects occur. The residue is difficult to remain.

(2) Since the cured film after curing has excellent mechanical properties, excellent adhesion between the coating film and the substrate, and excellent peelability between the coating film and the mold, when the mold is peeled off, a pattern collapse and a seal attraction occurs on the surface of the coating film. Since no roughness is caused, a good pattern can be formed.

(3) Since it is excellent in coating uniformity, it is suitable for the field of application | coating to a large board | substrate, a microprocessing, etc.

(4) Since the mechanical properties such as light transmittance, residual film resistance, and scratch resistance and solvent resistance are high, it can be preferably used as various permanent films.

For example, the composition of this invention is a microfabrication of the member for semiconductor integrated circuits and liquid crystal display devices which were difficult to develop until now (especially the thin film transistor of a liquid crystal display, the protective film of a liquid crystal color filter, a spacer, and other members for liquid crystal display devices). Application), and other uses, for example, magnetic recordings such as bulkheads for plasma display panels, flat screens, microelectromechanical systems (MEMS), sensor elements, optical disks, and high density memory disks. Medium, optical components such as diffraction grating yaref holograms, nanodevices, optical devices, optical films and polarizing elements, organic transistors, color filters, overcoat layers, substrates, liquid crystal alignment ribs, microlens arrays, immunity Assay chip, DNA separation chip, Micro reactor, Nano bio device, Optical waveguide, Optical filter, Photonic liquid crystal It can apply widely to manufacture of these etc., too.

The viscosity of the composition of this invention is demonstrated. The viscosity in this invention says the viscosity in 25 degreeC unless there is particular notice. The viscosity of 25 degrees C of the composition of this invention becomes like this. Preferably it is 3-18 mPa * s, More preferably, it is 5-15 mPa * s, More preferably, it is 7-12 mPa * s. By making the viscosity of the composition of this invention into 3 mPa * s or more, there exists a tendency which the problem of a board | substrate application | coating suitability and the fall of the mechanical strength of a film | membrane hardly arise. Specifically, the viscosity is 3 mPa · s or more, which is preferable in that it is possible to suppress surface unevenness during application of the composition or to prevent the composition from flowing out of the substrate during application. On the other hand, when the viscosity of the composition of the present invention is 18 mPa · s or less, even when a mold having a fine concavo-convex pattern is brought into close contact with the composition, the composition flows into the cavity of the mold concave portion, making it difficult to enter the atmosphere. It is hard to produce, and it is preferable because a residue becomes hard to remain after photocuring in a mold convex part.

The composition of this invention contains the monomer which has two or more types of curable functional groups in which the (A) reactivity differs in the same molecule, and (C) antioxidant. In addition, in this invention, you may contain the (B) surfactant. Moreover, only one type may be sufficient as (A) monomer and two or more types may be sufficient as it. The composition of the present invention preferably contains (A) monomer in the range of 10 to 99% by mass of the composition, more preferably 20 to 80% by mass. Moreover, the composition of this invention may contain another polymeric monomer, a photoinitiator, etc. Hereinafter, these contents are demonstrated in detail.

First, the compound which has two or more types of curable functional groups with different reactivity contained in the composition of this invention in the same molecule is demonstrated (Hereinafter, it may be called "the monomer in this invention."). Here, the curable functional groups which differ in two kinds of reactivity can be distinguished as follows, for example. As a 1st example, although superposition | polymerization (reaction) advances at the time of light irradiation, what differs in the reactivity of the functional group is mentioned. As such a curable functional group, an acrylic acid ester group, N-vinyl group, (meth) acryloylamide group is mentioned. As a 2nd example, group to which polymerization (reaction) advances at the time of light irradiation, and group to which polymerization (reaction) advances by heating are mentioned. Specifically, as a group which does not react at the time of light irradiation, a vinyl ether group, an allyl ether group, an allyl ester group, a cyclohexenyl group, a cyclopentenyl group, a dicyclopentenyl group, a styryl group, methacryloyloxy group, a vinylsilane group And maleimide groups. The methacryloyloxy group, the styryl group, and the vinyl ether group are usually radically polymerized. Since the polymerization at the time of light irradiation is carried out near room temperature, these polymerizable groups do not react and are polymerized by heating.

It is preferable that it is a monomer in which at least 1 of a curable functional group is an (alpha), (beta)-unsaturated ester group, and, as for the monomer in this invention, it is more preferable that it is a monomer represented by General formula (1).

(In general formula (1), R <^1> represents a hydrogen atom or a hydroxymethyl group, X represents an organic group. M shows the integer of 1-3, n shows the integer of 1-4. Y is A curable functional group having a carbon-carbon unsaturated bond, a curable functional group having a carbon-nitrogen unsaturated bond, a curable functional group having a cyclic group containing an oxygen atom, or a group represented by the following general formula (2).

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

The organic group represented by X represents a 2-7 valent organic group and is preferably a 3-6 valent organic group. Any of aliphatic and aromatic may be sufficient, 2-20 are preferable and, as for the total carbon number, it is more preferable that it is 3-9. When the total number of carbons is in the range of 3 to 9, the functional group density is increased, the crosslinking density of the cured film can be improved, and the molecular weight can be designed at low molecular weight. Thus, the viscosity of the composition of the present invention can be made a more preferable range. In addition, the organic group may be interrupted by an oxygen atom, a sulfur atom, an ester group and a urethane group. Specifically, aliphatic cyclic skeleton, benzene skeleton, etc. which are represented by a C3-C9 alkyl chain, a propanetriol skeleton, a pentaerythritol skeleton, a cyclohexane ring, a cyclopentane ring, etc. are mentioned.

The curable functional group which has a carbon-carbon unsaturated bond represented by Y may be any of a double bond and a triple bond, may have a substituent by an unsaturated bond, and either a chain type or a cyclic type may be sufficient as it. As for the total carbon number, 2-18 are preferable.

As Y, vinyl ether group, allyl ether group, allyl ester group, cyclohexenyl group, cyclopentenyl group, dicyclopentenyl group, styryl group, methacryloyloxy group, methacryloyl amide group, acrylamide group, vinylsilane A group, an N-vinyl heterocyclic group, and a maleimide group are mentioned, An allyl ether group, a cyclohexenyl group, and a dicyclopentenyl group are preferable, and an allyl ether group and an allyl ester group are more preferable.

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

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

m becomes like this. Preferably it is 1-3, More preferably, it is 1 or 2, n is preferably 1-4, More preferably, it is 1-3. When m is two or more, some R <^1> may be the same and may differ, respectively. Moreover, when n is two or more, some Y may be the same and may differ, respectively.

As an alkyl group represented by R <^2> , a C1-C8 alkyl group is preferable. As such an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a benzyl group are mentioned. As an aryl group, a C6-C12 aryl group is preferable. As such an aryl group, a phenyl group, p-tolyl group, and p-chlorophenyl group are mentioned.

In this invention, it is especially preferable that at least 1 of Y is an allyl ether group or an allyl ester group, the sum of n and m is 3-6, Moreover, at least 1 of Y is an allyl ether group or an allyl ester group, n and m It is more preferable that the sum is 3 to 6, and X is an organic group having 3 to 9 carbon atoms in total. By adopting such a monomer, the crosslinking density of a cured film can be improved, the mechanical properties and solvent resistance of a cured film can be improved, the viscosity of a composition can be set to a preferable range, and the effect that a pattern precision improves Obtained.

It is preferable that the compound represented by General formula (1) is also a compound represented by any 1 or more types of following General Formula (3)-(5).

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

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

Other polymerizable monomers

The composition of the present invention may further contain other polymerizable monomers for the purpose of improving composition viscosity, film hardness, flexibility, etc., and has a polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group (monofunctional It is preferable to use a polymerizable unsaturated monomer) together. Specifically, 2-acryloyloxyethyl phthalate, 2-acryloyloxy 2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-ethyl-2 -Butyl propanediol acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexylcarbitol (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, dimer acrylic acid, benzyl ( Meth) acrylate, butane diol mono (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, ethylene oxide modified (hereinafter referred to as "EO") cresol (Meth) acrylate, dipropylene Call (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl ( Meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate , Methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate, Neopentyl glycol benzoate (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polypropylene glycol (meth) acrylate, jade (Meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, epichlorohydrin (hereinafter referred to as "ECH") modified phenoxyacrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol ( Meth) acrylate, phenoxy hexaethylene glycol (meth) acrylate, phenoxy tetraethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (Meth) acrylate, stearyl (meth) acrylate, EO modified succinic acid (meth) acrylate, tert-butyl (meth) acrylate, tribromophenyl (meth) acrylate, EO modified tribromophenyl (meth ) Acrylate, tridodecyl (meth) acrylate, p-isopropenylphenol, styrene, α-methylstyrene, acrylonitrile, vinylcarbazole, urethane (meth) The methacrylate may be mentioned.

Moreover, it is also preferable to use the polyfunctional polymerizable unsaturated monomer which has 2 or more of ethylenically unsaturated bond containing groups as another polymerizable monomer.

Examples of the bifunctional polymerizable unsaturated monomer having two ethylenically unsaturated bond-containing groups which can be preferably used in the present invention include diethylene glycol monoethyl ether (meth) acrylate, dimethyloldicyclopentanedi (meth) acrylate and di (Meth) acrylic isocyanurate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanedioldi (meth) acrylate, EO-modified 1,6-hexanedioldi (meth) acrylate, ECH modified 1,6-hexanedioldi (meth) acrylate, allyloxypolyethylene glycol acrylate, 1,9-nonanedioldi (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 neopentylglycol 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 hydroxypivalic acid Ester neopentyl glycol, stearic acid modified pentaerythritol di (meth) acrylate, ECH modified phthalic acid di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol-tetra Methylene glycol) di (meth) acrylate, polyester (di) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ECH modified propylene glycol di (meth) acrylate, silicone di (Meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dimethyl All tricyclodecanedi (meth) acrylate, neopentylglycol modified trimethylolpropanedi (meth) acrylate, tripropylene glycoldi (meth) acrylate, EO modified tripropylene glycoldi (meth) acrylate, triglyceroldi (Meth) acrylate, dipropylene glycol di (meth) acrylate, divinyl ethylene urea, divinyl propylene urea, and urethane (meth) acrylate are illustrated.

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

Examples of the polyfunctional polymerizable unsaturated monomer having three or more ethylenically unsaturated bond-containing groups include ECH-modified glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, and penta Erythritol triacrylate, EO-modified phosphoric 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 (acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol Hydroxypenta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, dipene Erythritol poly (meth) acrylate, alkyl modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol tetra ( Meth) acrylate, urethane (meth) acrylate, and the like.

Among them, 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 ethoxy tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, urethane (meth) acrylate, and the like It is preferably used for.

As the urethane (meth) acrylate described above, mono (meth) acrylate or polyfunctional acrylate can be used. As a specific compound, U-2PPA, UA-4100, UA-5201, U-4H, U-4HA, U-6HA, U-15HA etc. by Shin-Nakamura Chemical Co., Ltd. are mentioned.

In the composition of the present invention, for the purpose of further increasing the crosslinking density, a polyfunctional oligomer or a polymer having a higher molecular weight than that of the other polymerizable monomer can be blended within the scope of achieving the object of the present invention. Examples of the polyfunctional oligomer having optical radical polymerizability include various acrylate oligomers such as polyester acrylate, polyurethane acrylate, polyether acrylate, and polyepoxy acrylate.

As another polymerizable monomer used by this invention, the compound which has an oxirane ring can also be employ | adopted. Examples of the compound having an oxysilane ring include polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, and polyglycidyl of aromatic polyols. Hydrogenated compounds of the ethers, urethane polyepoxy compounds, epoxidized polybutadienes, and the like. These compounds may be used individually by 1 type, and may mix and use 2 or more types.

Commercially available products which can be preferably used as the glycidyl group-containing compound include UVR-6216 (manufactured by Union Carbide), glycidol, AOEX24, cyclomer A200 (above, manufactured by Daicel Chemical Industry Co., Ltd.), Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (above, Emulsion Shell Co., Ltd.), KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2720, KRM-2750 ( Asahi Telephone Industry Co., Ltd.) etc. are mentioned above. These can be used individually by 1 type or in combination of 2 or more types.

Moreover, the compound which has these oxirane rings is irrespective of the manufacturing method, for example, Maruzen KK Publishing, 4th edition Experimental Chemistry Course 20 Organic Synthesis II, 213-, 4 years, Ed. by Alfred Hasfner, The chemistry of heterocyclic compounds-Small Ring Heterocycles part3 Oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, Adhesion, Vol. 29, No. 12, 32, 1985, Yoshimura, Adhesion, Volume 30 5, 42, 1986, Yoshimura, Adhesion, 30, 7, 7, 42, 1986, Japanese Patent Application Laid-Open No. 11-100378, Japanese Patent No. 2906245, Japanese Patent No. 2926262, etc. Can be.

You may use together a vinyl ether compound as another polymerizable monomer used by this invention.

What is necessary is just to select a vinyl ether compound suitably, For example, 2-ethylhexyl vinyl ether, butanediol- 1, 4- divinyl ether, diethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, tri Ethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether Neopentyl glycol divinyl ether, trimethylol propane trivinyl ether, trimethylol ethane trivinyl ether, hexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, penta Erythritol tetravinyl ether, sorbitol tetra vinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol di Ethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene vinyl ether, trimethylol propane triethylene vinyl ether, trimethylol propane diethylene vinyl ether, pentaerythritol diethylene vinyl ether, pentaerythritol triethylene vinyl ether Pentaerythritol tetraethylene vinyl ether, 1,1,1-tris [4- (2-vinyl oxyethoxy) phenyl] ethane, bisphenol A divinyl oxyethyl ether, and the like.

These vinyl ether compounds are described, for example, in Stephen. C. Lapin, Polymers Paint Color Journal. 179 (4237), 321 (1988) can be synthesized by the method described in the reaction of polyhydric alcohol or polyhydric phenol with acetylene, or reaction of polyhydric alcohol or polyhydric phenol with halogenated alkylvinyl ether, It can be used individually by 1 type or in combination of 2 or more types.

Moreover, a styrene derivative can also be employ | adopted as another polymerizable monomer used by this invention. As a styrene derivative, p-methoxy styrene, p-methoxy- (beta) -methyl styrene, p-hydroxy styrene, etc. are mentioned, for example.

In addition, as a styrene derivative which can be used together with the monofunctional polymer of this invention, styrene, p-methylstyrene, p-methoxystyrene, (beta) -methylstyrene, p-methyl- (beta) -methylstyrene, (alpha)- Methyl styrene, p-methoxy- (beta) -methylstyrene, p-hydroxy styrene, etc. are mentioned, As a vinyl naphthalene derivative, it is 1-vinyl naphthalene, (alpha) -methyl-1- vinyl naphthalene, (beta) -methyl-, for example. 1-vinyl naphthalene, 4-methyl-1- vinyl naphthalene, 4-methoxy-1-vinyl naphthalene, etc. are mentioned.

Moreover, for the purpose of improving peelability and applicability | paintability with a mold, trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, and purple Luorobutyl-hydroxypropyl (meth) acrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tetrafluoro The compound which has fluorine atoms, such as propyl (meth) acrylate, can also be used together.

As another polymerizable monomer used by this invention, propenyl ether and butenyl ether can be mix | blended. For example, 1-dodecyl-1-propenyl ether, 1-dodecyl-1-butenyl ether, 1-butenoxymethyl-2-norbornene, 1-4-di (1-butenoxy) Butane, 1,10-di (1-butenoxy) decane, 1,4-di (1-butenoxymethyl) cyclohexane, diethylene glycoldi (1-butenyl) ether, 1,2,3- Tri (1-butenoxy) propane, propenyl ether propylene carbonate and the like can be preferably applied.

It is preferable to contain another polymerizable monomer in the range of 10-90 mass% in a composition, and it is more preferable to contain in the range which is 20-80 mass%.

Next, the preferable blend form of the monomer in this invention and another polymerizable monomer (henceforth these may be called "polymerizable unsaturated monomer") is demonstrated. The composition of the present invention contains two or more kinds of curable functional groups having different reactivity in the same molecule, at least one of which is an α, β-unsaturated ester group as an essential component, and contains another polymerizable monomer. It is preferable.

A monofunctional polymerizable unsaturated monomer is usually used as a reactive diluent and effective for lowering the viscosity of the composition of the present invention, and is usually added at least 15% by mass of the total polymerizable unsaturated monomer. Preferably it is 20-80 mass%, More preferably, it is 25-70 mass%, Especially preferably, it is added in the range of 30-60 mass%.

Since the said monofunctional polymerizable unsaturated monomer is better as a reactive diluent, it is preferable to add 15 mass% or more of all the polymerizable unsaturated monomers.

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, particularly preferably 70% by mass or less of the total polymerizable unsaturated monomer. Is added. The proportion of the monofunctional and bifunctional polymerizable unsaturated monomers is preferably 1 to 95% by mass, more preferably 3 to 95% by mass, particularly preferably 5 to 90% by mass of the total polymerizable unsaturated monomer. do. The proportion of the polyfunctional polymerizable unsaturated monomer having three or more unsaturated bond-containing groups is preferably 80% by mass or less, more preferably 70% by mass or less, particularly preferably 60% by mass or less of the total polymerizable unsaturated monomer. Is added. Since the viscosity of a composition can be reduced by making the ratio of the polymerizable unsaturated monomer which has three or more polymerizable unsaturated bond containing groups into 80 mass% or less, it is preferable.

It is preferable that the surface tension is in the range of 18-30 mN / m, and, as for the composition of this invention, it is more preferable to exist in the range which is 20-28 mN / m. By setting it as such a range, the effect of improving surface smoothness is acquired.

Moreover, the water content at the time of preparation of the composition of this invention becomes like this. Preferably it is 2.0 mass% or less, More preferably, it is 1.5 mass%, More preferably, it is 1.0 mass% or less. By making the water content at the time of preparation into 2.0 mass% or less, the shelf life of the composition of this invention can be made more stable.

Moreover, it is preferable that content of the organic solvent of the composition of this invention is 3 mass% or less in all the compositions. That is, since the composition of the present invention preferably contains the above monofunctional and / or bifunctional other monomers as the reactive diluent, it is not necessary to necessarily contain the organic solvent for dissolving the components of the composition of the present invention. In addition, if the organic solvent is not contained, the baking process for the purpose of volatilizing the solvent becomes unnecessary, so that the merit of simplifying the process is large. Therefore, in the composition of this invention, content of the organic solvent becomes like this. Preferably it is 3 mass% or less, More preferably, it is 2 mass% or less, It is especially preferable not to contain. Thus, although the composition of this invention does not necessarily contain the organic solvent, you may add arbitrarily, such as when dissolving the compound etc. which do not melt | dissolve in a reactive diluent as a composition of this invention, and when adjusting a viscosity finely. As a kind of organic solvent which can be used suitably for the composition of this invention, it is a solvent generally used for the curable composition for photo nanoimprints and a photoresist, What is necessary is just to melt | dissolve and uniformly disperse the compound used by this invention, and these It will not specifically limit, if it does not react with the component of.

Examples of the organic solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycols such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether. Ethers; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, Diethylene glycols such as diethylene glycol monoethyl ether and diethylene glycol monobutyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; Acetone, Methylethylke Ketones such as methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and 2-heptanone; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, Ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-E Ester, such as lactic acid ester, such as methyl oxypropionate, ethyl 3-ethoxy propionate, ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate, etc. are mentioned.

In addition, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether , Dihexyl ether, acetyl acetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyro High boiling point solvents, such as lactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate, can also be added. These may be used individually by 1 type and may use 2 or more types together.

Among these, methoxy propylene glycol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxy propionate, ethyl 3-ethoxy propionate, ethyl lactate, cyclohexanone, methyl isobutyl ketone, 2-heptanone are particularly preferable. Do.

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

Photopolymerization initiator

It is preferable that a photoinitiator is contained in the composition of this invention. The photoinitiator used for this invention contains 0.1-15 mass%, for example in all the compositions, Preferably it is 0.2-12 mass%, More preferably, it is 0.3-10 mass%. When using two or more types of photoinitiators, the total amount becomes said range.

When the ratio of the photopolymerization initiator is 0.1% by mass or more, the sensitivity (fast curing property), resolution, line edge roughness, and coating film strength tend to be improved, which is preferable. On the other hand, by making the ratio of a photoinitiator into 15 mass% or less, there exists a tendency for light transmittance, coloring property, handleability, etc. to improve, and it is preferable. Until now, in the composition for inkjets and liquid crystal display color filters containing dyes and / or pigments, various addition amounts of preferred photopolymerization initiators and / or photoacid generators have been studied, but optical nanoimprints such as for nanoimprints have been studied. There is no report on the addition amount of the preferable photoinitiator and / or the photo-acid generator with respect to the curable composition. That is, in systems containing dyes and / or pigments, these may act as radical trapping agents and affect photopolymerization and sensitivity. In view of this, the addition amount of a photoinitiator is optimized in these uses. In addition, in the composition of this invention, dye and / or a pigment are not an essential component, and the optimal range of a photoinitiator may differ from what is the field of compositions, such as an inkjet composition and a composition for liquid crystal display color filters.

The photoinitiator used by this invention uses what has activity with respect to the wavelength of the light source to be used, and produces | generates suitable active species.

The radical photoinitiator used by this invention can use a commercially available initiator, for example. Examples thereof include Irgacure® 2959 (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, available from Ciba, Irgacure ( 184 (1-hydroxycyclohexylphenylketone), Irgacure® 500 (1-hydroxycyclohexylphenylketone, benzophenone), Irgacure® 651 (2,2-dimethoxy-1 , 2-diphenylethan-1-one), Irgacure® 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1), Irgacure® 907 (2-Methyl-1 [4-methylthiophenyl] -2-morpholinopropane-1-one, Irgacure (registered trademark) 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Irgacure 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphineoxide, 1-hydroxy-cyclohexyl-phenyl-ketone), Irgacure® 1800 ( Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentyl phosphine oxide, 2-hydroxy-2-methyl-1-phenyl -1-Propan-1-one), Irgacure® OXE01 (1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), Darocur® 1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Darocur® 1116, 1398, 1174 and 1020, CGI242 (ethanone, 1- [9-ethyl-6 -(2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) available from BASF, Lucirin TPO-L (2,4,6-trimethylbenzoylethoxyphenylphosphine oxide), ESACURE 1001M (1- [4-benzoylphenylsulfanyl] phenyl] -2-methyl- available from ESACUR Japan Siebel Heg Screw 2- (4-methylphenylsulfonyl) propan-1-one, adekaoptomer (registered trademark) N-1414 (carbazole phenone system), adekaoptomer (registered trademark) available from Asahi telephone company ) N-1717 (acridin-based), adekaoptomer (registered trademark) N-1606 (triazine-based), TFE-triazine (2- [2- ( Lan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), TME-triazine (2- [2- (5-methylfuran-) produced by acid and chemical 2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), MP-triazine (2- (4-methoxyphenyl) -4,6 from Sanwa Chemical -Bis (trichloromethyl) -1,3,5-triazine), Midori Chemical Co., Ltd. TAZ-113 (2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloro) Romethyl) -1,3,5-triazine), Midori Chemical Co., Ltd. TAZ-108 (2- (3,4-dimethoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5- Triazine), benzophenone, 4,4'-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 4-phenylbenzophenone, ethylmihilersketone , 2-chloro thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 1-chloro-4-propoxy Oxanthone, 2-methyl thioxanthone, thioxanthone ammonium salt, benzoin, 4,4'- dimethoxy benzo Phosphorus, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetophenone, diethoxyacetophenone and dibenzosverone, o Methyl benzoylbenzoate, 2-benzoylnaphtharene, 4-benzoylbiphenyl, 4-benzoyldiphenyl ether, 1,4-benzoylbenzene, benzyl, 10-butyl-2-chloroacridone, [4- (methylphenylthio ) Phenyl] phenylmethane), 2-ethylanthraquinone, 2,2-bis (2-chlorophenyl) 4,5,4 ', 5'- tetrakis (3,4,5-trimethoxyphenyl) 1, 2'-biimidazole, 2,2-bis (o-chlorophenyl) 4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, tris (4-dimethylaminophenyl) methane, Ethyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethylbenzoate, butoxyethyl-4- (dimethylamino) benzoate and the like.

Moreover, in addition to a photoinitiator, the photosensitizer can also be added to the composition of this invention, and the wavelength of a UV range can also be adjusted. Typical sensitizers that can be used in the present invention include cribero [J. V. Crivello, Adv. in Polymer Sci, 62,1 (1984)], specifically, pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavin, N- Vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives, and the like.

Surfactants

The composition of the present invention contains a surfactant. Surfactant used for this invention contains 0.001-5 mass% in the whole composition, Preferably it is 0.002-4 mass%, More preferably, it is 0.005-3 mass%. When using two or more types of surfactant, the total amount becomes said range. If the surfactant is less than 0.001 in the composition, the effect of coating uniformity is insufficient. On the other hand, if the surfactant exceeds 5% by mass, the mold transfer property is deteriorated, which is not preferable.

It is preferable that surfactant contains at least 1 sort (s) of a fluorine-type surfactant, a silicone type surfactant, and a fluorine-type silicone surfactant, and it is more preferable to contain both a fluorine type surfactant and a silicone type surfactant, or a fluorine-type silicone surfactant. It is most preferable to contain a fluorine-silicone surfactant.

Here, a fluorine-silicone surfactant means having both the requirements of a fluorine-type surfactant and a silicone type surfactant.

By using such a surfactant, the composition of this invention is used for the silicon wafer for semiconductor element manufacture, the glass angle board | substrate for liquid crystal element manufacture, chromium film, molybdenum film, molybdenum alloy film, tantalum film, tantalum alloy film, and nitride Streaks and scaly shapes (such as drying irregularities in the resist film) that occur during application on a substrate, such as silicon films, amorphous silicon films, tin oxide doped indium oxide (ITO) films, tin oxide films, etc. are formed. The purpose of solving the problem of poor application of the coating, the fluidity of the composition into the cavity of the mold recessed portion, the peelability between the mold and the resist is improved to improve the adhesion between the resist and the substrate, to lower the viscosity of the composition, etc. This becomes possible. In particular, by adding the surfactant in the composition of the present invention, the coating uniformity can be greatly improved, and in a coating using a spin coater or a slit scan coater, good coating suitability can be obtained without depending on the substrate size.

As an example of the nonionic fluorine-type surfactant used by this invention, brand name Florade FC-430, FC-431 (made by Sumitomo 3M company), brand name suffron "S-382" (made by Asahi Glass Company), EFTOP "EF-122A" , 122B, 122C, EF-121, EF-126, EF-127, MF-100 "(manufactured by Tochem Products Co., Ltd.), trade names PF-636, PF-6320, PF-656, PF-6520 (all of OMNOVA Corporation), Product name Pentgent FT250, FT251, DFX18 (all Neo's Corporation make), brand names Udine DS-401, DS-403, DS-451 (all Daikin Industries Co., Ltd. make), brand name Megapak 171, 172 , 173, 178K, 178A, (all manufactured by Dainippon Ink and Chemicals, Inc.); examples of the nonionic silicon-based surfactants include the trade name SI-10 series (manufactured by Takemoto Oil & Fat), Megapak Painttack 31 (Dainippon Ink; Chemical Industry Co., Ltd.) and KP-341 (made by Shin-Etsu Chemical Co., Ltd.) are mentioned.

As an example of the fluorine-type silicone surfactant used by this invention, brand name X-70-090, X-70-091, X-70-092, X-70-093, (all are the Shin-Etsu Chemical Co., Ltd. make), brand name Megapak R- 08 and XRB-4 (all are manufactured by Dainippon Ink and Chemicals, Inc.).

Antioxidant

The composition of the present invention also contains a known antioxidant. Content of antioxidant used for this invention becomes like this. Preferably it is 10 mass% or less in the whole composition, More preferably, it is 0.01-10 mass%, More preferably, it is 0.2-5 mass%. When using two or more types of antioxidant, the total amount becomes said range.

Antioxidants fade and ozone, active oxygen, NO _x, SO _x due to heat or light irradiation to suppress the discoloration caused by various oxidative gases, such as (X is a positive number). In particular, in the present invention, coloring of the cured film can be prevented by adding an antioxidant, and there is an advantage that the 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, thiocyanate salts and thio Urea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives and the like.

In the present invention, from the viewpoint of improving the permeability of the cured film and reducing the film thickness, in particular, a hindered phenol-based antioxidant, a hindered amine-based antioxidant and a thioether-based antioxidant are preferred, and a hindered phenol-based antioxidant and a hindered amine-based Antioxidants are more preferred.

As commercially available products of antioxidants, Irganox 1010, 1035, 1076, 1222 (above, manufactured by Chiba-Geigi Co., Ltd.), Antigene P, 3C, FR, Sumizer S, Sumizer GA80 (made by Sumitomo Chemical Industries), Adecaster AO70 And AO80, AO503 (manufactured by ADEKA Co., Ltd.), and the like, and these may be used alone or in combination.

Other ingredients

In addition to the above components, the composition of the present invention may contain a releasing agent, a silane coupling agent, a polymerization inhibitor, a ultraviolet absorber, a light stabilizer, an anti-aging agent, a plasticizer, an adhesion promoter, a thermal polymerization initiator, a colorant, an elastomer particle, a photoacid multiplier, and a photobase, as necessary. You may add a generator, a basic compound, a flow regulator, an antifoamer, a dispersing agent, etc.

You may mix | blend an organometallic coupling agent with the composition of this invention in order to improve the heat resistance of a surface structure which has a fine uneven | corrugated pattern, intensity | strength, or adhesiveness with a metal vapor deposition layer. Moreover, since an organometallic coupling agent also has the effect of accelerating a thermosetting reaction, it is effective. As an 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.

The said organometallic coupling agent can be mix | blended arbitrarily in the ratio of 0.001-10 mass% in solid content whole quantity of the curable composition for optical nanoimprints. By setting the ratio of the organometallic coupling agent to 0.001% by mass or more, there is a tendency to be more effective for improving the provision of heat resistance, strength, and adhesion to the vapor deposition layer. On the other hand, since the ratio of an organometallic coupling agent is 10 mass% or less, there exists a tendency which can suppress the stability of a composition and the film-forming defect, and is preferable.

Commercially available products for ultraviolet absorbers include Tinuvin P, 234, 320, 326, 327, 328, 213 (above, manufactured by Chiba-Gaigi Co., Ltd.), Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350, 400 (above, Sumitomo Chemical Industry Co., Ltd. product) etc. are mentioned. It is preferable to mix | blend a ultraviolet absorber in the ratio of 0.01-10 mass% arbitrarily with respect to the whole amount of the curable composition for photo nanoimprints.

Commercially available light stabilizers include Tinuvin 292, 144, 622LD (above, manufactured by Chiba-Geigi Co., Ltd.), Sanol LS-770, 765, 292, 2626, 1114, 744 (above, manufactured by Sankyo Chemical Industry Co., Ltd.), and the like. Can be mentioned. It is preferable to mix | blend an optical stabilizer in the ratio of 0.01-10 mass% with respect to the whole amount of a composition.

As a commercial item of an anti-aging agent, Antigene W, S, P, 3C, 6C, RD-G, FR, AW (above, Sumitomo Chemical Co., Ltd. product) etc. are mentioned. It is preferable to mix | blend anti-aging agent in the ratio of 0.01-10 mass% with respect to the whole amount of a composition.

It is possible to add a plasticizer to the composition of this invention in order to adjust adhesiveness with a board | substrate, flexibility of a film | membrane, hardness, etc. Specific examples of preferred plasticizers include, for example, dioctylphthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricredil phosphate, dioctyl adipate, dibutyl sebacate, triacetylglycerine, and dimethyl adipate. , Diethyl adipate, di (n-butyl) adipate, dimethyl suverate, diethyl suverate, di (n-butyl) suverate, 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 acquire the effect of adding a plasticizer, 0.1 mass% or more is preferable.

When hardening the composition of this invention, a thermal polymerization initiator can also be added as needed. As a preferable thermal polymerization initiator, a peroxide and an azo compound are mentioned, for example. Specific examples thereof include benzoyl peroxide, tert-butyl-peroxybenzoate, azobisisobutyronitrile and the like.

The composition of this invention may add a photobase generator as needed for the purpose of adjusting pattern shape, a sensitivity, etc. For example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoyl hydroxylamide, O-carbamoyl oxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] Cyclohexylamine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholino Benzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaammine cobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) -butanone, 2,6-dimethyl-3,5-diacetyl-4- (2'-nitrophenyl) -1,4-dihydropyridine, 2,6- Dimethyl-3,5-diacetyl-4- (2 ', 4'-dinitrophenyl) -1,4-dihydropyridine etc. are mentioned as a preferable thing.

You may add a coloring agent to the composition of this invention arbitrarily for the purpose of improving the visibility of a coating film. A coloring agent can use the pigment and dye used for UV inkjet composition, the composition for color filters, the composition for CCD image sensors, etc. in the range which does not impair the objective of this invention. As a pigment which can be used by this invention, the conventionally well-known various inorganic pigment or organic pigment can be used. Examples of the inorganic pigments are metal compounds represented by metal oxides, metal complex salts, and the like, and specific examples include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and metal complex oxides. have. As organic pigments, CIPigment Yellow 11, 24, 31, 53, 83, 99, 108, 109, 110, 138, 139, 151, 154, 167, CIPigment Orange 36, 38, 43, CIPigment Red 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, Cigigment Violet 19, 23, 32, 39, Cigigment Blue 1, 2, 15, 16, 22, 60, 66, CIPigment Green 7, 36 , 37, Cigigment Brown 25, 28, Cigigment Black 1, 7 and, carbon black can be exemplified. It is preferable to mix | blend a coloring agent in the ratio of 0.001-2 mass% with respect to the whole amount of a composition.

Moreover, in the composition of this invention, you may add elastomer particle as an arbitrary component for the purpose of improving mechanical strength, flexibility, etc.

As for the elastomer particle which can be added as an arbitrary component to the composition of this invention, average particle size becomes like this. Preferably it is 10 nm-700 nm, More preferably, it is 30-300 nm. For example, polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer, styrene / butadiene copolymer, styrene / isoprene copolymer, ethylene / propylene copolymer, ethylene / α-olefin copolymer, ethylene / α-olefin / It is particle | grains of elastomer, such as a polyene copolymer, an acrylic rubber, butadiene / (meth) acrylic acid ester copolymer, a styrene / butadiene block copolymer, and a styrene / isoprene block copolymer. Moreover, the core / shell type particle | grains which coat | covered these elastomer particles with the methyl methacrylate polymer, the methyl methacrylate / glycidyl methacrylate copolymer, etc. can be used. The elastomer particles may have a crosslinked structure.

These elastomer particles can be used alone or in combination of two or more thereof. Preferably the content rate of the elastomer component in the composition of this invention is 1-35 mass%, More preferably, it is 2-30 mass%, Especially preferably, it is 3-20 mass%.

You may add a basic compound arbitrarily to the composition of this invention for the purpose of suppressing hardening shrinkage, improving thermal stability, etc. Examples of the basic compound include an amine, a nitrogen-containing heterocyclic compound such as quinoline and quinolyzine, a basic alkali metal compound and a basic alkaline earth metal compound. Among these, an amine is preferable in view of the compatibility of a photopolymerizable monomer, For example, octylamine, naphthylamine, xylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, dimethylaniline, quinu Clydine, tributylamine, trioctylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine, hexamethylenetetramine, triethanolamine and the like.

In order to improve photocurability, you may add a chain transfer agent to the composition of this invention. Specifically, 4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and pentaerythritol tetrakis (3-mercaptobutylate) are mentioned.

Next, the formation method of the pattern (especially fine uneven | corrugated pattern) using the composition of this invention is demonstrated. In the present invention, the composition of the present invention can be applied and cured to form a pattern. Here, the composition of the present invention is usually cured by light irradiation or heat, preferably light irradiation and heat. Specifically, a pattern receptor is formed by applying a pattern forming layer made of at least the composition of the present invention on a substrate or a support, followed by drying to form a layer (pattern forming layer) made of the composition of the present invention to produce a pattern receptor. The mold is pressed on the surface of the pattern forming layer to transfer the mold pattern, and the fine uneven pattern forming layer is cured by light irradiation and heating. Usually, light irradiation and heating are performed in multiple times. Optical imprint lithography according to the pattern formation method of the present invention can also be laminated or multi-patterned, and can be used in combination with conventional thermal imprints.

Moreover, as an application of the composition of this invention, the composition of this invention is apply | coated on a board | substrate or a support body, and a permanent film, such as an overcoat layer and an insulating film, is produced by exposing, hardening, and drying (baking) the layer which consists of this composition as needed. You may.

In a permanent film (resist for structural member) used in a liquid crystal display (LCD) or the like, it is preferable to avoid mixing ionic impurities of metals or organic substances in the resist as much as possible so as not to impair the operation of the display, and the concentration thereof. As 1000 ppm or less, Preferably it is necessary to set it as 100 ppm or less.

Below, the pattern formation method and pattern transfer method using the composition of this invention are described. The composition of the present invention is generally well known coating methods, for example, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spin coating, slit scanning It can form by apply | coating by a method etc .. Although the film thickness of the layer which consists of a composition of this invention differs according to the use used, it is 0.05 micrometer-30 micrometers. Moreover, you may apply | coat multiple compositions of this invention.

The substrate or support for applying the composition of the present invention may be quartz, glass, optical film, ceramic material, deposited film, magnetic film, reflective film, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG, polyester film, poly Polymer substrates such as carbonate films, polyimide films, TFT array substrates, PDP electrode plates, glass or transparent plastic substrates, conductive substrates such as ITO and metals, insulating substrates, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon It does not restrict | limit especially, such as semiconductor manufacturing substrates. The shape of the substrate may be in the form of a plate or may be in the form of a roll.

Although it does not specifically limit as light which hardens the composition of this invention, Wavelength light or radiation of a region, such as high energy ionizing radiation, near-ultraviolet, far-ultraviolet, visible, and infrared, is mentioned. As the high energy ionizing radiation source, for example, electron beams accelerated by accelerators such as cokecroft accelerators, vandegraph accelerators, linear accelerators, betatrons, cyclotrons, etc. are used most industrially and economically. Radiation such as γ-rays, X-rays, α-rays, neutron rays, quantum rays, etc. emitted from a sonar reactor or the like can be used. As an ultraviolet source, 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, a solar lamp etc. are mentioned, for example. Radiation includes, for example, microwaves, EUV. Moreover, the laser beam used by the microfabrication of semiconductors, such as LED, a semiconductor laser beam, or 248 nm KrF excimer laser beam, a 193 nm ArF excimer laser, can also be used suitably for this invention. Monochrome light may be used for these lights, and light (mixed light) in which a some wavelength differs may be sufficient.

At the time of exposure, it is preferable to make exposure illumination into the range of 1mW / cm <2> -50mW / cm <2>. Since exposure time can be shortened by setting it as 1 mW / cm <2> or more, productivity improves, and since it is a tendency which can suppress deterioration of the permanent film characteristic by a side reaction generate | occur | producing by setting it as 50 mW / cm <2> or less, it is preferable. It is preferable to make exposure amount into the range of 5mJ / cm <2> -1000mJ / cm <2>. If it is less than 5 mJ / cm <2>, an exposure margin will become narrow and photocuring may become inadequate, and the problem of adhesion of an unreacted substance to a mold tends to arise. On the other hand, when it exceeds 1000 mJ / cm <2>, there exists a possibility of permanent film deterioration by decomposition | disassembly of a composition.

In addition, at the time of exposure, since the inhibition of radical polymerization by oxygen is prevented, an inert gas such as nitrogen or argon may be flowed to control the oxygen concentration to less than 100 mg / L.

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

Next, the mold material which can be used by this invention is demonstrated. In the optical nanoimprint using the composition of the present invention, at least one of the mold material and / or the substrate needs to select a light transmissive material. In the optical imprint lithography applied to the present invention, the curable composition for photo nanoimprint is applied onto a substrate, and the light-transmissive mold is pressed tightly to irradiate light from the back of the mold to cure the curable composition for photo nanoimprint. Moreover, the curable composition for optical nanoimprints may be apply | coated on a light transmissive board | substrate, a mold may be pressed tightly, the light may be irradiated from the back surface of a mold, and the curable composition for optical nanoimprints may be hardened.

Although light irradiation may be performed in the state which stuck a mold, and may be performed after mold peeling, in this invention, it is preferable to carry out in the state which stuck a mold.

As the mold usable in the present invention, a mold having a pattern to be transferred is used. The mold can form a pattern in accordance with a desired processing precision 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-transmissive mold material used in the present invention is not particularly limited, but may be one having a predetermined strength and durability. Specifically, light transparency resins, such as glass, quartz, PMMA, and a polycarbonate resin, the flexible film, such as a transparent metal vapor deposition film and polydimethylsiloxane, a photocuring film, a metal film, etc. are illustrated.

Although it does not specifically limit as a non-transmissive mold material used when the transparent substrate of this invention is used, What is necessary is just to have predetermined intensity | strength. Specific examples include ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, Fe, and substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, and the like. It is not restricted. The shape may be any of a plate mold and a roll mold. Roll-shaped molds are particularly applied where continuous productivity of transfer is required.

Since the mold used by the said invention improves peelability of the curable composition for optical nanoimprints, and a mold, you may use what performed the mold release process. Treatment with a silane coupling agent such as silicone or fluorine, for example, commercially available mold release agents such as Daikin Industries Co., Ltd., Offtool DSX, Sumitomo 3M Co., Novec EGC-1720, and the like can be preferably used.

When performing optical imprint lithography using the present invention, it is usually preferable to carry out the pressure of the mold to 10 atm or less. When the mold pressure is 10 atm or less, the mold and the substrate are hardly deformed and the pattern accuracy tends to be improved, and since the pressurization is low, the apparatus tends to be reduced, which is preferable. It is preferable to select the area | region which can ensure the uniformity of mold transfer in the range in which the residual film of the curable composition for photo nanoimprints of a mold convex part becomes small in the pressure of a mold.

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

Moreover, in the optical imprint lithography applied to this invention, although the board | substrate temperature at the time of light irradiation is normally performed at room temperature, you may irradiate light while heating in order to improve reactivity. When it is set as a vacuum layer as a front layer of light irradiation, it is effective in preventing bubble mixing, suppressing the reduction of the reactivity by oxygen mixing, and improving the adhesiveness between the mold and the curable composition for photo nanoimprint. Preferable vacuum degree in this invention is implemented in the range of 10 <^-1> Pa to normal pressure.

After mixing each said component, the composition of this invention can be prepared as a solution, for example by filtering by the filter of 0.05 micrometer-5.0 micrometers of pore diameters. The mixing and dissolution of the curable composition for optical nanoimprint is usually performed in the range of 0 ° C to 100 ° C. Filtration may be performed in multiple steps, and may be repeated several times. Moreover, the filtered liquid can also be filtered again. Although the material used for filtration can use a polyethylene resin, a polypropylene resin, a fluororesin, a nylon resin, etc., It does not specifically limit.

Permanent films (resist for structural members) used in liquid crystal displays (LCDs) and the like are bottled and transported and stored in containers such as gallon bottles and coat bottles after manufacture. In this case, inert containers are used to prevent deterioration. You may substitute by nitrogen, argon, etc. Moreover, although transport may be carried out at normal temperature at the time of storage, in order to prevent the deterioration of a permanent film | membrane, you may control temperature in the range of -20 degreeC-0 degreeC. Of course, it is necessary to shield the light at a level at which the reaction does not proceed.

The composition of the present invention can also be applied as an etching resist such as a semiconductor integrated circuit, a recording material, or a flat panel display.

Example

An Example is given to the following and this invention is demonstrated to it further more concretely. Materials, usage amounts, ratios, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific example shown below.

<Evaluation of optical nanoimprint>

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

<Viscosity measurement>

The viscosity was measured at 25 ± 0.2 ° C using a RE-80L rotary clay meter manufactured by Synchronous Industries, Ltd ..

Rotational speed at the time of measurement is more than 0.5 mPa · s less than 5 mPa · s 100 rpm, more than 5 mPa · s less than 10 mPa · s 50 rpm, more than 10 mPa · s less than 30 mPa · s 20 rpm, more than 30 mPa · s less than 60 mPa · s 10 rpm , 60 mPa · s or more and less than 120 mPa · s were performed at 5 rpm and 120 mPa · s or more at 1 rpm or 0.5 rpm, respectively.

<Observation of pattern precision>

Each composition which consists of a monomer, a photoinitiator, surfactant, and antioxidant shown to the following Tables 1-5 was adjusted, and it spin-coated on the glass substrate so that it might become set to 3.0 micrometers in film thickness. The spin-coated coating 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, and the mold pressing force was 0.8 kN and the degree of vacuum during exposure was 10 Torr. Having a groove depth of 4.0 µm and exposing it to a condition of 240 mJ / cm 2 from the surface of the mold made of a polydimethylsiloxane (made by Toray Dow Corning, Inc., cured SILPOT184 at 80 ° C. for 60 minutes) for 240 mJ / cm 2. The mold was removed to obtain a resist pattern. The obtained resist pattern was completely cured by heating at 230 ° C. for 30 minutes in an oven.

The pattern shape after transfer was observed with the scanning electron microscope or the optical microscope, and the pattern shape was evaluated as follows.

A: It is almost the same as the pattern of the original plate which becomes the basis of mold pattern shape.

B: There is a part (part less than 10% of the pattern of the disc) and the part different from the pattern shape of the disc on which the mold pattern shape is based.

C: There is a part different from the pattern shape of the original plate which is the basis of the mold pattern shape (the range of 10% or more and less than 20% of the pattern of the original plate)

D: The film thickness of the pattern which differs clearly from the pattern of the disk which is the basis of the mold pattern shape is 20% or more different from the pattern of the disk.

<Evaluation of peelability>

Using the same sample used for pattern precision observation, whether the composition component adhered to the mold used for pattern formation was observed with the scanning electron microscope or the optical microscope, and peelability was evaluated as follows.

A: The adhesion of the curable composition to the mold was not confirmed at all.

B: The adhesion of some curable composition to the mold was confirmed.

C: The adhesion of the curable composition of a mold was confirmed clearly.

<Evaluation of the hardness>

Each composition was spin-coated on a glass substrate so that the film thickness might be in the range of 3 to 10 μm, and the mold was exposed to an exposure dose of 240 mJ / cm 2 under a nitrogen atmosphere without pressing the mold, and then heated in an oven at 230 ° C. for 30 minutes to cure. The dynamic hardness was measured for the film | membrane made by the Shimadzu Corporation micro-hardness tester. Measurement conditions were made into triangular pyramid indenters, load 1 mN, and holding time 1 second.

Dynamic hardness

A ： 32 or more

B ： 28 or more, less than 32

C: 25 or more and less than 28

D ： Less than 25

<Evaluation of transmittance>

The film which spin-coated each composition on the glass substrate so that it might become a film thickness of 3.0 micrometers, was exposed by exposure amount 240mJ / cm <2> under nitrogen atmosphere, without pressing a mold, and the film which hardened by heating 230 degreeC and 270 minutes in oven after that was made by Shimadzu Corporation. , The transmittance at 400 nm was measured by UV-2400PC.

Transmittance

A ： 97% or more

B: 95% or more but less than 97%

C: 90 or more, less than 95%

D ： Less than 90

<Solvent resistance test>

Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 µm, and exposed to a light exposure amount of 240 mJ / cm 2 under a nitrogen atmosphere without pressing the mold, and then the film was cured by heating at 230 ° C. for 30 minutes in an oven at 25 ° C. It was immersed in N-methylpyrrolidone solvent for 30 minutes, and the change of the cured film before and behind immersion was evaluated as follows.

A: Less than 1% of film thickness change

B: Film thickness change 1% or more but less than 2%

C: 2% or more of film thickness change, less than 10%

D ： Surface roughness is generated

<Monomer having two or more kinds of curable functional groups having different reactivity in the same molecule>

Q-1: Compound (M-12) dicyclopentenyl acrylate (FA-511AS: the Hitachi Chemical company make)

Q-2: Compound (M-13) dicyclopentenyloxyethyl acrylate (FA-512AS:

Hitachi Chemical Co., Ltd.)

Q-3 ： Compound (M-32) 3-cyclohexenylmethyl acrylate

Q-4: Compound (M-22) acryloyloxyethyl isocyanate (Carens AOI: Showa Denko Corporation)

Q-5: Compound (M-24) (3-ethyl-3-oxetanyl) methyl acrylate (biscote OXE10: Osaka organic chemical industry company make)

Q-6 ： Compound (M-29) 3-trimethoxysilylpropyl acrylate (KBM-5103: manufactured by Shin-Etsu Chemical Co., Ltd.)

Q-7 ： Compound (M-30) allyl acrylate (Aldrich's reagent)

Q-8 ： Compound (M-33) acrylate-2-acryloyloxy-3-allyloxypropyl ester

Q-9 ： Compound (M-4) Acrylic acid-2,3-diallyloxypropyl ester

Q-10 ： Compound (M-34) acrylic acid-3,5-diallyloxycyclohexyl ester

Q-11 ： Compound (M-38) 3,5-bis (allyloxycarbonyl) phenyl acrylate

Q-12 ： Compound (M-39) 4-allyloxycarbonylphenyl acrylate

Q-13 ： Compound (M-40) allyloxycarbonyl-3,5-bis (acryloyloxy) benzene

Q-14: Compound (M-41) Bisacryloyloxymethylpropionate Allyl

Q-15: Compound (M-42) Bisallyloxycarbonylethyl acrylate

Q-16: Compound (M-43) Allyloxycarbonylmethyl Acrylate

Q-17: compound (M-44) allyloxycarbonylethyl acrylate

<Other monofunctional monomer>

R-1: benzyl acrylate (biscoat # 160: manufactured by Osaka Organic Chemical Co., Ltd.)

R-2 ： 2-naphthyl acrylate

R-3 ： 1-naphthylmethylacrylate

<Other bifunctional monomer>

S-01 ： Neopentyl glycol diacrylate

<Other trifunctional or higher monomer>

S-10: Trimethylolpropane triacrylate (Aronix M-309: Dong-A Synthetic Co., Ltd. product)

S-11: 1,3,5-trisacryloyloxybenzene

<Other trifunctional or higher monomer>

S-12 ： 4-functional urethane acrylate (U-4HA: manufactured by Shin-Nakamura Chemical Co., Ltd.)

<Other polymerizable monomer>

S-23: HOA-MS (2-acryloyloxyethyl succinic acid, Kyoi Corporation Chemical Co., Ltd. product)

<Photoinitiator>

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

BASF Corporation)

<Surfactant>

W-1 ： Non-fluorine type surfactant (Takemoto Oils & Fats Co., Ltd. make: Pionine D6315)

W-2: Fluorine-type surfactant (DIC Corporation make: Megapak F780F)

<Antioxidant>

A-1 ： Sumilizer GA80, hindered phenol-based (manufactured by Sumitomo Chemical Co., Ltd.)

A-2 ： Adecaster AO503, hindered phenol type + thioether type (made by Adeka Japan Corporation)

A-3 ： Irganox 1035FF, Hindered phenol type + thioether type (made by Chiba Specialty Chemical Co., Ltd.)

A-4: Adecaster LA-57, hindered amine type (made by ADEKA Corporation)

A-5: TINUVIN144, hindered amine type + hindered phenol type (made by Chiba specialty chemical company)

<Silicone oil>

X-1 ： X-22-3710 (manufactured by Shin-Etsu Chemical Co., Ltd.)

The monomer mentioned above was mix | blended so that it might become the composition of the said table | surface, the composition of the Example was manufactured, and it measured about the viscosity, pattern precision, peelability, hardness, transmittance, and solvent resistance. The results are shown in Table 9 below.

Comparative example  One

The composition described in Example 6 of the inkjet composition disclosed in International Publication WO2004 / 099272 was carried out in the same manner as in the present example, and measured for pattern precision, peelability, hardness, transmittance, and solvent resistance. Table 8 shows the compounding table of the composition, and Table 9 shows the test results.

Comparative example  2

The composition described in Example 1 of the composition for nanoimprints disclosed in Unexamined-Japanese-Patent No. 2007-84625 was implemented similarly to this Example, and was measured about pattern precision, peelability, hardness, transmittance, and solvent resistance. Table 8 shows the compounding table of the composition, and Table 9 shows the test results.

Comparative example  3

The composition described in Example 3 of the photocurable composition disclosed by Unexamined-Japanese-Patent No. 2005-255854 was implemented similarly to this Example, and was measured about pattern precision, hardness, transmittance, and solvent resistance. Table 8 shows the test results of the composition table of the composition.

Comparative example  4

The composition described in Example 2 of the photocurable resin composition disclosed in Unexamined-Japanese-Patent No. 2007-186570 was implemented similarly to this Example, and was measured about pattern precision, hardness, and transmittance | permeability. Table 8 shows the compounding table of the composition, and Table 9 shows the test results.

Comparative example  5

The composition described in Example 6 of the photocurable resin composition disclosed in Unexamined-Japanese-Patent No. 2007-186570 was implemented similarly to this Example, and was measured about pattern precision, hardness, and transmittance | permeability. Table 8 shows the compounding table of the composition, and Table 9 shows the test results.

All the said Comparative Examples 1-5 do not contain antioxidant. In addition, Comparative Example 2 and Comparative Example 4 do not include two or more kinds of curable functional groups having different reactivity.

In the composition of this invention, all of pattern precision, peelability, hardness, and transmittance | permeability were excellent. On the other hand, in the composition of the comparative example, hardness fell in all. Moreover, in the comparative example 1, it also fell about pattern precision and transmittance | permeability.

According to the present invention, when used as a permanent film, it has become possible to provide a composition which is excellent overall in terms of permeability, mechanical strength, peelability, pattern shape, coatability, and solvent resistance after heat curing. Moreover, when used as a permanent film, such as a transparent protective film and a spacer, it becomes possible to provide the composition which has mechanical characteristics, such as outstanding residual film property, light transmittance, and scratch resistance, and solvent resistance.

Claims (23)

(A) Curable composition for nanoimprint containing the monomer which has at least 2 type of reactivity different curable functional group in the same molecule, and (C) antioxidant. The method of claim 1, Curable composition for nanoimprints in which at least 1 is an (alpha), (beta)-unsaturated ester group among the said curable functional groups. The method of claim 1, Furthermore, (B) curable composition for nanoimprints containing surfactant. The curable composition for nanoimprint according to claim 1, wherein the composition has a viscosity of 3 to 18 mPa · s. (A) It contains at least two types of curable functional groups which differ in reactivity in the same molecule, and at least 1 of those curable functional groups contains the monomer which is an (alpha), (beta)-unsaturated ester group, (B) surfactant, and (C) antioxidant. The curable composition for nanoimprint, wherein the composition has a viscosity of 3 to 18 mPa · s. The method of claim 1, Curable composition for nanoimprints in which the monomer is represented by the following General Formula (1).

(In general formula (1), R <^1> represents a hydrogen atom or a hydroxymethyl group, X represents an organic group. M shows the integer of 1-3, n shows the integer of 1-4. Y is A curable functional group having a carbon-carbon unsaturated bond, a curable functional group having a carbon-nitrogen unsaturated bond, a curable functional group having a cyclic group containing an oxygen atom, or a group represented by the following general formula (2).

(R ² represents an alkyl group or an aryl group, respectively.) The method of claim 6, In general formula (1), at least 1 of Y is a vinyl ether group, an allyl ether group, an allyl ester group, a cyclohexenyl group, a cyclopentenyl group, a dicyclopentenyl group, a styryl group, methacryloyloxy group, methacryloyl Curable composition for nanoimprints chosen from the group which consists of an amide group, an acrylamide group, a vinylsilane group, an N-vinyl heterocyclic group, and a maleimide group. The method of claim 6, The curable composition for nanoimprint in which at least one of Y in General Formula (1) is selected from an allyl ether group, a cyclohexenyl group, and a dicyclopentenyl group. The method of claim 6, At least one of Y in General formula (1) is an allyl ether group, and the curable composition for nanoimprints whose sum of n and m is 3-6. The method of claim 6, Curable composition for nanoimprints in which at least 1 of Y in General formula (1) is an isocyanate group or a nitrile group. The method of claim 6, Curable composition for nanoimprints chosen from the group which at least 1 of Y in General formula (1) consists of an oxetane ring, an oxirane ring, and an ethylene carbonate group. The method of claim 6, The curable composition for nanoimprint in which X represents an organic group having 3 to 9 carbon atoms in general formula (1). The method of claim 6, Curable composition for nanoimprints in which the compound represented by the said General formula (1) is any 1 or more types of following General Formula (3)-(5).

(In General Formulas (3) to (5), R ³ represents a hydrogen atom or a methyl group, respectively, and R ⁴ represents a methyl group or an ethyl group, respectively.) The method of claim 1, Curable composition for nanoimprints containing polymerizable monomers other than the said monomer (A), and a photoinitiator. The method of claim 1, The curable composition for nanoimprint, wherein the antioxidant is selected from at least a hindered phenol-based antioxidant or a hindered amine-based antioxidant. The method of claim 1, Curable composition for nanoimprints whose content of the said antioxidant is 10 mass% or less. The method of claim 1, Curable composition for nanoimprints which does not contain the compound whose molecular weight exceeds 1000. The method of claim 1, Curable composition for nanoimprint in which the surface tension of the said composition exists in the range of 18-30 mN / m. The method of claim 1, Curable composition for nanoimprints, which is cured by performing light irradiation and heating. Hardened | cured material which hardened the curable composition for nanoimprints in any one of Claims 1-19. The manufacturing method of the hardened | cured material containing what hardens | cures the curable composition for nanoimprints in any one of Claims 1-19 by performing light irradiation and heating multiple times. The member for liquid crystal display devices using the hardened | cured material of Claim 20. The manufacturing method of the member for liquid crystal display devices which hardens | cures a composition in any one of Claims 1-19 by performing light irradiation and heating multiple times.