KR20080069553A - Curable composition for optical nanoimprint lithography and pattern formation method using the same - Google Patents

Abstract

It provides a novel curable composition for photo nanoimprint lithography excellent in photocurability. 0.00-50 mass% of at least 1 sort (s) of 35-99 mass% of polymerizable unsaturated monomers, 0.1-15 mass% of photoinitiators, a fluorine-type surfactant, a silicone type surfactant, and a fluorine-type silicone surfactant, and 0.1-50 mass% of inorganic oxide fine particles. Curable composition for optical nanoimprint lithography comprising a.

Description

Curable composition for optical nanoimprint lithography and pattern formation method using same {CURABLE COMPOSITION FOR PHOTO NANO-IMPRINT LITHOGRAPHY AND PATTERN FORMING METHOD USING THE SAME}

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

The nanoimprint method develops an embossing technique that is well known in optical disc fabrication, and presses a mold original (commonly called a mold, a stamper, or a template) in which a pattern of irregularities is formed, and mechanically deforms the micro pattern by pressing it with a resist. It is the technique to transfer precisely. Once a mold is produced, since the nanostructure can be simply and repeatedly formed, it is economical and nano-processing technology with less harmful wastes and discharges. Therefore, application to various fields is expected in recent years.

The nanoimprint method uses a thermoplastic resin as a work material (S. Chou et al .: Appl. Phys. Lett. Vol. 67, 3114 (1995)) and a curable composition for photo nanoimprint lithography (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 the mold onto the polymer resin heated to the glass transition temperature or higher, and peeling the mold after cooling. Since it is applicable to various resin materials and glass materials, application to various aspects is expected. US Patent Nos. 5,772, 905 and 5,956, 216 disclose methods of nanoimprint using thermoplastic resins to form nanopatterns at low cost.

On the other hand, in the optical nanoimprint system which irradiates light through a transparent mold and photocures the curable composition for optical nanoimprint lithography, imprint at room temperature becomes possible. In recent years, new developments such as a nanocasting method combining 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, which has a function, and can be applied as an element part or structural member of various nanotechnology, is used in various micro-nano optical elements, high-density recording media, optical films, and flat panel displays. Structural members and the like. The second is to build a laminated structure by simultaneous integral molding of micro structure and nano structure or simple interlayer position combination, and to apply it to the production of μ-TAS or biochip. Third, it is intended to be applied to the fabrication of high-density semiconductor integrated circuits, the fabrication of transistors in liquid crystal displays, or the like instead of conventional lithography, by high-precision positioning and high integration. In recent years, the countermeasure to the practical use of the nanoimprint method regarding these applications is becoming active.

As an application example of the nanoimprint method, first, an application example to the production of a high density semiconductor integrated circuit 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, the processing method is close to the wavelength of the light source of photoexposure, and lithography has also reached its limit. Therefore, in order to advance new miniaturization and high precision, the electron beam drawing apparatus which is a kind of charged particle beam apparatus can be used instead of the lithography technique. Pattern formation using an electron beam is different from the batch exposure method in pattern formation using a light source such as i-rays or excimer lasers, and a method of drawing a mask pattern is taken. It takes time and takes time for pattern formation to become a drawback. Therefore, as the integration degree is dramatically increased to 256 megabytes, one gigabyte, and four gigabytes, the partial pattern formation time also becomes remarkably long, resulting in remarkably inferior throughput. 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 to them, and forms the electron beam of a complicated shape is advanced. However, while miniaturization of the pattern has progressed, besides the necessity of increasing the size of the electron beam drawing device, a disadvantage arises in that the device price is high, such as a mechanism for more precisely controlling the mask position.

On the other hand, proposed nanoimprint lithography has been proposed as a technique for performing fine pattern formation at low cost. For example, U.S. Patent Nos. 5,772,905 and U.S. Patents 5,259,926 use a silicon wafer as a stamper, and a nanoimprint that forms a microstructure of 25 nanometers or less by transfer. Techniques are disclosed.

In addition, Japanese Patent Laid-Open No. 2005-527110 discloses a composite composition using nanoimprint applied to the field of semiconductor microlithography. On the other hand, studies to apply nanoimprint lithography to semiconductor integrated circuit fabrication such as fine mold fabrication technology, mold durability, mold fabrication cost, mold release from resin, imprint uniformity and alignment accuracy, and inspection technology are being actively promoted. Started to.

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

BACKGROUND ART In accordance with the trend of large-sized and high-definition LCDs and PDP substrates, photo-nanoimprint lithography 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 is required.

Moreover, as a structural member of LCD, etc., it is an optical nano 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. Imprint lithography applications are also being considered. 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 different from the etching resist and is an element remaining in a semiconductor element, a recording medium, a flat display panel, or the like as it is. For example, as a transparent protective film material for color filters used for a liquid crystal panel, the transparent protective film was conventionally formed by the process using photocurable resins and thermosetting resins, such as a siloxane polymer, a silicone polyimide, an epoxy resin, and an acrylic resin ( Japanese Patent Laid-Open No. 2000-39713, Japanese Patent Laid-Open No. 6-43643). In forming the protective film by photolithography, properties such as uniformity of the coating film, substrate adhesion, high light transmittance after heat treatment exceeding at least 200 ° C, planarization properties, solvent resistance, and imaging resistance are also required.

A spacer defining a cell gap in a liquid crystal display is also a kind of permanent film. In conventional photolithography, a photocurable composition composed of a resin, a photopolymerizable monomer and an initiator has been widely used (Japanese Patent Laid-Open No. 2004-240241). ). Spacers require high mechanical properties, hardness, developability, pattern accuracy, and adhesion to external pressure.

However, until now, the preferred composition of the transparent protective film or photocurable composition for spacer formation used by the nanoimprint method was not disclosed at all.

In addition, the coating film uniformity has been increasingly demanded in various parts such as the uniformity of the coating film thickness for the center portion and the periphery of the substrate and the dimensional uniformity, the film thickness, and the shape due to the high resolution. Conventionally, in the field of manufacturing a liquid crystal display device 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 1 m square glass, the amount of resist dropped and discarded during rotation (spinning) is considerably increased and high-speed rotation is performed. This causes problems such as cracking of the substrate and securing of tact time. In addition, since the coating performance in the method of spin after central dropping depends on the rotational speed at the time of spin and the coating amount of the resist, there is no general-purpose motor which can obtain the required acceleration when it is further applied to the fifth generation substrate to be enlarged. There was a problem that a special order increased the parts cost. In addition, even if the substrate size and the device size are enlarged, the required performance in the coating process hardly changes, for example, coating uniformity ± 3% and tact time 60 to 70 seconds / sheet. In this case, it has become difficult to meet the requirements other than the coating uniformity. From this phenomenon, a resist coating method by a discharge nozzle type has been proposed as a new resist coating method that can be applied to a large substrate after the fourth generation substrate, in particular after the fifth generation substrate. The resist coating method by the discharge nozzle method is a method of applying the photoresist composition to the entire application surface of the substrate by moving the discharge nozzle and the substrate relatively, for example, in the form of a discharge or slit in which a plurality of nozzle holes are arranged in a column. A method of using a discharge nozzle having a discharge port and capable of discharging the photoresist composition in a band state has been 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 spinning the said board | substrate is also proposed. Therefore, in order to replace the conventional photolithography resist with a nanoimprint composition and apply it to these liquid crystal display device manufacturing fields, the uniformity of coating on a substrate becomes important.

In positive type photoresists used in semiconductor integrated circuit fabrication or liquid crystal display fabrication, pigment dispersion photoresist for color filter fabrication, and the like, fluorine-based and / or silicon-based surfactants are added and coating properties, specifically, occur at the time of application on a substrate. It is well known to solve problems of coating defects such as striation and scaly patterns (dry stains on resist films) (Japanese Patent Laid-Open No. 7-230165, Japanese Patent Laid-Open No. 2000-181055, and Japanese Patent Laid-Open). 2004-94241). Moreover, in order to improve the abrasion property and applicability | paintability of protective films, such as a compact disc and a magneto-optical disc, adding fluorine type surfactant and a silicone type surfactant to a solvent-free photocurable composition is disclosed (Japanese Patent Laid-Open No. 2004-94241). , Japanese Patent Application Laid-open No. Hei 4-149280, Japanese Patent Application Laid-open No. Hei 7-62043, Japanese Patent Application Laid-Open No. 2001-93192). Similarly, Japanese Patent Laid-Open No. 2005-8759 discloses adding a nonionic fluorine-based surfactant in order to improve ink discharge stability of an inkjet composition. Further, Japanese Patent Laid-Open No. 2003-165930 discloses that when embossing a painting composition coated with a thick film with a brush, brush, bar coater or the like into a mold for hologram processing, at least 1% of a polymerizable unsaturated double bond-containing surfactant, The example which adds 3% or more preferably and improves the water swellability of a cured film is disclosed. Thus, the technique which adds surfactant to protective films, such as positive type photoresist, pigment dispersion photoresist for color filter manufacture, and a magneto-optical disk, and improves applicability | paintability is a well-known technique. Moreover, as shown to the said inkjet or painting composition, the technique of adding surfactant to a solvent-free photocurable resin and adding a surfactant for the improvement of the characteristic in each use is also known. Japanese Patent Application Laid-Open No. 2007-84625 discloses an example of using a photocurable resin containing a fluorine-based surfactant as an etching resist using the photo nanoimprint method for preparing a semiconductor integrated circuit.

However, the method for improving the substrate coating property of the photocurable nanoimprint resist composition which does not contain the pigment, dye, and organic solvent which are used for a permanent film as an essential component is 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. It is necessary to make it good. It was difficult to make this fluidity | liquidity, peelability, and adhesiveness compatible.

The prior art regarding the photo nanoimprint which is the application range of this invention is demonstrated in more detail. In photo nanoimprint lithography, a liquid curable composition for photo nanoimprint lithography is added dropwise onto a substrate such as a silicon wafer, quartz, glass, film, or other material, for example, a ceramic material, a metal, or a polymer. After coating with a film thickness of 탆, pressing while pressing a mold having a fine concavo-convex of a pattern size of about several tens of nm to several tens of 탆, and irradiating in a pressurized state to cure the composition, the mold is peeled off from the coating film and transferred It is common to get a printed pattern. Therefore, in the case of photo nanoimprint lithography, at least one of the substrate or the mold needs to be transparent when light is irradiated. Usually, when irradiated with light from the mold side, the inorganic material which permeate | transmits UV light, such as quartz and sapphire, light-transmitting resin etc. is used for a mold material.

In the photo nanoimprint method, (1) the heating / cooling process is unnecessary and high throughput is expected with respect to the thermal nano imprint method. (2) Imprint at low pressure is possible because the liquid composition is used. (3) There are no dimensional changes due to thermal expansion, (4) the mold is transparent, alignment is easy, and (5) major advantages such as a rigid three-dimensional crosslinked product are obtained after curing. It is particularly suitable for semiconductor micromachining applications and micromachining applications in the field of flat panel displays so that alignment accuracy is required.

As another feature of the optical nanoimprint method, since the resolution does not depend on the light source wavelength as compared with conventional optical lithography, an expensive device such as a stepper or an electron beam drawing device is not required even when the nanometer order is finely processed. Is characteristic. On the other hand, the photo-nanoimprint method requires an equal-fold mold, and the mold and the resin contact each other, which is concerned about the durability and cost of the mold.

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

Molds used in photo nanoimprint lithography can be manufactured from a variety of materials, such as metals, semiconductors, ceramics, spin on glass (SOG), or certain plastics. For example, a mold of a flexible polydimethylsiloxane having a desired microstructure described in pamphlet of WO 99/22849 has been proposed. In order to form a three-dimensional structure on one surface of the mold, various lithographic methods can be used depending on the size of the structure and the specification for its resolution. Lithography of electron beams and X-rays is commonly used for structural dimensions of 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 lithography is important, and the surface treatment of the mold and the mold, specifically, is carried out using a hydrogenated silsesquioxane or a fluorinated ethylene propylene copolymer mold. Attempts to solve the problem have been made so far.

Here, the photocurable resin used for photo nanoimprint lithography is demonstrated. Photocurable resins applied to nanoimprints are largely classified into radical polymerization type, ion polymerization type, or hybrid type thereof from the difference in reaction mechanism. Either composition can be imprinted, but a radical polymerization type having a wide range of materials is generally used (F. Xu et al .: SPIE Microlithography Conference, 5374, 232 (2004)). In the radical polymerization type, a composition including a monomer (monomer) or oligomer having a radical polymerizable vinyl group or a (meth) acryl group and a photopolymerization initiator is generally used. When irradiated with light, radicals generated by the photopolymerization initiator attack the vinyl group, thereby causing chain polymerization to form a polymer. When a bifunctional or higher polyfunctional group monomer or oligomer is used as a component, a crosslinked structure is obtained. DJ Resnick et al .: J. Vac. Sci. Technol. B, Vol. 21, No. 6, 2624 (2003), a composition capable of imprinting at low pressure and room temperature by using a low viscosity UV curable monomer. Is disclosed.

The properties of the materials used for optical nanoimprint lithography are described in detail. Although the required properties of the material vary depending on the application to be applied, the demands on the process characteristics do not depend on the use but have something in common. For example, the main required items shown in the latest resist material handbook, P1, 103-104 (2005, Information Equipment Publication) are coating properties, substrate adhesion, low viscosity (<5 mPa · s), peelability, and low curing. Shrinkage, fast curing, and the like. In particular, as a necessary use for low pressure imprint and reduction of residual film ratio, it is known that the demand for low viscosity material is strong. On the other hand, the required characteristics for each application include, for example, refractive index, light 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 properties and balance all the properties is key to material design. Since at least the required characteristics 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 an optical nanoimprint lithography application, in the latest resist material handbook, P1, 103-104 (2005), a photocurable material having a viscosity of about 60 mPa · s (25 ° C.) is disclosed. And is known. Similarly, CMC Publication: Development and Application of Nanoimprint P159-160 (2006) discloses a fluorine-containing photosensitive resin having a viscosity of 14.4 mPa · s as the main component of monomethacrylate as the main component.

As mentioned above, although there is a description of the request regarding viscosity regarding the composition used for the photo nanoimprint, there have been no reports on the design guide of the material for each application.

An example of a photocurable resin applied to photo nanoimprint lithography will now be described. Japanese Patent Laid-Open No. 2004-59820 and Japanese Patent Laid-Open 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, Japanese Patent Laid-Open No. 2006-114882 discloses a curable composition for photo nanoimprint lithography for imprint that includes 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.

N. Sakai et al .: J. Photopolymer Sci. Technol. Vol. 18, No. 4, 531 (2005) include (1) functional acrylic monomers, (2) functional acrylic monomers, and (3) functional acrylic monomers. A photocurable radical polymerizable composition comprising a photopolymerization initiator and a photopolymerization initiator, a photocationic polymerizable composition containing a photocurable epoxy compound and a photoacid generator, and the like are applied to nanoimprint lithography to investigate thermal stability and mold peelability. have.

M. Stewart et al .: MRS Buletin, Vol. 30, No. 12, 947 (2005) discuss problems such as peelability of photocurable resins and molds, film shrinkage after curing, and reduction in sensitivity by inhibiting photopolymerization in the presence of oxygen. As a study for improvement, the curable composition for optical nanoimprint lithography containing (1) a functional acrylic monomer, (2) a functional acrylic monomer, a silicone containing monofunctional acrylic monomer, and a photoinitiator is disclosed.

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

B. Vratzov et al .: J. Vac. Sci. Technol. B21 (6), 2760 (2003) disclose a curable composition for photo nanoimprint lithography comprising a silicone monomer, a trifunctional acrylic monomer and a photopolymerization initiator on a silicon substrate. A composition excellent in high resolution and uniformity of coating is disclosed by a SiO ₂ mold.

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

However, N. Sakai et al .: J. Photopolymer Sci. Technol. Vol. 18, No. 4, 531 (2005), M. Stewart et al .: MRS Buletin, Vol. 30, No. 12, 947 (2005). ), T. Beiley et al .: J. Vac. Sci. Technol. B18 (6), 3572 (2000), B. Vratzov et al .: J. Vac. Sci. Technol. B21 (6), 2760 (2003) ), EKKim et al .: J. Vac. Sci. Technol, B22 (1), 131 (2004), a scene in which acrylic monomers, acrylic polymers and vinyl ether compounds having different functional groups are applied to photo nanoimprint lithography. Although various types of chemical conversion resins have been disclosed, there are guidelines for designing materials such as a preferred kind as a composition, an optimal monomer type, a combination of monomers, an optimum viscosity of a monomer or a resist, a preferable solution property of a resist, and improved coating properties of a resist. It is not disclosed at all. Therefore, a preferable composition for widely applying the composition to photo nanoimprint lithography applications is not known, and it is a fact that a photo nanoimprint resist composition which can never be satisfied is not proposed until now.

B.Vratzov et al .: J.Vac.Sci.Technol. B21 (6), 2760 (2003), EKKim et al .: J.Vac.Sci.Technol, B22 (1), 131 Although some of the compositions of (2004) have a low viscosity, all of them are photocured to form a pattern, and the transmittance of the cured film in the case of being subsequently heat-treated is low (colored), and the hardness is also insufficient, thus enduring practical use as a permanent film. Not to pay The composition is unknown. Proc.SPIE Int.Soc.Opt.Eng., Vol.6151, No.Pt2, 61512F (2006), Science and Industry, Vol. 80, No.7, 322 (2006), silica sol treated with optically functional crosslinking material , An inorganic / organic hybrid material composed of a mixture of a (meth) acrylic monomer and a photopolymerization initiator has been proposed, and its application to optical nanoimprint lithography has been reported. Proc. SPIE Int. Soc. Opt. Eng., Vol. 6151, No. Pt2, 61512F (2006), Science and Industry, Vol. 80, No. 7, No. 7, 322 (2006). It has been reported that as a mold material, it can be patterned to a line width of 600 nm. By the way, there existed a problem, such as peelability with a mold and hardness of a cured film, and was not necessarily satisfying.

In addition, the composition of Proc. SPIE Int. Soc. Opt. Eng., Vol. 6171, No. Pt2, 61512F (2006), Science and Industry, Vol. 80, No. 7, 322 (2006) also has a low viscosity. However, the light transmittance of the cured film in the case where all of them are photocured to form a pattern and subsequently heat treated is low (colored), and the hardness is also insufficient. In particular, the composition which endures practical use as a permanent film is not known.

In addition, Japanese Patent Application Laid-Open No. 2000-143924 discloses a hard coat composition containing a surface-treated colloidal silica, a specific (meth) acrylic monomer, a leveling agent, and a photopolymerization initiator, in which both film hardness and low curing shrinkage are achieved. Although application to optical disks has been reported, these compositions have insufficient peelability with a mold and substrate coating properties, and application to optical nanoimprint lithography has been difficult. Moreover, the transmittance | permeability at the time of heat processing after photocuring is low (colored), and it cannot endure use as a permanent film.

Thus, the resist composition which can endure practical use as a permanent film and to which the photo nanoimprint method can be applied is the fact which has not been proposed until now.

Major technical challenges as permanent films include pattern accuracy, adhesion, transparency after heat treatment above 200 ° C, high mechanical properties (strength to external pressure), imaging resistance, planarization properties, solvent resistance, and outgas reduction during heat treatment. There are many problems. When applying the curable composition for photo nano imprint lithography for a 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) transparency after heat treatment

(3) image resistance

The grant of is important.

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

(4) It is necessary to secure the fluidity of the resist to the recess of the mold and to lower the viscosity under the use of a solvent-free or small amount of solvent.

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

Although various materials are disclosed about the curable composition for optical nanoimprint lithography for nanoimprint, the composition known for the use of the composition for inkjets, the protective film for a magneto-optical disk, or the optical nanoimprint lithography used as an etching resist so far The curable composition has a part in common with the curable composition for optical nanoimprint lithography and materials used for permanent films, but differs greatly in terms of high temperature heat treatment, mechanical strength, and the like, and is applied to inkjet, protective films for magneto-optical disks, and etching resists. If the photocurable resin is applied as a resist for a permanent film as it is, hardly enduring practicality with transparency, solvent resistance, etc. is hardly obtained.

The present invention has been accomplished in view of the above-described fact, and an object thereof is to provide a curable composition for photo nanoimprint lithography excellent in novel photocurability. In particular, it aims at providing the composition comprehensively excellent in photocurability, adhesiveness, peelability, residual film property, pattern shape, applicability | paintability, and etching ability. Moreover, when used as a permanent film, such as a protective film and a spacer, it aims at providing the composition which has mechanical characteristics, solvent resistance, such as outstanding residual film property, light transmittance, and imaging resistance.

As a result of earnestly examining the inventors by the above problems, the inventors have found that the above problems can be solved by the following means.

(1) 0.001-5 mass% and inorganic oxide fine particle of 35-99 mass% of polymerizable unsaturated monomers, 0.1-15 mass% of photoinitiators, at least 1 sort (s) of a fluorine-type surfactant, a silicone type surfactant, and a fluorine-type silicone surfactant. Curable composition for optical nanoimprint lithography containing -50 mass%.

(2) The composition as described in (1), wherein the polymerizable unsaturated monomer contains, as a polymerizable unsaturated monomer, a moiety containing a moiety having an ethylenically unsaturated bond in a molecule and a moiety having at least one of an oxygen atom, a nitrogen atom, and a sulfur atom. Curable composition for optical nanoimprint lithography which contains a monomer at least 15 mass% or more in the said composition, and contains 48-99 mass% of said polymerizable unsaturated monomers.

(3) The composition as described in (2) containing at least 1 sort (s) of the compound chosen from following (a), (b) and (c) as a monofunctional polymerizable unsaturated monomer.

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

(b) a polymerizable unsaturated monomer having a moiety having an ethylenically unsaturated bond in one molecule and a -C (= O) -bond and an NR bond (R is a hydrogen atom or a methyl group)

(c) a polymerizable unsaturated monomer having a moiety having an ethylenically unsaturated bond in one molecule and an alicyclic moiety having 6 to 12 carbon atoms

(4) The composition according to (3), wherein the hetero atom of the monofunctional polymerizable unsaturated monomer of (a) is at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.

(5) The composition according to any one of (2) to (4), wherein the monofunctional polymerizable unsaturated monomer is any one or more selected from the following General Formulas (I) to (VIII).

Formula (I)

(In General Formula (I), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, and an ethoxy group. represents. n1 is 1 or 2, m1 is 0, 1, represents any one of 2. Z ¹¹ represents a methylene group, an oxygen atom, -NH-, Z ¹¹ is a single 2 may be different from each other. W ¹¹ is -C (= O)-or -SO ₂ -R ¹² and R ¹³ and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring.)

Formula (II)

(In General Formula (II), R ²¹ represents a hydrogen atom or a methyl group, and R ²² , R ²³ , R ^24, and R ²⁵ each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group, An ethoxy group is represented by R ²² and R ²³ ; And R ²⁴ and R ²⁵ may be bonded to each other to form a ring. n2 is any one of 1, 2, 3, and m2 represents any of 0, 1, 2. Y ²¹ represents a methylene group or an oxygen atom.)

General formula (III)

(In Formula (III), R ³² , R ³³ , R ³⁴ and R ³⁵ each represent a hydrogen atom, a methyl group, an ethyl group, an propyl group, a butyl group, a halogen atom, a methoxy group and an ethoxy group. N3 represents 1, 2, 3 and any of one, m3 is 0, 1, represents any one of the 2 X ³¹ is -C (= O) -.. , represents a methylene, ethylene, 2 X ³¹ is Y or different from each other is ^32-methylene Group or oxygen atom.)

General formula (IV)

(In General Formula (IV), R ⁴¹ represents a hydrogen atom or a methyl group. R ⁴² and R ⁴³ each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group, an ethoxy group.) ⁴¹ represents a single bond, no bond, or -C (= 0)-n4 represents any of 2, 3 and 4. X ⁴² represents -C (= 0)-, -C = C-,- C = N- or a methylene group, and each X ⁴² may be the same or different, M ⁴¹ may represent a hydrocarbon linking group, an oxygen atom or a nitrogen atom having 1 to 4 carbon atoms, and each M ⁴¹ may be the same or different.)

General formula (V)

(In formula (V), R ⁵¹ represents a hydrogen atom or a methyl group. Z ⁵² represents an oxygen atom, —CH = N- or a methylene group. W ⁵² represents a methylene group or an oxygen atom. Y ⁵² represents a single bond) Or —C (C═O) — Y ⁵³ represents a single bond or —C (C═O) — R ⁵⁴ and R ⁵⁵ each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen An atom, a methoxy group, an ethoxy group, R ⁵⁴ and R ⁵⁵ may be bonded to each other to form a ring X ⁵¹ may be a single bond or an unbonded m5 is any one of 0, 1, and 2. W ⁵² , At least one of Z ⁵² , R ⁵⁴ , and R ⁵⁵ contains an oxygen atom or a nitrogen atom.)

General formula (VI)

(In formula (VI), R ⁶¹ is a hydrogen atom or a methyl group, R ⁶² and R ⁶³ are each a hydrogen atom, a methyl group, an ethyl group, a hydroxyethyl group, a propyl group, (CH ₃ ) ₂ N- (CH ₂ ) m _6- (m6 is 1, 2 or 3), CH ₃ CO- (CR ⁶⁴ R ⁶⁵ ) _p6- (R ⁶⁴ and R ⁶⁵ each represent a hydrogen atom or a methyl group, p6 is either 1, 2 or 3), ( CH ₃ ) ₂ -N- (CH ₂ ) _p6- (p6 is either 1, 2 or 3.) provided that -NR ⁶² (R ⁶³ ) in Formula (VI) is -N = C Or a group O. R ⁶² and R ⁶³ are not hydrogen atoms at the same time, and X ⁶ is -CO-, -COCH _2- , -COCH ₂ CH _2- , -COCH ₂ CH ₂ CH ₂ -,- COOCH ₂ CH ₂ -is any one.)

Formula (VII)

(In formula (VII), R ⁷¹ and R ⁷² each represent a hydrogen atom or a methyl group, and R ⁷³ represents a hydrogen atom, a methyl group or an ethyl group.)

General formula (VIII)

(In formula (VIII), R ⁸¹ represents a hydrogen atom, a methyl group, or a hydroxymethyl group. R ⁸² , R ⁸³ , R ⁸⁴ , and R ⁸⁵ each represent a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, a hydroxymethyl group, or a hydroxyethyl group.) , A propyl group and a butyl group, and at least two of R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ may be bonded to each other to form a ring, wherein W ⁸¹ is a methylene group, -NH-, -N (CH ₃ )-, -N (C ₂ H ₅ )-W ⁸² represents a single bond or -C (= O)-When W ⁸² is a single bond, R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ are all hydrogen atoms. No. n7 represents an integer from 0 to 8.).

(6) The composition according to any one of (1) to (5), wherein the second polymerizable unsaturated monomer containing a moiety having at least one ethylenically unsaturated bond and a silicon atom and / or a person atom is polymerized. The composition according to any one of (1) to (5), which contains 0.1% by mass or more in the monomer.

(7) The composition according to any one of (1) to (6), wherein the inorganic oxide fine particles are colloidal silica.

(8) The composition as described in (7), wherein the colloidal silica is a surface treated colloidal silica.

(9) The composition according to (8), wherein the colloidal silica is colloidal silica surface-treated with a compound having a reactive (meth) acrylate group.

(10) The composition according to any one of (1) to (9), which contains an antioxidant.

(11) The composition according to any one of (1) to (10), wherein the viscosity at 25 ° C. is 25 mPa · S or less.

(12) The process of apply | coating the composition in any one of (1)-(11), the process of pressurizing a light-transmissive mold to the resist layer on a board | substrate, and deforming the said apply | coated composition, the back surface of a mold, or a board | substrate back surface Irradiating, curing the coating film, forming a resist pattern according to a desired pattern, and removing the light-transmissive mold from the coating film.

According to the present invention, when used as an etching resist, it is possible to provide a composition which is excellent in overall photocurability, adhesiveness, peelability, residual film property, pattern shape, coating property, and etching ability. Moreover, when used as a permanent film, it became possible to obtain the composition excellent in mechanical properties, such as residual film property, light transmittance, and imaging resistance, and solvent resistance comprehensively.

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

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail. In addition, in this specification, a meta (acrylate) shows an acrylate and a methacrylate, a meta (acryl) shows an acryl and methacryl, and a meta (acryloyl) shows acryloyl and a methacryloyl. Indicates. 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 a mass mean molecular weight says the compound which is 1,000 or less. In this specification, a functional group refers to the group which participates in superposition | polymerization.

In addition, the nanoimprint referred to in this invention means pattern transfer of the size of about several micrometers to several tens of nm. That is, needless to say, it is not limited to the imprint of the nano order.

The curable composition for optical nanoimprint lithography of the present invention (hereinafter may be referred to only as the "composition of the present invention") is, for example, high in light transmittance before curing, and has an ability to form a fine rough pattern, coating aptitude and In addition to excellent workability, after curing, sensitivity (fast curing), resolution, line edge roughness, film strength, peelability with a mold, residual film properties, etching resistance, low curing shrinkage, substrate adhesion, or all other points In general, excellent coating film physical properties are obtained. Therefore, the composition of the present invention can be widely used for photo nanoimprint lithography.

That is, when the composition of this invention is used for photo nanoimprint lithography, 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 the atmosphere is hardly mixed, it does not cause bubble defects. It is hard to leave residue after anger.

(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, pattern collapse and cobwebbing occur on the surface of the coating film when the mold is peeled off. Since it does not cause surface roughness, a good pattern can be formed.

(3) Since the volume shrinkage after photocuring is small and the mold transfer characteristic is excellent, accurate shaping of a fine pattern is possible.

(4) Because of the uniformity of coating, it is suitable for application to large substrates and fine processing.

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

(6) Since the etching processing accuracy, the etching resistance and the like are excellent, it can be suitably used as an etching resist for processing substrates such as semiconductor devices and transistors.

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

(8) Since the mechanical properties such as light transmittance, residual film resistance, and imaging resistance and solvent resistance are high, it can be suitably used as permanent films of various kinds.

It is possible to have such characteristics as.

For example, the composition of the present invention can be suitably applied to microfabricated applications such as semiconductor integrated circuits and thin film transistors of liquid crystal displays, protective films of liquid crystal color filters, and spacers, which have been difficult to develop until now, and other applications, examples For example, bulkheads for plasma display panels, flat screens, microelectromechanical systems (MEMS), sensor elements, optical disks, magnetic recording media such as high density memory disks, optical components such as diffraction gratings and relief holograms, nanodevices, optical devices, Optical film, polarizing element, organic transistor, color filter, overcoat layer, base material, liquid crystal alignment rib material, microlens array, immunoassay chip, DNA separation chip, micro reactor, nano bio device, optical waveguide, optical filter, photonic The present invention can be widely applied to production of liquid crystals and the like.

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 the composition of the present invention at 25 ° C is preferably 25 mPa · s or less, more preferably 20 mPa · s or less, and still more preferably 3 to 18 mPa · s or less. By setting it as such a viscosity, the formation ability, application | coating suitability, and other processing ability of the fine uneven | corrugated pattern before hardening can be provided, and after hardening, it is excellent in resolution, line edge roughness, residual film characteristic, board | substrate adhesiveness, or everything else. Coating film properties can be imparted. By making the viscosity of the composition of this invention into 3 mPa * s or less, 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 set to 3 mPa · s or more, so that there is a tendency that surface unevenness may occur during application of the composition, or that the composition may flow out of the substrate during application, which is preferable. On the other hand, when the viscosity of the composition of the present invention is 25 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 recessed portion of the mold, and the atmosphere becomes difficult to mix. It is preferable to cause bubble defects and to make the residue difficult after photocuring in the mold convex portion.

The composition of the present invention comprises 35 to 99% by mass of the polymerizable unsaturated monomer, 0.1 to 15% by mass of the photopolymerization initiator, 0.001 to 5% by mass of at least one of the fluorine-based surfactant, the silicone-based surfactant and the fluorine-silicone-based surfactant, and the inorganic oxide fine particles. It contains 0.1-50 mass%.

Polymerizable unsaturated monomers

The composition of the present invention preferably takes a polymerizable unsaturated monomer and comprises a monofunctional polymerizable unsaturated monomer containing a moiety having an ethylenically unsaturated bond in the molecule and a moiety having at least one of an oxygen atom, a nitrogen atom and a sulfur atom. It is a composition which the content of the polymerizable unsaturated monomer containing the said monofunctional polymerizable unsaturated monomer is 48-99 mass%. More preferably, it is a composition which contains 15 mass% or more, more preferably 25-60 mass% of monofunctional polymerizable unsaturated monomers.

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

(a) a polymerizable unsaturated monomer having a moiety having an ethylenically unsaturated bond in one molecule and an aliphatic cyclic moiety containing a hetero atom (preferably an oxygen atom, a nitrogen atom and a sulfur atom)

(b) a polymerizable unsaturated monomer having a moiety having an ethylenically unsaturated bond in one molecule and a -C (= 0) -bond and an NR bond (R is a hydrogen atom or a methyl group);

(c) a polymerizable unsaturated monomer having a moiety having an ethylenically unsaturated bond in one molecule and an alicyclic moiety having 6 to 12 carbon atoms

The monofunctional polymerizable unsaturated monomer used in the present invention is preferably a polymerizable unsaturated monomer represented by any one of the following general formulas (I) to (VIII).

Formula (I)

(In General Formula (I), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, and an ethoxy group. represents. n1 is 1 or 2, m1 is 0, 1, represents any one of 2. Z ¹¹ represents a methylene group, an oxygen atom, -NH-, Z ¹¹ is a single 2 may be different from each other. W ¹¹ is -C (= O)-or -SO _2-, R ¹² and R ¹³ , And R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring.)

Here, R ¹¹ is preferably a hydrogen atom. R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. m1 is preferably 0 or 1. At least one of Z ¹¹ is preferably an oxygen atom. W ¹¹ is preferably -C (= 0)-.

When n1 is two or more, R <^14> , R <^15> may be the same respectively and may differ.

Specific examples of the compound represented by General Formula (I) include the following Formulas (I-1) to (I-19).

Formula (II)

(In Formula (II), R ²¹ represents a hydrogen atom or a methyl group, and R ²² , R ²³ , R ^24, and R ²⁵ each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group, and an ethoxy group). R ²² and R ²³ and R ²⁴ and R ²⁵ may be bonded to each other to form a ring, n2 is any one of 1, 2 and 3, and m2 represents any one of 0, 1 and 2. Y ²¹ represents a methylene group or an oxygen atom.

R ²¹ is preferably a hydrogen atom. R ²² , R ²³ , R ²⁴ and R ²⁵ are each preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group, and more preferably a hydrogen atom, a methyl group or an ethyl group. n2 is preferably 1 or 2. m2 is preferably 0 or 1.

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

General formula (III)

(In General Formula (III), R ³² , R ³³ , R ³⁴ and R ³⁵ each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group and an ethoxy group. N3 is 1, 2). , and any one of three, m3 is 0, 1, represents any one of the 2 X ³¹ is -C (= O) -.. , represents a methylene, ethylene, 2 X ³¹ is Y or different from each other is ³² Methylene group or oxygen atom.)

R ³² , R ³³ , R ³⁴ and R ³⁵ are each preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group, and more preferably a hydrogen atom. n3 is preferably 1 or 2.

As a specific example of a compound represented by general formula (III), following formula (III-1)-(III-11) can be mentioned.

General formula (IV)

(In Formula (IV), R ⁴¹ represents a hydrogen atom or a methyl group. R ⁴² and R ⁴³ each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group, or an ethoxy group.) W ⁴¹ Represents a single bond, an unbonded bond, or -C (= 0)-n4 represents any one of 2, 3 and 4. X ⁴² represents -C (= 0)-, -C = C-, -C = N- or a methylene group, and each X ⁴² may be the same or different, M ⁴¹ represents a C1-C4 hydrocarbon linking group, an oxygen atom or a nitrogen atom, and each M ⁴¹ may be the same or different.)

R ⁴¹ is preferably a hydrogen atom. R ⁴² and R ⁴³ are each preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom. M ⁴¹ is preferably any one of a methylene group, an ethylene group, a propylene group, and a butylene group.

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

General formula (V)

(In formula (V), R ⁵¹ represents a hydrogen atom or a methyl group. Z ⁵² represents an oxygen atom, —CH = N- or a methylene group. W ⁵² represents a methylene group or an oxygen atom. Y ⁵² represents a single bond) Or —C (C═O) — Y ⁵³ represents a single bond or —C (C═O) — R ⁵⁴ and R ⁵⁵ each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen An atom, a methoxy group, an ethoxy group, R ⁵⁴ and R ⁵⁵ may be bonded to each other to form a ring X ⁵¹ may be a single bond or an unbonded m5 is any one of 0, 1, and 2. W ⁵² , At least one of Z ⁵² , R ⁵⁴ , and R ⁵⁵ contains an oxygen atom or a nitrogen atom.)

Here, the case where X ⁵¹ is a nonbonding means the coupling | bonding form like (V-7) and (V-8) of the exemplary compound of general formula (V) mentioned later.

R ⁵¹ is preferably a hydrogen atom. R ⁵⁴ and R ⁵⁵ are each preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom or a methyl group. m5 is preferably 1 or 2.

As a specific example of a compound represented by general formula (V), following formula (V-1)-(V-8) can be mentioned.

General formula (VI)

(In formula (VI), R ⁶¹ is a hydrogen atom or a methyl group, R ⁶² and R ⁶³ are each a hydrogen atom, a methyl group, an ethyl group, a hydroxyethyl group, a propyl group, (CH ₃ ) ₂ N- (CH ₂ ) m _6- (m6 is 1, 2 or 3), CH ₃ CO- (CR ⁶⁴ R ⁶⁵ ) _p6- (R ⁶⁴ and R ⁶⁵ each represent a hydrogen atom or a methyl group, p6 is either 1, 2 or 3), (CH ₃ ) ₂ -N- (CH ₂ ) _p6- (p6 is any one of 1, 2 or 3.) provided that the portion of -NR ⁶² (R ⁶³ ) in the formula (VI) is -N = Or a C═O group, and R ⁶² and R ⁶³ are not simultaneously hydrogen atoms, and X ⁶ represents —CO—, —COCH ₂ —, —COCH ₂ CH ₂ —, —COCH ₂ CH ₂ CH ₂ —, -COOCH ₂ CH ₂ -is any one.)

Formula (VII)

As a specific example of a compound represented by general formula (VI), following formula (VI-1)-(VI-10) can be mentioned.

Formula (VII)

(In General Formula (VII), R ⁷¹ and R ⁷² each represent a hydrogen atom or a methyl group, and R ⁷³ represents a hydrogen atom, a methyl group, or an ethyl group.)

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

General formula (VIII)

(In formula (VIII), R ⁸¹ represents a hydrogen atom, a methyl group, or a hydroxymethyl group. R ⁸² , R ⁸³ , R ⁸⁴ , and R ⁸⁵ each represent a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, a hydroxymethyl group, or a hydroxyethyl group.) , A propyl group and a butyl group, and at least two of R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ may be bonded to each other to form a ring, wherein W ⁸¹ is a methylene group, -NH-, -N (CH ₃ )-, -N (C ₂ H ₅ )-W ⁸² represents a single bond or -C (= O)-When W ⁸² is a single bond, R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁴ are all hydrogen atoms. No. n7 represents an integer from 0 to 8.).

R ⁸¹ is preferably a hydrogen atom.

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

Secondary polymerizable unsaturated monomers

In this invention, you may contain the other polymerizable unsaturated monomer of the said polymerizable unsaturated monomer. For example, polymerizable unsaturated monomers containing a site having an ethylenically unsaturated bond and a silicon atom and / or a person group are enumerated. The second polymerizable unsaturated monomer may be a monofunctional polymerizable unsaturated monomer or a polyfunctional polymerizable unsaturated monomer. It is preferable that such a polymerizable unsaturated monomer contains 0.1 mass% or more in a polymerizable unsaturated monomer.

As a 2nd polymerizable unsaturated monomer, following (IX-1)-(IX-23) can be employ | adopted, for example.

The composition of this invention may use together the polymerizable unsaturated monomer (monofunctional polymerizable unsaturated monomer) which has one ethylenically unsaturated bond containing group for the purpose of improving film hardness, flexibility, etc. Specifically, 2-acryloyloxyethyl phthalate, 2-acryloyloxy 2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-ethyl- 2-butylpropanediol acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acrylic acid dimer, Aliphatic epoxy (meth) acrylate, benzyl (meth) acrylate, butanediol mono (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, ethylene oxide modified (Hereinafter referred to as "EO") Cresol ( (2) acrylate, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) ) Acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylic Late, methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, octyl (meth) acrylate, Paracumylphenoxyethylene glycol (meth) acrylate, epichlorohydrin (henceforth "ECH") Modified phenoxyacrylate, phenoxyethyl (meth) arc Relate, 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, isocyanate methyl (meth) acryl Elate, isocyanate ethyl (meth) acrylate, isocyanate n-propyl (meth) acrylate, isocyanate isopropyl (meth) acrylate, this Isocyanate alkyl (meth) acrylates such as isocyanate n-butyl (meth) acrylate, isocyanate isobutyl (meth) acrylate, isocyanate sec-butyl (meth) acrylate and isocyanate tert-butyl (meth) acrylate; (Meth) acryloylmethyl isocyanate, (meth) acryloylethyl isocyanate, (meth) acryloyl n-propyl isocyanate, (meth) acryloyl isopropyl isocyanate, (meth) acryloyl n-butyl isocyanate, (Meth) acryloyl alkyl isocyanates, such as (meth) acryloyl isobutyl isocyanate, (meth) acryloyl sec-butyl isocyanate, and (meth) acryloyl tert- butyl isocyanate, are illustrated.

As another polymerizable unsaturated monomer used by this invention, it is preferable to use the polyfunctional polymerizable unsaturated monomer which has 2 or more of ethylenically unsaturated bond containing groups.

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, di ( Meta) acrylated isocyanurate, 1,3-butylene glycoldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, EO-modified 1,6-hexanedioldi (meth) acrylate, ECH modified 1,6-hexanediol di (meth) acrylate, aryloxypolyethylene glycol acrylate, 1, 9-nonanediol di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A Di (meth) acrylate, modified bisphenol A di (meth) acrylate, EO modified bisphenol Fdi (meth) acrylate, ECH modified hexahydrophthalic acid diacrylate, hydroxy pivalate neopentyl glycol di (meth) acrylic Yate, neopentyl glycol di (meth) acrylate, EO modified neopentyl glycol diacrylate, propylene oxide (hereinafter referred to as "PO") modified neopentyl glycol diacrylate, caprolactone modified hydroxy pivaric acid ester Neopentylglycol, stearic acid modified pentaerythritol di (meth) acrylate, ECH modified phthalic acid di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol-tetramethylene glycol) Di (meth) acrylate, polyester (di) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ECH modified propylene glycol di (meth) acrylate, silicone di (meth) Acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dimethylol tricyclode Di (meth) acrylate, neopentyl glycol modified trimethylolpropanedi (meth) acrylate, tripropylene glycoldi (meth) acrylate, EO-modified tripropylene glycoldi (meth) acrylate, triglyceroldi (meth) acrylic Laterate, dipropylene glycol di (meth) acrylate, divinyl ethylene urea, divinyl propylene urea are exemplified.

Among these, 1, 9-nonanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and hydroxy pivarine neopentyl glycol di (meth) acryl Elate, 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 phosphate triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethyl All propane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, capurolactone modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol hydroxypenta (Meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, dipentaeryth Lithol poly (meth) acrylate, alkyl modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol ethoxy tetra (meth) acrylate, pentaerythritol tetra (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 trimethylol Propane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol ethoxy tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like are preferably used in the present invention.

When using two or more photopolymerizable functional groups in one molecule, since a large amount of photopolymerizable functional groups are introduce | transduced into a composition as mentioned above, the crosslinking density of a composition becomes very large and the effect of improving all the physical properties after hardening is high. Among all the physical properties after curing, in particular, heat resistance and durability (wear resistance, chemical resistance, water resistance) are improved by increasing the crosslinking density, and even when exposed to high heat, friction, or solvent, deformation, loss and damage of the fine uneven pattern are less likely to occur. .

In the composition of the present invention, for the purpose of further improving the crosslinking density, a polyfunctional oligomer or polymer having a higher molecular weight than that of the polyfunctional polymerizable unsaturated monomer can be blended in a range that achieves 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, phosphogen skeleton, adamantane skeleton, cardo skeleton, Oligomers or polymers having a bulky structure such as a norbornene skeleton and the like.

As a polymerizable unsaturated 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. Ethers, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, 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.

As an epoxy compound which can be used preferably, Bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, Bisphenol S diglycidyl ether, Brominated bisphenol A diglycidyl ether, Brominated bisphenol F diglycol, for example Cedyl ether, brominated bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 1, 4-butanediol diglycidyl ether 1, 6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether; Polyglycidyl ethers of polyether polyols obtained by adding one or two or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; Diglycidyl esters of aliphatic long-chain dibasic acids; Monoglycidyl ethers of aliphatic higher alcohols; Monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide to phenol, cresol, butylphenol or these; And glycidyl esters of higher fatty acids.

As a commercial item which can be used suitably as a glycidyl-group containing compound, UVR-6216 (made by Union Carbide), glycidol, AOEX24, the cyclomer A200 (above, the Daicel Chemical Co., Ltd. make), Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (above, manufactured by Yuka Cell), KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2720, KRM-2750 Asahi Denka Kogyo Co., Ltd.) etc. are mentioned above. These can be used individually by 1 type or in combination of 2 or more types.

In addition, although the compound which has these oxirane rings is not related to 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, 12, 32, 1985, Yoshimura, Adhesion, Vol. 30, 5, 42 , 1986, Yoshimura, Adhesion, 30, 7, 42, 1986, Japanese Patent Laid-Open No. 11-100378, Japanese Patent No. 2906245, Japanese Patent No. 2926262, and the like.

As a polymerizable unsaturated monomer used by this invention, you may use a vinyl ether compound together.

The vinyl ether compound may be appropriately selected. For example, 2-ethylhexyl vinyl ether, butanediol-1, 4-divinyl ether, diethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, Triethylene glycol divinyl ether, 1, 2- propanediol divinyl ether, 1, 3- propanediol divinyl ether, 1, 3- butanediol divinyl ether, 1, 4- butanediol divinyl ether, tetramethylene glycol divinyl Ether, neopentyl glycol divinyl ether, trimethylol propane trivinyl ether, trimethylol ethane trivinyl ether, hexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol Tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol Cold diethylene 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, etc. are mentioned.

These vinyl ether compounds are described, for example, in the methods described in Stephen. C. Lapin, Polymers Paint Color Journal. 179 (4237), 321 (1988), i.e., reactions of polyhydric alcohols or polyhydric phenols with acetylene, or polyhydric alcohols. Or it can synthesize | combine by reaction of polyhydric phenol and a halogenated alkyl vinyl ether, These can be used individually by 1 type or in combination of 2 or more types.

As a polymerizable unsaturated monomer used by this invention, a styrene derivative can also be employ | adopted. As a styrene derivative, p-methoxy styrene, p-methoxy- (beta) -methylstyrene, 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, 1-vinyl naphthalene, (alpha) -methyl- 1-vinyl naphthalene, (beta) -methyl, for example. -1-vinyl naphthalene, 4-methyl-1-vinyl naphthalene, 4-methoxy-1-vinylnaphthalene, etc. are mentioned.

Moreover, trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, and perfluoro for the purpose of improving peelability and applicability | paintability with a mold. Robutyl-hydroxypropyl (meth) acrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tetrafluoropropyl Compounds having fluorine atoms such as (meth) acrylate can also be used in combination.

As the polymerizable unsaturated monomer used in the present invention, propenyl ether and butenyl ether can be blended. For example, 1-dodecyl-1-propenyl ether, 1-dodecyl-1-butenyl ether, 1-buteneoxymethyl-2-norbornene, 1-4-di (1-buteneoxy) butane , 1,10-di (1-buteneoxy) decane, 1,4-di (1-buteneoxymethyl) cyclohexane, diethylene glycoldi (1-butenyl) ether, 1, 2, 3-tri (1 -Buteneoxy) propane, propenyl ether propylene carbonate, etc. can be preferably applied.

Next, the preferable blend form of a polymerizable unsaturated monomer in the composition of this invention is demonstrated. It is preferable that the composition of this invention contains the polyfunctional polymerizable unsaturated monomer further as a essential component the polymerizable unsaturated monomer containing the site | part which has at least 1 type of oxygen, nitrogen, or a sulfur element.

A monofunctional polymerizable unsaturated monomer is normally used as a reactive diluent and is effective in lowering the viscosity of the composition of the present invention, and usually 15% by mass or more of the total polymerizable unsaturated monomer is added. 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%.

 By setting the proportion of the monofunctional polymerizable unsaturated monomer selected from the above (a), (b) and (c) to 80 mass% or less, the mechanical strength, etching resistance, and heat resistance of the cured film cured of the composition of the present invention When it is used as a mold material of an optical nanoimprint, it exists in the tendency to become more favorable, and since it exists in the tendency which can suppress that a mold swells and deteriorates, it is preferable. On the other hand, since the said monofunctional polymerizable unsaturated monomer is more favorable 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.

In particular, in the composition of this invention, 15-80 mass% of monofunctional polymerizable unsaturated monomers, 0-60 mass% of bifunctional polymerizable unsaturated monomers, and 1 to 60 mass of polyfunctional polymerizable unsaturated monomers more than trifunctional It is preferable that it is comprised by the ratio of%, and 20-50 mass% of monofunctional polymerizable unsaturated monomers, 0-50 mass% of bifunctional polymerizable unsaturated monomers, and 2-50 mass% of polyfunctional polymerizable unsaturated monomers more than trifunctional It is more preferable that it is comprised by the ratio.

In particular, in the composition of the present invention, it is preferable to blend a site having at least one ethylenically unsaturated bond and a polymerizable unsaturated monomer containing a silicon atom and / or a person group. The polymerizable unsaturated monomer containing the site | part which has the said at least 1 ethylenically unsaturated bond, and a silicon atom and / or a person group is usually contained in all the polymerizable unsaturated monomers for the purpose of improving peelability with a mold and adhesiveness with a board | substrate. 0.1 mass% is added. Preferably it is 0.2-10 mass%, More preferably, it is 0.3-7 mass%, Especially preferably, it is added in the range of 0.5-5 mass%. As for the number (number of functional group) of the site | part which has an ethylenically unsaturated bond, 1-3 are preferable.

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 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 a specific monofunctional and / or bifunctional monomer as a reactive diluent, the organic solvent for dissolving the components of the composition of the present invention does not necessarily need to be contained. In addition, if the organic solvent is not contained, a baking step for volatilization of the solvent is 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 an 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, 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 in the curable composition for photo nanoimprint lithography, 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.

As said organic solvent, For example, Alcohol, such as methanol and ethanol; Ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as acetone, methyl ethyl ketone, 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 hydroxyacetic acid, 2-hydroxy-2-methylbutanoic acid Esters such as lactic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate This is listed.

Furthermore, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether , Dihexyl ether, acetonyl acetone, isoform, capuronic acid, capuryl acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone And high boiling point solvents such as ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate. These may be used individually by 1 type and may use two or more types together.

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

Photopolymerization initiator

A photoinitiator can be used for the composition of this invention. The photoinitiator used by this invention contains 0.1-15 mass% in whole composition, 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.

Since the ratio of a photoinitiator shall be 0.1 mass% or more, since it exists in the tendency for a sensitivity (fast curing property), resolution, line edge roughness, and coating film strength to improve, it is preferable. On the other hand, when the ratio of a photoinitiator is 15 mass% or less, there exists a tendency for light transmittance, coloring property, handleability, etc. to improve, and it is preferable. Until now, various addition amounts of preferred photopolymerization initiators and / or photoacid generators have been studied in the composition for inkjets and liquid crystal display color filters containing dyes and / or pigments, but for photo nanoimprint lithography such as for nanoimprints. There is no report on the addition amount of the preferable photoinitiator and / or the photo-acid generator to 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 by these uses. On the other hand, 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 the thing of the field | areas, such as a composition for inkjets and a composition for liquid crystal display color filters.

As a photoinitiator used by this invention, what has activity with respect to the wavelength of the light source to be used is mix | blended, and the thing which produces suitable active species is used. In addition, you may use only one type or two or more types of photoinitiators.

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 (R) 500 (1-hydroxycyclohexylphenylketone, benzophenone), Irgacure (R) 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-morpholinopropan-1-one, Irgacure® 819 (bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide, Irgacure (registered) 1800 (bis (2, 6-dimethoxybenzoyl) -2, 4, 4-trimethyl-pentylphosphineoxide, 1-hydroxycyclohexyl-phenylketone), Irgacure® 1800 (bis (2) , 6-dimethoxybenzoyl) -2, 4, 4-trimethyl-pentylphosphineoxide, 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-trimethylbenzoylphenylethoxyphosphine oxide), ESACURE 1001M (1- [4-benzoylphenylsulfanyl] phenyl] -2-methyl-2- (4-methylphenylsulfonyl) available from ESACUR Nihon Siberhegner ) Propan-1-one, adekaoptomer (registered trademark) N-1414 (carbazole phenone system), adekaoptomer (registered trademark) N-1717 (acridine system) available from Asahi Denkasha ), Adekaoptomer (registered trademark) N-1606 (triazine type), TFE-triazine (2- [2- (furan-2-yl) vinyl] -4, 6-bis (trichloro) produced by Sanwa Chemical Methyl) -1,3,5-triazine), TME-triazine (2- [2- (5-methylfuran-2-yl) vinyl] -4, 6-bis (trichloromethyl) manufactured by Sanwa Chemical -1, 3, 5-triazine), MP-triazine (2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine) manufactured by Sanwa Chemical , TAZ-113 (2- [2- (3,4-dimethoxyphenyl) ethenyl] -4, 6-bis (trichloromethyl) -1, 3, 5-triazine) produced by Midori Kagaku, Midori Kaga Co., Ltd. TAZ-108 (2- (3, 4-dimethoxyphenyl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine), benzophenone, 4, 4'-bisdiethyl Aminobenzophenone, methyl-2-benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 4-phenylbenzophenone, ethylmylerus ketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2 Isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 1-chloro-4-propoxycytoxanthone, 2-methyl thioxanthone, thioxanthone ammonium salt, benzo Phosphorus, 4, 4'-dimethoxybenzoin, benzoinmethyl Tere, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, 1, 1, 1-trichloroacetophenone, diethoxyacetophenone and dibenzosverone, methyl o-benzoyl benzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyldiphenylether, 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- (dimethyl Amino) benzoate, 2- (dimethylamino) ethyl benzoate, butoxyethyl-4- (dimethylamino) benzoate, etc. are mentioned.

In addition to the photopolymerization initiator, the photosensitizer may be added to the composition of the present invention to adjust the wavelength of the UV region. As a typical sensitizer which can be used in this invention, what is disclosed by J. Crivello, Adv. In Polymer Sci, 62, 1 (1984) is mentioned, Specifically, pyrene, perylene, and acre Dean orange, thioxanthone, 2-chlorothioxanthone, benzoflavin, N-vinylcarbazole, 9, 10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, campaquinone, phenothiazine Derivatives and the like.

It is preferable that the content rate of the photosensitizer in the composition of this invention is 15 mass% or less in the said composition, More preferably, it is 8 mass% or less, Especially preferably, 5 mass% or less is preferable. Although the minimum of a photosensitizer content rate is not specifically limited, In order to express an effect, the minimum of a photosensitizer content rate is about 0.1 mass%.

You may add the photo-acid generator which starts photopolymerization to the composition of this invention by receiving energy rays, such as an ultraviolet-ray, for the purpose of accelerate | stimulating a photocuring reaction.

As a commercial item of a photo-acid generator, IRGACURE261, IRGACURE OXE01, IRGACURE CGI-1397 (above, Chiba Specialty Chemicals make), etc. are mentioned. Said photo-acid generator can be used individually by 1 type or in combination of 2 or more types.

In addition, the said acid generator can be used in combination as said photoinitiator. In this case, it is preferable to use a photo-acid generator in the range of 0.05-3.0 mass%, use a photoinitiator and a photo-acid generator together, and to use in the range of 0.5-15.0 mass%. The light for initiating the polymerization of the present invention includes not only light or electromagnetic waves in the wavelength range of ultraviolet light, near ultraviolet light, far ultraviolet light, visible light, infrared light and the like, but also radiation, and the radiation includes, for example, microwaves, electron beams, EUV and X-rays are included. Moreover, laser beams, such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser, can also be used. These light may use monochromatic light (single wavelength light) through an optical filter, and may be other light of multiple wavelengths (composite light). Multiple exposure is also possible, and after forming a pattern for the purpose of raising film strength, etching resistance, etc., it is also possible to expose whole surface further.

Although the photoinitiator used by this invention needs to be selected timely with respect to the wavelength of the light source to be used, it is preferable not to generate gas during mold pressurization and exposure. When the gas is generated, the mold is contaminated, so that the mold must be frequently cleaned, or the curable composition for photo nanoimprint lithography deforms in the mold, and deteriorates the accuracy of the transfer pattern. The absence of gas is preferable from the viewpoint of making the mold hard to be contaminated, reducing the frequency of cleaning of the mold, or making it difficult to deform the curable composition for photo nanoimprint lithography in the mold, thereby deteriorating the transfer pattern precision.

Surfactants

The composition of this invention contains 0.001-5 mass% of at least 1 sort (s) of a fluorine-type surfactant, a silicone type surfactant, and a fluorine-silicone surfactant. 0.002-4 mass% is preferable, and, as for the said surfactant ratio in a composition, 0.005-3 mass% is especially preferable.

If the fluorine-based surfactant, the silicone-based surfactant, and the fluorine-silicone-based surfactant are less than 0.001 in the composition, the effect of uniformity of coating is insufficient. On the other hand, if the content exceeds 5% by mass, the mold transfer property is deteriorated. The fluorine-based surfactant, silicone-based surfactant, and fluorine-silicone-based surfactant used in the present invention may be used alone or in combination of two or more kinds thereof. In this invention, it is preferable to contain both a fluorine-type surfactant and a silicone type surfactant, or a fluorine-silicone surfactant.

In particular, 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 together.

By using such a surfactant, the composition of this invention is used for the silicon wafer for semiconductor element manufacture, the board | substrate whose glass is four sides for liquid crystal element manufacture, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, a tantalum alloy film, a silicon nitride film, Coatings such as striations or scaly patterns (dry stains on the resist film) that occur during application on the substrate, such as an amorphous silicon film, an indium oxide (ITO) film doped with tin oxide, or a tin oxide film are formed. The purpose of solving the problem of the defect, and to improve the fluidity of the composition into the cavity of the mold recess, to improve the peelability between the mold and the resist, to lower the viscosity of the composition to improve the adhesion between the resist and the substrate, and the like It becomes possible. In particular, in the composition of the present invention, by adding the surfactant, coating uniformity can be greatly improved, and in a coating using a spin coater or a slit scan coater, good coating aptitude not depending on the substrate size is obtained. .

Examples of the nonionic fluorine-based surfactants used in the present invention include the brand name Floride FC-430, FC-431 (manufactured by Sumitomo ThreeM Co., Ltd.), the brand name Supreon "S-382" (manufactured by Asahi Glass Co., Ltd.), and the EFTOP "EF-122A". , 122B, 122C, EF-121, EF-126, EF-127, MF-100 '' (manufactured by Tochem Products, Inc.), product name PF-636, PF-6320, PF-656, PF-6520 (all manufactured by OMNOVA Corporation) ), Brand name gent 250, FT251, DFX18 (all made by Neos Co., Ltd.), brand name Unidine DS-401, DS-403, DS-451 (all made by Daikin Kogyo Co., Ltd.), brand name Mega Pack 171 , 172, 173, 178K, 178A (both manufactured by Dainippon Ink & Chemicals, Inc.) are listed, and examples of nonionic silicon-based surfactants include the trade name SI-10 series (manufactured by Takemoto Yuji Co., Ltd.) and MegaPack Painttack 31 ( Dainippon Ink and Chemical Industries, Ltd.) and KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) are listed.

Examples of the fluorine-silicone surfactant used in the present invention include trade names X-70-090, X-70-091, X-70-092, and X-70-093 (all manufactured by Shin-Etsu Chemical Co., Ltd.), trade name Megapack R. -08 and XRB-4 (all are manufactured by Dainippon Ink & Chemicals, Inc.).

You may use together another nonionic surfactant for the composition of this invention in order to improve the flexibility, etc. of the curable composition for optical nanoimprint lithography in addition to the above. As a commercial item of a nonionic surfactant, it is poly, such as D-3110, D-3120, D-3412, D-3440, D-3510, D-3605 of the pioneer series by Takemoto Yuji Co., Ltd., for example. Polyoxyethylene alkyl, such as D-1305, D-1315, D-1405, D-1420, D-1504, D-1508, D-1518 of the oxyethylene alkylamine and the pionein series by Takemoto Yuji Co., Ltd. Ether, polyoxyethylene monofatty acid esters, such as D-2112-A, D-2112-C, and D-2123-C of the pioneine series by Takemoto Yuji Co., Ltd. and pionein by Takemoto Yuji Co., Ltd. Polyoxyethylene difatty acid esters, such as D-2405-A, D-2410-D, and D-2110-D of the series, and D-406, D-410, and D- of the Pioneer series manufactured by Takemoto Yuji Co., Ltd. Polyoxyethylene alkyl phenyl ethers, such as 414 and D-418, Polyoxyethylene tetramethyl decyne diol diethyl, such as 104S, 420, 440, 465, 485 of SUFINOL series made by Nisshin Chemical Co., Ltd., etc. are mentioned. Is illustrated. Moreover, the reactive surfactant which has a polymerizable unsaturated group can also be used together with surfactant used in this invention. For example, allyloxy polyethylene glycol monomethacrylate (Japanese fats and oils brand name: Bremermer PKE series), nonylphenoxy polyethylene glycol monomethacrylate (Japanese fats and oils company brand name: Bremermer PNE series), nonyl Phenoxy polypropylene glycol monomethacrylate (Japanese fats and oils) brand name: Bremmer PNP series, nonyl phenoxy poly (ethylene glycol-propylene glycol) monomethacrylate (Japanese fats and oils) brand name: Bremmer PNEP- 600), Aquaron RN-10, RN-20, RN-30, RN-50, RN-2025, HS-05, HS-10, HS-20 (made by Daiichi Kogyo Pharmaceutical Co., Ltd.) do. 0.001-5 mass% is preferable, and, as for the addition amount of another nonionic surfactant, 0.005-3 mass% is more preferable.

Inorganic oxide fine particles

The composition of the present invention contains inorganic oxide fine particles.

The inorganic oxide fine particles useful in the composition of the present invention are mainly added for the purpose of improving the heat resistance, the tackiness, the hardness, and the mechanical strength such as the imaging resistance, the wear resistance, the mechanical properties, etc. of the photocurable resin composition, and the resulting composition is transparent. If it becomes, the kind, particle size, and form will not be restrict | limited in particular. In addition, the addition of the inorganic oxide fine particles is also effective for improving the deterioration of the substrate adhesion due to the curing shrinkage. Examples of the inorganic oxide fine particles include silica (especially colloidal silica), alumina, titanium oxide, tin oxide, hetero element dope tin oxide (ATO, etc.), indium oxide, hetero element dope indium oxide (ITO, etc.), cadmium oxide, antimony oxide, Zinc oxide, cerium oxide, zirconium oxide and the like. These may be used independently and may be used in combination of 2 or more types. These inorganic oxide fine particles can use either powder form or a solvent dispersion sol. In the case of a solvent dispersion sol, the organic solvent is preferably used as the dispersion medium from the viewpoint of compatibility with other components and dispersibility. As such an organic solvent, For example, Alcohol, such as methanol, ethanol, isopropanol, butanol, an octanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Esters such as ethyl acetate, butyl acetate, ethyl lactate and γ-butyrolactone; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like can be enumerated. Especially, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, and xylene are preferable. When mix | blending a solvent dispersion sol with the composition of this invention, since a solvent is also mix | blended simultaneously, it is preferable to mix | blend so that content of the organic solvent may be 3 mass% or less in all the compositions. As described above, if the organic solvent is not contained, the baking step for volatilization of 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. Therefore, it is particularly preferable to add the particles dispersed in the powder or the reactive monomer (diluent) of the present invention rather than adding the solvent dissolving sol. Moreover, in order to improve the dispersibility of particle | grains, you may add various surfactant, a dispersing agent, and amines.

Although the shape of the inorganic oxide fine particle used for this invention is not specifically determined, spherical shape, hollow shape, porous shape, rod shape, plate shape, fibrous form, or irregular shape is mentioned, Preferably it is spherical shape.

It is preferable that the particle size of an inorganic oxide fine particle is 200 nm or less normally from a transparency viewpoint of the photocurable resin composition layer obtained. More preferably, it is 100 nm or less, More preferably, it is 50 nm or less. In addition, the addition amount of an inorganic oxide microparticle is included in the range of 0.1-50 mass% with respect to the composition of this invention. Preferably, it is 1-40 mass%, More preferably, it is preferable to include in the range of 5-30 mass%. When the addition amount of the inorganic oxide fine particles is less than 0.1% by mass, the effect of improving mechanical strength such as imaging resistance, abrasion resistance, and mechanical properties may not be confirmed, and when the addition amount exceeds 50% by mass, the photocurable resin The liquid viscosity of a composition may become high and storage stability and transparency may fall.

As a commercial item of the inorganic oxide microparticles | fine-particles used by this invention, As a water dispersion product of an alumina, Nissan Chemical Industries, Ltd. make, brand names: alumina sol-100, -200, -520; As an aqueous dispersion of titanium oxide, Ishihara Sangyo Co., Ltd. make, brand name: TTO-W5; As a water dispersion product of the zinc antimonate powder, Nissan Chemical Co., Ltd. make, brand names: Celnax; As powder and solvent dispersion products, such as an alumina, a titanium oxide, a tin oxide, an indium oxide, and a zinc oxide, the product made by Shia Kasei Co., Ltd., brand name: Nanotech; As a water dispersion product of the composite oxide of titanium oxide and tin oxide, Nissan Chemical Co., Ltd. make, brand name: HIT-15W1; As an aqueous dispersion sol of antimony dope tin oxide, Ishihara Sangyo Co., Ltd. make, brand names: SN-100D; As ITO powder, the product made by Mitsubishi Material Co., Ltd .; As the cerium oxide water dispersion, Takigaku Co., Ltd. make, brand name: nidoral, and tin oxide are water dispersion products, Ishihara Sangyo Co., Ltd. make, brand names: SN-38F, SN-88F; As a water dispersion product of zirconium oxide, Sumitomo Osaka Cement Co., Ltd. make, brand name: FFT-150W, Nissan Chemical Industries, Ltd. make, brand name: HZ-307W6; Etc. can be mentioned.

Among the inorganic oxide fine particles used in the present invention, from the viewpoint of the availability and the price, the transparency of the photocurable resin composition layer obtained and the expression of the mechanical properties, (omitted), for example, as colloidal silica, Nalcoag 1034A (Nalco Chemical, USA) Company brand name), Nissan Gakugyo Co., Ltd. product name: methanol silicazol, IPA-ST, MEK-ST, MIBK-ST, NBA-ST, XBA-ST, DMAC-ST, EAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, Fusogakuku Kogyo Co., Ltd. make, brand name: PL-1-MA, PL -1-TOL, PL-1-IPA, PL-1-MEK, PL-1-PGME, PL-2L-MA, PL-2L-IPA and the like. Moreover, as powder silica, Nippon Aerosil Co., Ltd. make, a brand name: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Asahi glass ( Co., Ltd. make, brand name: Sildex H31, H32, H51, H52, H121, H122, Nippon Silica High School Co., Ltd. make, brand name: E220A, E220, Fuji Silysia Co., Ltd. make, brand name: SYLYSIA 470, Nippon sheet glass The make, brand name: SG flake etc. are mentioned. If colloidal silica dispersed in commercial water or an organic solvent is used as it is in the composition of the present invention, water or an organic solvent is also blended as it is. Therefore, when a commercial colloidal silica dispersion is used as it is, a compounding amount of 5 mass% or less is used as a silica component. desirable.

CH ₂ = C (R ² ) COO (CH ₂ ) _p SiR ³ n (OR ¹ ) _3-n (1)

Wherein R ¹ represents a hydrogen atom or a hydrocarbon residue of 1 to 10 carbon atoms, R ² represents a hydrogen atom or a methyl group, and R ³ represents an ether bond, ester bond, epoxy bond, mercapto bond or amino bond Hydrocarbon residues having 1 to 10 carbon atoms, which may have n, n is an integer of 0 to 2, and p is an integer of 1 to 6.

When several R <^1> and / or R <^3> is included in a formula, these R <^1> and / or R <^3> may be same or different, respectively.

The silane compound which has an allyl group is represented, for example by following structural formula (2).

CH ₂ = CHCH ₂ R ² SiR ³ _n (OR ¹ ) _3-n (2)

Wherein R ¹ represents a hydrogen atom or a hydrocarbon residue of 1 to 10 carbon atoms, and R ² and R ³ each represent 1 to 10 carbon atoms which may have an ether bond, an ester bond, an epoxy bond, a mercapto bond or an amino bond. 10 hydrocarbon residues are represented, n is an integer of 0-2.)

When several R <^1> and / or R <^3> is included in a formula, these R <^1> and / or R <^3> may be same or different, respectively.

CH ₂ = CHSiR ² _n (OR ¹ ) _3-n (3)

Wherein R ¹ represents a hydrogen atom or a hydrocarbon residue of 1 to 10 carbon atoms, and R ² represents a hydrocarbon residue of 1 to 10 carbon atoms which may have an ether bond, an ester bond, an epoxy bond, a mercapto bond or an amino bond. N is an integer of 0 to 2).

When several R <^1> and / or R <^2> is included in a formula, these R <^1> and / or R <^2> may be same or different, respectively.

Wherein R ¹ represents a hydrogen atom or a hydrocarbon residue of 1 to 10 carbon atoms, R ² represents a hydrogen atom or a methyl group, R ³ has an ether bond, an ester bond, an epoxy bond, a mercapto bond or an amino bond Hydrocarbon residues having 1 to 10 carbon atoms may be present, and n is an integer of 0 to 2).

When several R <^1> and / or R <^3> is included in a formula, these R <^1> and / or R <^3> may be same or different, respectively.

When c is 2 or more, each R ¹ may be the same or different.

Moreover, you may use together with a radically polymerizable silane compound and a non-radically polymerizable silane compound, It is preferable that the use molar ratio exists in the range of 1: 99-99: 1, and the range of 2: 98-98: 2 is More preferably, the range of 5: 95-95: 5 is still more preferable, The range of 10: 90-80: 20 is especially preferable.

In addition, it is preferable to use a solvent in order to perform a hydrolysis-condensation reaction gently or uniformly. As this solvent, the dispersion medium of silica may be used as it is, and a required amount of new solvent may be added. As a newly added solvent, Water; Alcohol, such as methanol, ethanol, and isopropyl alcohol; Ketones such as acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); And ethers such as dioxane and tetrahydrofuran (THF).

Antioxidant

Moreover, the composition of this invention can contain a well-known antioxidant. Antioxidant suppresses the discoloration by heat or light irradiation and the discoloration by various oxidizing gases, such as ozone, active oxygen, NOx, and SOx (X is an integer). In particular, in the present invention, by adding the antioxidant, there is an advantage that the coloring of the cured film can be prevented or the reduction in film thickness due to decomposition can be reduced. Examples of such antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, and thiocyanate salts. , Thiourea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives and the like. Among these, especially a hindered phenol type antioxidant and a thioether type antioxidant are preferable from a viewpoint of coloring of a cured film, and reduction of a film thickness.

As a commercial item of antioxidant, Irganox 1010, 1035, 1076, 1222 (above, Chiba-Geigi Co., Ltd. product), Antigene P, 3C, FR, Sumiiser S, Sumiiser GA-80 (Sumitomo Kogyo Gakuku Co., Ltd.), Adeka stop AO70, AO80, AO503 (made by ADEKA Corporation) etc. are mentioned, These may be used independently and may be used in mixture. It is preferable to mix | blend antioxidant in the ratio of 0.01-10 mass% with respect to the whole amount of the composition of this invention, and it is more preferable to mix | blend in the ratio of 0.2-5 mass%.

Other ingredients

In the composition of the present invention, a release 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 elastomeric particle, a photoacid multiplier, a light, as necessary, in addition to the above components You may add a base 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 organic metal 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 nanoimprint lithography. By making the ratio of an organometallic coupling agent into 0.001 mass% or more, there exists a tendency which is more effective about the improvement of provision of heat resistance, intensity | strength, and adhesiveness with a 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 defect of stability of a composition, and film formation, and it is preferable.

As a commercial item of a ultraviolet absorber, Tinuvin P, 234, 320, 326, 327, 328, 213 (above, Chiba-Geigi Co., Ltd.), Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350 , 400 (above, Sumitomo Chemical Co., Ltd. make) 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 nanoimprint lithography.

Commercially available products of the light stabilizer include Tinuvin 292, 144, 622LD (above, produced by Chiba-Geigi Co., Ltd.), Sanol LS-770, 765, 292, 2626, 1114, 744 (above, manufactured by Sankyo Kasei Kogyo Co., Ltd.), etc. This is listed. 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.

Examples of commercially available anti-aging agents include Antigene W, S, P, 3C, 6C, RD-G, FR and AW (above, manufactured by Sumitomo Chemical Co., Ltd.). It is preferable to mix | blend an antioxidant at the ratio of 0.01-10 mass% with respect to the whole amount of a composition.

In order to adjust adhesiveness with a board | substrate, flexibility of a film | membrane, hardness, etc., it is possible to add a plasticizer to the composition of this invention. Specific examples of preferred plasticizers include, for example, dioctylphthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresylphosphate, dioctyl adipate, dibutyl sebacate, triacetylglycerine, and dimethyl adipate. , Diethyl adipate, di (n-butyl) adipate, dimethyl suberate, diethylsverate, di (n-butyl) sverate, and the like, and the plasticizer is optionally 30 mass% or less in the composition. Can be added. 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-carbamoylhydroxyamide, 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-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidin, hexaammine cobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) -butanone, 2, 6-dimethyl-3, 5-diacetyl-4- (2 ', 4'-dinitrophenyl) -1, 4-dihydropyridine, 2, 6 -Dimethyl-3, 5-diacetyl-4- (2 ', 4'-dinitrophenyl) -1, 4-dihydropyridine and the like are listed as preferred.

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 which are 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, various conventionally well-known inorganic pigments or organic pigments 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. do. 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, CIPigment Brown 25, 28, CIPigment 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 system / polyene copolymer, an acrylic rubber, butadiene / (meth) acrylic acid ester copolymer, a styrene / butadiene block copolymer, and a styrene / isoprene block copolymer. In addition, core / cell type particles in which these elastomer particles are coated with a methyl methacrylate polymer, a methyl methacrylate / glycidyl methacrylate copolymer, or the like can be used. The elastomer particles may have a crosslinked structure.

These elastomer particles may 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 arbitrarily add a basic compound to the composition of this invention for the purpose of suppressing hardening shrinkage, improving thermal stability, etc. Examples of the basic compound include nitrogen-containing heterocyclic compounds such as amine, quinoline, and quinolysin, basic alkali metal compounds, basic alkaline earth metal compounds, and the like. Among these, an amine is preferable from a compatibility with a photopolymerizable monomer, For example, octylamine, naphthylamine, xylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, dimethylaniline, qui Nuclidine, 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-mercapto butyloxyethyl) 1, 3, 5-triazine-2, 4, 6 (1H) , 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate) can be enumerated.

You may add antistatic agent to the composition of this invention as needed.

Next, the formation method of the pattern (especially fine concavo-convex 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. Specifically, at least a pattern forming layer made of the composition of the present invention is applied onto a substrate or a support, dried as necessary to form a layer (pattern forming layer) made of the composition of the present invention to form a pattern acceptor, and the pattern acceptor The mold is pressed onto the surface of the pattern forming layer of C, and a process of transferring the mold pattern is performed to expose the fine concave-convex pattern forming layer and to harden it. The 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 a normal thermal imprint.

On the other hand, as an application of the composition of the present invention, the composition of the present invention is applied onto a substrate or a support, and a layer made of the composition is exposed and cured, and if necessary, drying (baking), an overcoat layer or an insulating film can be produced. It may be.

Below, the pattern formation method and pattern transfer method using the composition of this invention are demonstrated.

The composition of the present invention is generally well known coating methods, for example, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion molding method, spin coating method, slit scan It can be formed by coating, for example. Although the film thickness of the layer which consists of a composition of this invention changes with uses, it is 0.05 micrometer-30 micrometers. In addition, the composition of the present invention may be multi-coated.

The substrate or support for applying the composition of the present invention may be quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflecting 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 a board | substrate may be plate shape, and a roll shape may be sufficient as it.

Although it does not specifically limit as light which hardens the composition of this invention, Light or radiation of the wavelength of the area | regions, 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 cockcroft accelerators, van degraf accelerators, linia accelerators, betatrons and cyclotrons are used most industrially and economically. Radiation such as γ-rays, X-rays, α-rays, neutron rays, quantum rays and the like emitted from isotopes, nuclear reactors and the like can also be used. Examples of the ultraviolet source include ultraviolet fluorescent lamps, low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, xenon lamps, carbon arc lamps and solar lamps. Radiation includes, for example, microwave and EUV. In addition, laser light used for microfabrication of semiconductors such as LED, semiconductor laser light, or 248 nm KrF excimer laser light or 193 nm ArF excimer laser can also be preferably used in the present invention. Monochrome light may be used for these lights, and other lights (mixed light) of several wavelength may be sufficient as them.

Next, the mold material which can be used for this invention is demonstrated. In optical nanoimprint lithography 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 optical imprint lithography applied to the present invention, a curable composition for photo nanoimprint lithography is applied onto a substrate, the light-transmissive mold is pressed, light is irradiated from the back side of the mold, and the curable composition for photo nanoimprint lithography is cured. Moreover, the curable composition for optical nanoimprint lithography may be apply | coated on a transparent substrate, a mold may be pressed, the light may be irradiated from the back surface of a mold, and the curable composition for optical nanoimprint lithography may be hardened.

Although light irradiation may be performed in the state to which a mold was affixed, you may carry out after mold peeling, but 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. Although the mold can form a pattern according to desired processing precision, for example by photolithography, an electron beam drawing method, etc., the mold pattern formation method is not specifically limited in this invention.

The light-transmissive mold material used in the present invention is not particularly limited, but may be one having predetermined strength and durability. Specific examples include light-transparent resins such as glass, quartz, PMMA, and polycarbonate resins, flexible films such as transparent metal vapor deposition films, and polydimethylsiloxane, photocuring films, and metal films.

The non-transmissive mold material to be used in the case of using the transparent substrate of the present invention is not particularly limited, but may be one having a predetermined strength. Specific examples include ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, Fe, substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, and the like. It is not particularly limited. The shape may be either a plate mold or a roll mold. Roll-shaped molds are especially applied where continuous productivity of transfer is required.

The mold used in the present invention may be one that has been subjected to a release treatment in order to improve the peelability between the curable composition for optical nanoimprint lithography and the mold. Treatment with a silane coupling agent such as silicon or fluorine, for example, commercial release agents such as manufactured by Daikin Kogyo Co., Ltd., OPTOOL DSX, Sumitomo 3M, and Novec EGC-1720 can be preferably used.

In the case of performing optical imprint lithography using the present invention, it is usually preferable to perform 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, 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 uniformity of mold transfer in the range in which the residual film of the curable composition for optical nanoimprint lithography 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 dose required for curing is determined by examining the consumption of unsaturated bonds in the curable composition for photo nanoimprint lithography or the tackiness 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. As a pre-light irradiation step, when placed in a vacuum state, it is effective in preventing bubble mixing, suppressing a decrease in reactivity due to oxygen mixing, and improving adhesion between the mold and the curable composition for photo nanoimprint lithography. Therefore, light irradiation may be performed in a vacuum state. In the present invention, the preferred degree of vacuum is performed in the range of 10 ⁻¹ Pa to atmospheric pressure.

After mixing each said component, the composition of this invention can be prepared as a solution by filtering with a filter of 0.05 micrometer-5.0 micrometers in diameter, for example. The mixing and dissolution of the curable composition for photo nanoimprint lithography are usually performed in the range of 0 ° C to 100 ° C. Filtration may be performed in multiple stages, and may be repeated many times. The filtrate 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.

The case where the composition of this invention is applied to an etching resist is demonstrated. As an etching process, it can carry out by the method suitably selected from the well-known etching process methods, and is performed in order to remove the undercoat part which is not covered by a resist pattern, and obtains a thin film pattern. Either a treatment with an etchant (wet etching) or a treatment (dry etching) in which the reactive gas is activated by plasma discharge under reduced pressure is performed.

As the etchant in the case of performing the wet etching, a large number of etchants have been developed and used, for example, ferric chloride / hydrochloric acid, hydrochloric acid / acetic acid, hydrobromic acid, and the like. A mixture of cerium ammonium nitrate solution or cerium nitrate / hydrogen peroxide solution for Cr, dilute hydrofluoric acid, arsenic acid / nitrate mixture solution for Ti, a mixture solution of ammonium solution and hydrogen peroxide solution for Ta, hydrogen peroxide solution, ammonia solution A mixture of hydrogen peroxide solution, a mixture of phosphoric acid and nitric acid, a mixture of phosphoric acid and nitric acid for MoW and Al, a mixture of arsenic acid and nitric acid, and a mixture of phosphoric acid and nitric acid and acetic acid. Buffered hydrofluoric acid, a mixture of fluoric acid and ammonium fluoride in SiO2, a mixture of arsenic acid, nitric acid and acetic acid in Si and poly Si, a mixture of ammonia water and hydrogen peroxide in W, a mixture of nitric acid and fluoric acid in PSG, and fluoric acid and BSG in BSG Ammonium fluoride liquid mixture and the like are used.

Although wet etching may be a shower system or a dip system, the precision of an etching rate, in-plane uniformity, and wiring width largely depends on processing temperature, and it is necessary to optimize conditions according to a board type, a use, and a line width. In addition, when performing the said wet etching, it is preferable to perform post-baking in order to prevent the undercut by the penetration of etching liquid. Usually, these post-baking is performed about 90 to 140 degreeC, but it is not necessarily limited to these.

Dry etching basically has a pair of parallelly arranged electrodes in a vacuum apparatus, and a parallel flat type dry etching apparatus is used in which a substrate is provided on one electrode. The high-frequency power source for generating the plasma is connected to the electrode on the side where the substrate is placed or to the opposite electrode, so that the reactive ion etching (RIE) mode mainly involving ions and the plasma etching mainly involving radicals are generated. Are classified into (PE) mode.

As the etchant gas used in the dry etching, an etchant gas suitable for each film type is used. Carbon tetrafluoride (chlorine) + oxygen for a-Si / n ⁺ or s-Si, carbon tetrafluoride (sulfur hexafluoride) + hydrogen chloride (chlorine), carbon tetrafluoride + oxygen for a-SiNx, a-SiOx Carbon tetrafluoride + oxygen, carbon trifluoride + oxygen, carbon tetrafluoride (sulfur hexafluoride) + oxygen for Ta, carbon tetrafluoride + oxygen for MoTa / MoW, chlorine + oxygen for Cr, trichloride for Al Boron + chlorine, hydrogen bromide, hydrogen bromide + chlorine, hydrogen iodide and the like. In the dry etching process, the structure of the resist may be largely altered by ion bombardment or heat, which also affects the peelability.

The method of peeling the resist used for pattern transfer to the underlayer substrate after etching will be described. Peeling is removed by liquid (wet peeling), or oxidized by plasma discharge of oxygen gas under reduced pressure to be removed in gaseous form (dry peeling / ashing), or oxidized by ozone and UV light to be removed in gaseous form (dry Resist removal can be performed by several peeling methods, such as peeling / UV ashing). As the stripping solution, aqueous solutions such as sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and ozone dissolved water and organic solvent systems such as a mixture of amine and dimethyl sulfoxide or N-methylpyrrolidone are generally known. As the latter example, a monoethanolamine / dimethylsulfoxide mixture (mass mixing ratio = 7/3) is well known.

The resist peeling rate is largely involved in temperature, liquid amount, time, pressure, and the like, and can be optimized according to the substrate type and application. In this invention, it is preferable to immerse a board | substrate (a few minutes-several ten minutes) in the temperature range of room temperature-about 100 degreeC, and to perform solvent rinsing, such as butyl acetate, and water washing. Only water washing may be sufficient from a viewpoint of improving the rinse property, particle removal property, and corrosion resistance of peeling liquid itself. Water washing, pure water showering and drying are listed as preferred examples of air knife drying. When amorphous silicon is exposed on the substrate, since an oxide film is formed in the presence of water and air, it is preferable to block the air. Moreover, you may also apply the method of using ashing (painting) and peeling by a chemical liquid together. Ashing includes plasma ashing, downflow ashing, ashing with ozone, UV / ozone ashing. For example, when the Al substrate is processed by dry etching, a chlorine-based gas is generally used, but aluminum chloride, which is a product of chlorine and Al, may corrode Al. In order to prevent these, you may use the peeling liquid containing preservative.

There is no restriction | limiting in particular as said etching process, a peeling process, a rinse process, and other processes other than water washing, What selects suitably among the processes in well-known pattern formation is mentioned. For example, a hardening process process etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. There is no restriction | limiting in particular as a hardening process process, Although it can select suitably according to the objective, For example, a whole surface heat processing, a whole surface exposure process, etc. are mentioned preferably.

As a method of the said whole surface exposure process, the method of exposing the whole surface of the formed pattern is mentioned, for example. By whole surface exposure, hardening in the composition which forms the said photosensitive layer is accelerated | stimulated, and since the surface of the said pattern hardens, etching tolerance can be improved. There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned preferably.

(Example)

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

Polymerizable unsaturated monomers

<Monofunctional monomer>

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

R-2: Compound (I-3) α-acryloyloxy-β, β-dimethyl-γ-butyrolactone (Aldrich's reagent)

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

R-4: Compound (II-3) 4-acryloyloxymethyl-2-methyl2-ethyl-1,3-dioxolane (Bisco MEDOL 10: manufactured by Osaka Organic Chemicals Co., Ltd.)

R-5: Compound (II-5) 4-acryloyloxymethyl-2-cyclohexyl 1,2-dioxolane (made by Biscot HDOL10 Osaka Organic Chemical Industries)

R-6: Compound (II-7) (3-methyl3-oxetanyl) methylacrylate (made by Biscot OXE10 Osaka Organic Industries)

R-7: Compound (III-2) N-vinylsuccinimide (synthetic product) Synthesis according to Doklady Akademii Nauk Respubliki Uzbekistan (1), 39 Water-49 (1993)

R-8: Compound (III-6) N-piperidinoethylacrylate (synthetic) Synthesis according to Journal fuer Praktische Chemie (Leipzig), 7, 308-10. (1959)

R-9: Compound (III-7) 2-propenoic acid 2-methyloxyranylmethyl ester (synthetic) Synthesis according to Gaofen zi Xuebao (1), 109-14, (1993)

R-10: Compound (III-8) N-morpholinoethylacrylate (synthetic) Synthesis according to American Chemical Society, 71, 3164-5, (1949)

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

R-12: Compound (IV-2) N-vinyl capurolactone (Aldrich's reagent)

R-13: Compound (IV-3) N-vinylsuccinimide (synthetic) Synthesis according to Kunststoffe Plastics, 4, 257-64, (1957)

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

R-15: Compound (IV-8) N-acryloyl morpholine (ACMO: Co., Ltd. product)

R-16: Compound (V-1) 4-vinyl-1-cyclohexane-1,2-epoxide (Celoxide 2000 produced by Daicel Chemical Co., Ltd.)

R-17: Compound (V-2) 2-vinyl 2-oxazoline (VOZO: Co., Ltd. product)

R-18: Compound (V-6) 4-vinyl-1,3-dioxolane2-one (Reagent manufactured by Aldrich)

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

R-20: Compound (VI-10) 2-methacryloyloxyethyl isocyanate (Kains MOI: manufactured by Showa Denko)

R-21: Compound (VII-2) N-hydroxyethylacrylamide (HEAA: Co., Ltd. product)

R-22: Compound (VII-1) N-vinylformamide (Beamset 770: manufactured by Arakawa Chemical Industries, Ltd.)

R-23: compound (IX-2) acrylic acid 3- (trimethoxysilyl) propyl ester (Tokyo Kasei reagent)

R-24: compound (IX-20) 2-methacryloxyethyl acid phosphate (light ester P-1M: the Kyowa Co., Ltd. make)

R-25: ethoxyji ethylene glycol acrylate (light acrylate EC-A: the Kyogisha Co., Ltd. make)

R-26: benzyl acrylate (BISCOTT # 160: manufactured by Osaka Organic Chemical Industries, Ltd.)

R-27: Phenoxyethyl acrylate (light acrylate PO-A: the Kyoeisha Oil Corporation)

R-28: Epoxyacrylate (Ebecryl 3701: manufactured by Daicel UCB)

R-29: α-methylstyrene (a reagent obtained from Tokyo Kasei Co., Ltd.)

R-30: compound (IX-20) 2-methacryloxyethyl acid phosphate (light ester P-1M: the Kyogisha Co., Ltd. make)

<Bifunctional monomer>

S-01: compound (IX-23) ethylene oxide modified phosphate dimethacrylate (Kayama PM-21: produced by Nippon Kayaku Co., Ltd.)

S-02: hydroxy pivaline neopentyl glycol diacrylate (color yard MANDA: Nihon Kayaku Co., Ltd.)

S-03: Polyethylene glycol diacrylate (New Frontia PE-300: Daiichichikyo Seiyaku Co., Ltd.)

S-04: tripropylene glycol diacrylate (color yard TPGDA: produced by Nihon Kayaku Co., Ltd.)

S-05: Ethylene oxide modified neopentyl glycol diacrylate (Photoma 4160: manufactured by Sanofoko Corp.)

S-06: 1,6-hexanediol diacrylate (Frontia HDDA: produced by Daiichi-kyo Kogyo Seiyaku Co., Ltd.)

S-07: ethylene oxide modified bisphenol A diacrylate (SR-602: manufactured by Kayaku Satoma Co., Ltd.)

S-08: ethylene oxide modified bisphenol A diacrylate (Aronix M-211B: manufactured by Toagosei Co., Ltd.)

S-09: tricyclodecane dimethanol acrylate (color yard R684: made by Nihon Kayaku Co., Ltd.)

S-10: Ethylene Glycol Dimethacrylate (Light Ester EG: manufactured by Kyoeisha Co., Ltd.)

<3-functional monomer or oligomer>

S-11: ethylene oxide modified trimethylolpropane triacrylate (SR-454: manufactured by Kayakusato Co., Ltd.)

S-12: Propylene oxide modified trimethylolpropane triacrylate (New Frontia TMP-3P: Dai-ichi Kogyo Seiyaku Co., Ltd.)

S-13: pentaerythritol ethoxy tetraacrylate (Ebercryl 40: manufactured by Daicel UCB)

S-14: dipentaerythritol hexaacrylate (color yard DPHA: produced by Nihon Kayaku Co., Ltd.)

S-15: trimethylol propane triacrylate (Aronix M-309: manufactured by Toagosei Co., Ltd.)

S-16: Aquaron RN-20: Daiichichikyo Seiyakusa

The symbol of the photoinitiator and the photo-acid generator used for the Example and comparative example of this invention is as follows.

<Photoinitiator>

P-1: 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide (Lucirin TPO-L: manufactured by BASF Corporation)

P-2: 2, 2-dimethoxy- 1, 2-diphenyl ethane- 1-one (Irgacure 651: Chiba Specialty Chemicals company make)

P-3: 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocure1173: Chiba Specialty Chemicals Co., Ltd.)

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

P-5: A mixture of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2,2-dimethoxy-1,2-diphenylethan-1-one (Irgacure1 300: Chiba specialty chemicals company production)

P-6: 1- [4-benzoylphenylsulfanyl] phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one (ESACUR 1001M: manufactured by Nippon Seeber Hegner)

P-7: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane "(Irgacure-907: produced by Chiba Specialty Chemicals Co., Ltd.)

P-8: hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals make: Irgacure-184)

The symbol of surfactant and additive used in the Example and comparative example of this invention is as follows.

<Surfactant>

W-1: Fluorine-type surfactant (Tochem Products Co., Ltd. make: Fluorine-type surfactant)

W-2: Silicone type surfactant (Dainippon Ink Chemical Co., Ltd. make: Mega Pack Fine Tide 31)

W-3: Fluorine-silicone surfactant (Dainippon Ink Chemical Co., Ltd. make: Megapack R-08)

W-4: Fluorine-silicone surfactant (Dainippon Ink Chemical Co., Ltd. make: Megapack XRB-4)

W-5: Fluorine-type surfactant (made by Dainippon Ink & Chemicals, F-173)

W-6: Fluorine-based surfactant (Sritomo Three M Co., Ltd .: FC-430)

CS-1: colloidal silica (Nissan Chemical Industries, Ltd .: MIBK-ST, 30% methyl isobutyl ketone solution)

CS-2: A solution in which propylene carbonate solvent is converted into an aqueous dispersion of tin oxide (manufactured by Ishihara Sangyo: SN-38F), 30% by mass

CS-3: Surface-treated silica synthesized in Synthesis Example 1

CS-4: Surface-treated silica synthesized in Synthesis Example 2

CS-5: Surface-treated silica synthesized in Synthesis Example 3

CS-6: Surface-treated silica synthesized in Synthesis Example 4

CS-7: Surface-treated silica synthesized in Synthesis Example 5

CS-8: Surface-treated silica synthesized in Synthesis Example 6

CS-9: Surface-treated silica synthesized in Synthesis Example 7

CS-10: Surface-treated silica synthesized in Synthesis Example 8

<Additive>

A-1: 2-chlorothioxanthone

A-2: 9, 10-dibutoxy anthracene (made by Kawasaki Kasei Co., Ltd.)

A-3: Silane Coupling Agent (Vinyl Triethoxy Silane) (Shin-Etsu Silicone Co., Ltd.)

A-4: silicone oil (made by Nippon Unicar Company: L-7001)

A-5: 2-dimethylaminoethylbenzoate

A-6: Benzophenone

A-7: 4-dimethylamino benzoate

A-8: modified dimethyl polysiloxane (Bikkemi Japan company make: BYK-307)

A-9: Red 225 (Sdan III)

A-10: polyether modified dimethylsilicone oil (by Big Chemie, Judge make: BYK302)

<Evaluation of the curable composition for optical nanoimprint lithography>

About each of the compositions obtained by Examples 1-27 and Comparative Examples 1-13, it measured and evaluated in accordance with the following evaluation methods.

Table 1 and Table 4 show the compounding ratios (Examples and Comparative Examples) of the polymerizable unsaturated monomers used in the composition.

Table 2 and Table 5 show the compounding ratios (Examples and Comparative Examples) of various components of the composition, respectively.

Table 3 and Table 6 show evaluation methods (Examples and Comparative Examples) of the compositions, respectively.

<Viscosity measurement>

The viscosity was measured at 25 ± 0.2 ° C using a RE-80L rotary viscometer manufactured by Toki Sangyo Co., Ltd.

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

<Measurement of photocuring speed (photocurability)>

The measurement of photocurability is carried out using a high-pressure mercury lamp as a light source, a change in absorption of 810 cm ^-1 of a monomer using a free-transform infrared spectrometer (FT-IR), and the curing reaction rate (monomer consumption) in real time. It was. A represents a case where the curing reaction rate is 0.2 / second or more, and B represents a case where the curing reaction rate is less than 0.2 / second.

<Adhesiveness>

Adhesiveness was affixed on the surface of the photocurable resist pattern which photocured, and it was judged by visual observation whether the photocurable resist pattern photocurable adhered to the tape side when peeling, and evaluated as follows.

A: No sticking of the pattern on the tape side

B: Very thin on the tape side, but the pattern is confirmed

C: The pattern is firmly confirmed on the tape side

Peelability

When peeling a mold after photocuring, the peelability observed with an optical microscope whether the unhardened | cured material remains in a mold, and evaluated as follows.

A: no residue

B: partially residue

C: residue on entire surface

Observation of Remnant and Pattern Shape

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

(Residuality)

A: No residue was observed

B: Some residue is observed

C: Many residues are observed

(Pattern shape)

A: Almost same as original pattern of original of pattern shape of mold

B: The original pattern shape of the mold is different from the original pattern shape and some parts (less than 20% of the original pattern shape)

C: Certainly different from the original pattern of the original pattern shape of the mold, or the film thickness of the pattern is 20% or more different from the original pattern

<Spin coating suitability>

Applicability (I)

After spin-coating the composition of this invention so that thickness may be set to 5.0 micrometers on the 4-inch 0.7 mm-thick glass substrate which formed the aluminum (Al) film of 4,000 angstrom of film thickness, the said glass substrate was left to stand for 1 minute, and it was planar. Observation was performed and it evaluated as follows.

A: No coating defects (stripes) were observed

B: Application defects are slightly observed

C: Striking or application defects are strongly observed

<Slit application suitability>

Applicability (II)

0.7 mm of 4 inches which formed the aluminum (Al) film of 4000 angstroms of film thickness using the slit coat resist coating apparatus (the head coater system made by Hirata Koku Co., Ltd.) for the application of a large size board | substrate for the composition of this invention. It applied on the glass substrate (550 mm x 50 mm) of thickness, the resist film of 3.0 micrometers in thickness was formed, the presence or absence of the stripe-shaped nonuniformity which emerged vertically and horizontally was evaluated, and it evaluated as follows.

A: No striped irregularity was observed

B: Stripe unevenness was weakly observed

C: Stripe unevenness was strongly observed or shock was observed on the resist film

<Etchability>

After forming and hardening the composition of this invention in the pattern shape on the electric aluminum (Al) formed in the glass substrate, the aluminum thin film is etched with a phosphate etchant, and 10 micrometers line / space is observed visually and a microscope, It evaluated as follows.

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

B: Line deviation of the line width of the line (difference) ± 2.0 μm is obtained

C: The missing part of a line is partially present or partly connected between lines

D: Defects existed on the whole surface or lines were connected

<Comprehensive Evaluation>

The comprehensive evaluation was performed based on the following criteria. Withstands practical use above actual B rank.

A: Rank 1 is less than 1 item.

B: B rank is 2 items.

C: 3 or more items of B rank or 1 item of C rank.

D: When there is even one item of D rank.

Synthesis Example 1 Surface Treatment of Colloidal Silica; Synthesis of CS-3

A mixture of 120 g of isopropanol, 60.6 g of Nalcoag 1034A (manufactured by Nalco Chemical Co., 35% colloidal silica aqueous dispersion), and 5.8 g of γ-methacryloxypropyltrimethoxysilane was heated to reflux at 80 ° C for 3 hours, and then under reduced pressure. The solvent was half removed, and 140 g of butoxyethanol was added to this solution to remove the solvent, thereby obtaining a 30 mass% solution of ethoxybutanol (CS-3) of silica whose surface was treated with a silane compound.

Synthesis Example 2 Surface Treatment of Colloidal Silica; Synthesis of CS-4

A mixture of 50 parts of tert-butanol, 16.6 g of Nalcoag 1034A and 1.4 g of γ-methacryloxypropyltrimethoxysilane was heated to reflux for 5 minutes, and then the solvent was removed halfway under reduced pressure. Toxic ethanol was added and the solvent was removed under reduced pressure to obtain a 30 mass% solution (CS-4) of ethoxy butanol of silica whose surface was treated with a silane compound.

Synthesis Example 3: Surface treatment of colloidal silica; Synthesis of CS-5

In a flask equipped with a stirrer, a condenser and a thermometer, 63.0 g of IPA-ST (isopropanol-dispersed colloidal silica sol, manufactured by Nissan Chemical Industries, Ltd., silica particle size 15 nm, silica solid content 30 mass%) and MEHQ as 0.0013 were used as a polymerization inhibitor. In addition, 50 g of diluted hydrochloric acid aqueous solution was added as a hydrolysis catalyst, and the temperature of the warm bath was heated up at 80 degreeC, stirring. At the same time as reflux, γ-acryloyloxypropyl trimethoxysilane (made by Shin-Etsu Chemical Co., Ltd., brand name KBM 503, molecular weight 290) 11.7g, trimethyl methoxysilane (made by Shin-Etsu Chemical Co., Ltd.) 1.6 g of a mixed solution of trade name LS-510, molecular weight 104) was added dropwise over about 30 minutes, and after the dropping was completed, the mixture was heated and stirred for about 2 hours to disperse in isopropanol, and the surface was treated with a silane compound. Mass% solution (CS-5) was obtained.

Synthesis Example 4 Surface Treatment of Colloidal Silica; Synthesis of CS-6

0.6 g of trimethylmethoxysilane (made by Toray Dow Corning Co., Ltd.) was added to 20.0 g of methanol dispersion colloidal silica of 20.0 mass% of solid content, and it stirred at 60 degreeC for 3 hours. Thereafter, 14.0 g of methoxypropanol was added, and the mixture was concentrated at a temperature of 80 ° C to obtain dispersed colloidal silica (CS-6) having a solid content of 30.0% by mass.

Synthesis Example 5 Surface Treatment of Colloidal Silica; Synthesis of CS-7

300 g of PL-1-IPA (isopropanol dispersed colloidal silica, manufactured by Fusogakuku Kogyo Co., Ltd., 12.5% by weight of silica) 1200 g of isopropanol, 15 g of acetic acid, 9.20 g of γ-acryloyloxypropyltrimethoxysilane, and n- 8.20 g of hexyltrimethoxysilane was added and heated to reflux. After that, isopropanol was removed to obtain surface-treated silica (CS-7) dispersed in a solid content of 12% by mass.

Synthesis Example 6 Surface Treatment of Colloidal Silica; Synthesis of CS-8

To 30 g of MEK-ST (methyl ethyl ketone dispersed colloidal silica, manufactured by Nissan Chemical Industries, Ltd., 30% by weight of silica), 200 g of methyl ethyl ketone, 2.0 g of dilute hydrochloric acid solution, and γ-methacryloyloxypropyl trimethoxysilane 2.5 g was added and heated to reflux to obtain surface treated silica (CS-8).

Synthesis Example 7 Surface Treatment of Colloidal Silica; Synthesis of CS-9

In 300 g of methanol, 100 g of methanol-dispersed colloidal silica having 20% by weight of silica solids, 5.0 g of formic acid, 1.00 g of gamma -acryloyloxypropyltrimethoxysilane and 2.60 g of n-decyltrimethoxysilane were added, and at room temperature, 24 g was added. Stirred for time. Thereafter, 80 g of methyl isobutyl ketone was added while heating to 80 degrees to remove methanol, thereby obtaining methyl isobutyl ketone dispersed surface-treated silica (CS-9).

Synthesis Example 8: Surface treatment of colloidal silica; Synthesis of CS-10

1.0 g of 1% acetic acid aqueous solution and 8.35 g of γ-acryloyloxypropyltrimethoxysilane were added to 91.3 g of IPA-ST, followed by heating to reflux for 3 hours, and then 1.47 g of hexamethyldisilazane was added thereto, followed by heating under reflux for 1 hour. To obtain surface-treated silica (CS-10).

Example 1

As the polymerizable unsaturated monomer, 19.096 g of gamma-butyrolactone acrylate monomer (R-01), 66.84 g of tripropylene glycol diacrylate monomer (S-04), ethylene oxide modified trimethylolpropane triacrylate monomer (S- 11) 9.548 g, as a photopolymerization initiator, 2.50 g of 2,4,6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (Lucirin TPO-L, manufactured by BASF) (P-1), as a surfactant, EFTOP EF- 0.02 g of 122 A (fluorine-based surfactant, W-1) and 6.67 g of colloidal silica (manufactured by Nissan Chemical Co., Ltd .: MIBK-ST, 30% methyl isobutyl ketone solution) were weighed, and methyl ethyl ketone was less than 2% by mass at room temperature. It stirred until it became and used as a homogeneous solution. The composition ratio of the polymerizable unsaturated monomer used here is shown in Table 1, and the solid content compounding ratio of the composition is shown in Table 2.

This adjusted composition was spin-coated so as to be 5.0 micrometers in thickness on the 4-inch 0.7-mm-thick glass substrate in which the aluminum (Al) film of 4,000 angstroms of film thickness was formed. 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, a mold pressing force of 0.8 kN, a vacuum degree of exposure of 10 Torr, and a 10 μm line / space pattern. Exposed to a condition of 100 mJ / cm ² from the back surface of the mold made of polydimethylsiloxane having a groove depth of 5.0 μm (made by Toray Dow Corning, Inc., cured SILPOT 184 at 80 ° C. for 60 minutes). Then, the mold was peeled off to obtain a resist pattern. Subsequently, the aluminum (Al) part which is not coat | covered with a resist by the phosphate etchant was removed, and the electrode pattern made from aluminum (Al) was formed. Moreover, resist peeling was immersed for 3 minutes at 80 degreeC using the monoethanolamine / dimethyl sulfoxide mixed peeling liquid. The results are shown in Table 3. From the result of Table 3, the composition of this invention was able to satisfy all of adhesiveness, peelability, residual film property, pattern shape, coating property (spin coating property, slit coating property), and etching property.

Example 2

As a polymerizable unsaturated monomer, 38.11 g of (alpha)-acryloyloxy- (beta)-(beta)-dimethyl- (gamma)-butyrolactone monomers (R-2), and hydroxy pivarin neopentyl glycol diacrylate monomer (S-2) 47.74 g, propylene oxide modified trimethylolpropane triacrylate (S-12), 2, 4, 6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (Lucirin TPO-L manufactured by BASF) as a photopolymerization initiator (P-1) 2.5g, as a surfactant, Megapack R-08 (fluorine-silicone-based surfactant) (W-3) manufactured by Dainippon Ink & Chemicals Co., Ltd., and 6.67 g of a 30 mass% solution of surface-treated colloidal silica. Was weighed and stirred until the methyl ethyl ketone was less than 2% by mass at room temperature to obtain a homogeneous solution. The composition was exposed and patterned in the same manner as in Example 1, and the properties of the composition were examined. The results are shown in Table 3. From the result of Table 3, it was confirmed that the composition of this invention can satisfy | fill comprehensively about adhesiveness, peelability, residual film property, pattern shape, applicability | paintability (spin coating property, slit coating property), and etching property.

Example 3-Example 27

In the same manner as in Example 1, the polymerizable unsaturated monomer was mixed at a ratio shown in Table 1, and the compositions described in Table 2 were adjusted. This adjusted composition was patterned in the same manner as in Example 1, and the properties of the composition were examined. The results are shown in Table 4. All the compositions of Examples 3-27 were able to satisfy | fill comprehensively about photocurability, adhesiveness, peelability, residual film property, pattern shape, applicability | paintability (spin coating property, slit coating property), and etching property.

Comparative Example 1

The composition described in Example 4 of the ultraviolet curable coating material for an optical disc protective film disclosed in Japanese Patent Application Laid-Open No. 7-70472 is the same as that in Example 1 of the present invention, and the polymerizable unsaturated monomer is shown in Table 4. It mixed and the composition of Table 5 was adjusted. This adjusted composition was patterned in the same manner as in Example 1, and the properties of the composition were examined. The results are shown in Table 6.

As shown in Table 6, the composition of Comparative Example 1 was not generally satisfactory.

Comparative Example 2

The composition described in the examples of the optical disc overcoat composition disclosed in Japanese Patent Laid-Open No. 4-149280 was the same as in Example 1 of the present invention, and the polymerizable unsaturated monomers were mixed in the proportions shown in Table 5 to obtain the composition. Adjusted. This adjusted composition was patterned in the same manner as in Example 1, and the properties of the composition were examined. The results are shown in Table 6.

As shown in Table 6, the composition of Comparative Example 2 was not generally satisfactory.

Comparative Example 3

The composition described in Example 1 of the protective coat composition disclosed in Japanese Patent Application Laid-Open No. 7-62043 is the same as that in Example 1 of the present invention, and the polymerizable unsaturated monomer is mixed at a ratio shown in Table 5, and the composition Was adjusted. This adjusted composition was patterned in the same manner as in Example 1, and the properties of the composition were examined. The results are shown in Table 6.

As shown in Table 6, the composition of Comparative Example 3 was not generally satisfactory.

Comparative Example 4

The composition described in Comparative Example 2 of the protective coat composition disclosed in JP 2001-93192 was made in the same manner as in Example 1 of the present invention, and the polymerizable unsaturated monomers were mixed in the proportions shown in Table 5 to prepare the composition. Adjusted. This adjusted composition was patterned in the same manner as in Example 1, and the properties of the composition were examined. The results are shown in Table 6.

As shown in Table 6, the composition of Comparative Example 4 was not comprehensively satisfactory.

Comparative Example 5

The composition described in Example 2 of the ultraviolet ray and electron beam curable composition disclosed in JP 2001-270973 was made the same as in Example 1 of the present invention, and the polymerizable unsaturated monomer was mixed at a ratio shown in Table 5 to obtain a composition. Was adjusted. This adjusted composition was patterned in the same manner as in Example 1, and the properties of the composition were examined. The results are shown in Table 6.

As shown in Table 6, the composition of Comparative Example 5 was not satisfactory overall in addition to being poor in residual film property, pattern shape, coating property (I), and etching property.

Comparative Example 6

The composition described in Example 1 of the protective coat composition disclosed in Japanese Patent Laid-Open No. 7-53895 was the same as in Example 1 of the present invention, and a polymerizable unsaturated monomer was mixed at a ratio shown in Table 5 to prepare a composition. Adjusted. This adjusted composition was patterned in the same manner as in Example 1, and the properties of the composition were examined. The results are shown in Table 6.

As shown in Table 6, the composition of Comparative Example 6 was not generally satisfactory.

Comparative Example 7

The composition described in Example 1 of the painting composition disclosed in Japanese Unexamined Patent Publication No. 2003-165930 is made the same as in Example 1 of the present invention, and the polymerizable unsaturated monomers are mixed in the proportions shown in Table 5 to adjust the composition. It was. This adjusted composition was patterned in the same manner as in Example 1, and the properties of the composition were examined. The results are shown in Table 6.

As shown in Table 6, the composition of Comparative Example 7 was not good enough in terms of adhesiveness, residual film property, pattern shape, and etching property, but was not generally satisfactory.

Comparative Example 8

The Society of Industrial Engineers, 2005. The Beginners Book 38 patterned the composition containing NVP (N-vinylpyrrolidone) described on page 157 of the first nanoimprint technology in the same manner as in Example 1 of the present application, and the composition characteristics Was investigated. The results are shown in Table 6.

As shown in Table 6, the composition of Comparative Example 8 was not satisfactory overall in addition to being poor in applicability and etching property.

Comparative Example 9

The composition (viscosity 35cP) of Example 5 of the resin composition for hard-coats disclosed by Unexamined-Japanese-Patent No. 2006-63244 is made the same as Example 1 of this invention, and the polymerizable unsaturated monomer is shown in Table 5. The composition was adjusted by mixing with. This adjusted composition was patterned in the same manner as in Example 1, and the properties of the composition were examined. The results are shown in Table 6.

As shown in Table 6, in addition to being poor in applicability | paintability, it was not able to be satisfied also comprehensively.

Comparative Example 10

Proc. The optical nanoimprint composition (sample name: KRIP-09, viscosity 8.29 cP) disclosed in SPIE Int. Soc. Opt. Eng., Vol. 6151, No. Pt2, 61512F (2006) was compared with Example 1 of the present invention. In the same manner, the polymerizable unsaturated monomers were mixed in the proportions shown in Table 5, and the compositions were adjusted. Since the chemical name of a specific (meth) acryl monomer is not described in the said document, a commercial monomer was arbitrarily selected and the composition was adjusted. As a monofunctional monomer, the acrylic monomer, the bifunctional monomer, the (meth) acryl monomer, and the trifunctional monomer selected the acrylic monomer. The photopolymerization initiator was compounded with 1.25% of the compound (DAROCURE 4265) disclosed in the above document. Since the said surfactant is not mix | blended, it was not mix | blended. As shown in Table 6, the composition of Comparative Example 10 was not satisfactory in general except for being poor in peelability and coating property (II).

Comparative Example 11

The photonanoimprint composition (sample name: KRIP-11, viscosity 9.7 cP) disclosed in Proc. SPIE Int. Soc. Opt. Eng., Vol. 6171, No. Pt2, 61512F (2006) was used as an example of the present invention. It carried out similarly to 1, the polymerizable unsaturated monomer was mixed in the ratio shown in Table 5, and the composition was adjusted. Since the chemical name of a specific (meth) acryl monomer is not described in the said document, a commercial monomer was arbitrarily selected and the composition was adjusted. As the monofunctional monomer, an acrylic monomer was selected, a bifunctional monomer was a methacryl monomer, and the trifunctional monomer was an acrylic monomer. The photopolymerization initiator blended 1.25% of the compound (DAROCURE 4265) disclosed in the above document. Since the said surfactant is not mix | blended, it was not mix | blended. As shown in Table 6, the composition of Comparative Example 11 was not satisfactory in general except for being poor in peelability and coating property (II).

Comparative Example 12

As a monofunctional polymerizable unsaturated monomer different from the monofunctional polymerizable unsaturated monomer of this invention (monofunctional polymerizable unsaturated monomer which has a site | part which has an ethylenically unsaturated bond in a molecule, and at least 1 sort (s) of oxygen, nitrogen, or a sulfur atom), α- The monofunctional monomer of Example 9 was substituted using methyl styrene (reagent), it carried out similarly to Example 1 of this invention, the polymerizable unsaturated monomer was mixed in the ratio shown in Table 5, and the composition was adjusted. However, in Comparative Example 12, inorganic oxide particles were not added. This adjusted composition was patterned in the same manner as in Example 1, and the properties of the composition were examined. The results are shown in Table 6. As shown in Table 6, the composition of Comparative Example 12 was not satisfactory in terms of photocurability, residual film properties, and pattern shape, but could not be comprehensively satisfied.

Comparative Example 13

Surface-treated silica (CS-3) was blended with the composition used in Comparative Example 12, and the composition was adjusted in the same manner as in Example 1 of the present invention. This adjusted composition was patterned in the same manner as in Example 1, and the properties of the composition were examined. The results are shown in Table 6. As shown in Table 6, the composition of Comparative Example 13 was not comprehensively satisfactory.

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

<Evaluation of Photocurable Composition-II>

The composition of this invention was evaluated as a permanent film (protective film).

<Remnant Rate>

The photocurable composition of this invention is spin-coated so that it may become a film thickness of 4 micrometers on a glass substrate, it is set to the nanoimprint apparatus which uses a high pressure mercury lamp as a light source, it exposes on the conditions of 500mJ / cm <^2> from the back surface of a mold, and exposes it. Then, the mold was peeled off and heated for 150 minutes in 230 degreeC oven. The film thickness of the pattern part of the photocurable resin before and after heating was measured by the profiler P11 by Tenkor company, and the residual film rate after heating was calculated | required. The results are shown in Table 7.

A: Remaining film rate exceeds 90%

B: Residual rate 85-90%

C: Remnant ratio less than 85

<Transmittance>

Spin coating the photocurable composition of the present invention on a glass substrate so as to have a film thickness of 4 µm, and setting it in a nanoimprint apparatus using a high-pressure mercury lamp as a light source, and exposing ultraviolet light under a condition of 500 mJ / cm ² from the back of the mold. And a cured film were formed. After exposure, the mold was peeled off and heated for 150 minutes in an oven at 230 deg. The light transmittance (T /%) in wavelength 550nm was measured for the light transmittance of the pattern part of the photocurable resin after heating using the spectrophotometer, and the transmittance | permeability after heating was calculated | required. The obtained light transmittance was judged on the following references | standards. The results are shown in Table 7.

A: The value is 90% or more.

B: The light transmittance is less than 85 to 90%.

C: The light transmittance is less than 85.

<Image resistance test>

After rotationally coating the photocurable composition on a silicon wafer, a high-pressure mercury lamp was used to irradiate ultraviolet rays so that the exposure amount was 300 mJ / cm ² , and a cured film having a thickness of 5 μm was formed. The cured film was placed in a Hakjin wear tester, and it was reciprocated by applying a 200g load on steel wool. The situation of imaging was visually determined by the following criteria. The results are shown in Table 7.

A: No flaw at all

B: 1 to 3 flaws

C: 4 to 10 flaws

D: 10 or more flaws

<Contents Resistance>

The photocurable composition of this invention is spin-coated so that it may become a film thickness of 4 micrometers on a glass substrate, it is set to the nanoimprint apparatus which uses a high pressure mercury lamp as a light source, it exposes on the conditions of 500mJ / cm <^2> from the back surface of a mold, and exposes it. Then, the mold was peeled off and heated for 150 minutes in 230 degreeC oven. After heating, it was immersed in each solution of N-methylpyrrolidone (NMP), 5% sodium hydroxide, and 5% hydrochloric acid for 30 minutes, and the film thickness change after before immersion was calculated | required. The results are shown in Table 7.

A: Almost no change in film thickness was observed (less than 1%).

B: slight change in film thickness is observed (less than 1-5%)

C: Some change in film thickness was observed (more than 5%).

<Comprehensive Evaluation>

Overall evaluation was performed based on the following criteria. Withstand practical use above real B rank. The results are shown in Table 7.

A: B rank is within 2 items.

B: Three ranks of B ranks.

C: 4 or more items of B rank or 1 item of C rank.

D: C rank is two or more items or D rank is one item.

Example 36

2 mass% of antioxidant (made by ADEKA, Adeka stop AO503) was added to the composition, without changing the kind of monomer, photoinitiator, surfactant, inorganic oxide particle, and compounding ratio used in Example 3, and it carried out similarly to Example 1 And the composition was adjusted. The adjusted composition was spin-coated to a film thickness of 4 µm on a glass substrate, and 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. The mold pressure is 10 kN / cm ² , the vacuum degree during exposure is 0.2 Torr, and the mold is made of polydimethylsiloxane (cured SILPOT 184 manufactured by Toray Dow Corning Inc. at 80 ° C. for 60 minutes) having a square pattern of 5 mm. It exposed on the back surface on 500 mJ / cm <^2> conditions, and after exposure, the mold was peeled off and the residual film ratio, the transmittance | permeability, and the imaging resistance of the pattern part of the photocurable resin before and after heating were measured. Thereafter, solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 36 was excellent in residual film rate, transmittance | permeability, imaging resistance, and solvent resistance, and was also excellent in the characteristic as a permanent film.

Example 37

2 mass% of antioxidant (made by ADEKA, Adeka stop AO 503) was added to the composition, and the same amount as that of Example 1 was not changed without changing the type, compounding ratio of the monomer, photopolymerization initiator, surfactant, and inorganic oxide particles used in Example 7. To adjust the composition. The adjusted composition was spin-coated to a film thickness of 4 µm on a glass substrate, and 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. The mold pressure is 10 kN / cm ² , the vacuum degree during exposure is 0.2 Torr, and the mold is made of polydimethylsiloxane having a 5 mm square pattern (hardened SILPOT 184 manufactured by Toray Dow Corning Inc. at 80 ° C. for 60 minutes). It exposed on the conditions of 500mJ / cm <^2> from the back surface, and after exposure, the mold was peeled off and the residual film ratio, transmittance | permeability, and imaging resistance of the pattern part of the photocurable resin before and after heating were measured. Thereafter, solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 37 was excellent in residual film rate, transmittance | permeability, imaging resistance, and solvent resistance, and was also excellent in the characteristic as a permanent film.

Example 38

2.0 mass% of antioxidant (Sumitomo Kagaku Kogyo Co., Ltd., Sumiiser GA80) was added to the composition, without changing the kind, compounding ratio of the monomer, photoinitiator, surfactant, inorganic oxide particle used in Example 15, and Example 1 The same was done and the composition was adjusted. The adjusted composition was spin-coated to a film thickness of 4 µm on a glass substrate, and 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. The mold pressure is 10 kN / cm ² , the vacuum degree during exposure is 0.2 Torr, and the mold is made of polydimethylsiloxane having a 5 mm square pattern (hardened SILPOT 184 manufactured by Toray Dow Corning Inc. at 80 ° C. for 60 minutes). It exposed on the condition of 500mJ / cm <^2> from the back surface, and after exposure, the mold was peeled off and the residual film rate, transmittance | permeability, and imaging resistance of the pattern part of the photocurable resin before and after heating were measured. Thereafter, solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 38 was excellent in residual film rate, transmittance | permeability, imaging resistance, and solvent resistance, and was also excellent in the characteristic as a permanent film.

Example 39

2.0 mass% of antioxidant (Sumiiser GA80 Sumitomo Chemical Co., Ltd. product) was added to the composition, and the kind, compounding ratio of the monomer, photoinitiator, surfactant, and inorganic oxide particle used in Example 17 were added, and it was the same as Example 1. And the composition was adjusted. The adjusted composition was spin-coated to a film thickness of 4 µm on a glass substrate, and 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. The mold pressure is 10 kN / cm ² , the vacuum degree during exposure is 0.2 Torr, and the mold is made of polydimethylsiloxane having a 5 mm square pattern (made by Toray Dow Corning Inc., cured SILPOT 184 at 80 ° C. for 60 minutes). It exposed on the conditions of 500mJ / cm <^2> from the back surface of, and after exposure, the mold was peeled off and the residual film ratio, transmittance | permeability, and imaging resistance of the pattern part of the photocurable resin before and after heating were measured. Thereafter, solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 39 was excellent in residual film rate, transmittance | permeability, imaging resistance, and solvent resistance, and was also excellent in the characteristic as a permanent film.

Example 40

The monomers, photopolymerization initiators, surfactants, inorganic oxide particles, and sensitizers used in Example 19 were not changed, and the compounding ratio was not changed, and the composition (2.0% by mass of Sumitomo Chemical Chemical Co., Ltd., Smizer GA80, ADEKA, 0.5 mass% of adeka stop AO503) was added, and it carried out similarly to Example 1, and adjusted the composition. The adjusted composition was spin-coated to a film thickness of 4 µm on a glass substrate, and 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. The mold back pressure is 10 kN / cm ² , the vacuum degree during exposure is 0.2 Torr, and the back side of the mold made of polydimethylsiloxane (cured SILPOT184 manufactured by Toray Dow Corning Inc. at 80 ° C. for 60 minutes) having a square pattern of 5 mm. It exposed on 500 mJ / cm <^2> conditions, and after exposure, the mold was peeled off and the residual film rate, transmittance | permeability, and imaging resistance of the pattern part of the photocurable resin before and after heating were measured. Thereafter, solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 40 was excellent in residual film rate, transmittance | permeability, imaging resistance, and solvent resistance, and was also excellent in the characteristic as a permanent film.

Example 41

2.0 mass% of antioxidant (Sumitomo Chemical Co., Ltd. product, Sumifier GA80) was added to the composition, without changing the kind, compounding ratio of the monomer, photoinitiator, surfactant, inorganic oxide particle, sensitizer used in Example 22, and it carried out. The composition was adjusted in the same manner as in Example 1. The adjusted composition was spin-coated to a film thickness of 4 µm on a glass substrate, and 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. The mold pressure is 10 kN / cm ² , the vacuum degree during exposure is 0.2 Torr, and the mold is made of polydimethylsiloxane having a 5 mm square pattern (made by Toray Dow Corning Inc., cured SILPOT 184 at 80 ° C. for 60 minutes). It exposed on the conditions of 500mJ / cm <^2> from the back surface of, and after exposure, the mold was peeled off and the residual film ratio, transmittance | permeability, and imaging resistance of the pattern part of the photocurable resin before and after heating were measured. Thereafter, solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 41 was excellent in residual film rate, transmittance | permeability, imaging resistance, and solvent resistance, and was also excellent in the characteristic as a permanent film.

Example 42

As the polymerizable unsaturated monomer, 28 g of benzyl acrylate monomer (R-26), neopentyl glycol diacrylate monomer (KAYARAD NPGDA; manufactured by Nihon Kayaku), 1.9 g of trimethylolpropane triacrylate monomer (S-15) 2, 4, 6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (Lucirin TPO-L by BASF) (P-1) 3.0g as a photoinitiator, EFTOP EF-122A (fluorine-type interface as a surfactant) 0.05 g of the activator, W-1), 2.0 g of an antioxidant (manufactured by Sumitomo Chemical Co., Ltd., Smizer GA80) and 83.3 g of a 30% by mass solution of surface-treated colloidal silica were weighed, and 2% by mass of methyl ethyl ketone at room temperature. It stirred until it became less than and set it as the homogeneous solution. The adjusted composition was spin-coated to a film thickness of 4 µm on a glass substrate, and 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. The mold pressure is 10 kN / cm ² , the vacuum degree during exposure is 0.2 Torr, and the mold is made of polydimethylsiloxane having a 5 mm square pattern (hardened SILPOT 184 manufactured by Toray Dow Corning Inc. at 80 ° C. for 60 minutes). It exposed on the conditions of 500mJ / cm <^2> from the back surface, and after exposure, the mold was peeled off and the residual film ratio, transmittance | permeability, and imaging resistance of the pattern part of the photocurable resin before and after heating were measured. Thereafter, solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 42 was excellent in residual film rate, transmittance, imaging resistance, and solvent resistance, and also excellent in properties as a permanent film.

Example 43

2 mass% of antioxidant (made by Adeka, Adeka stop AO503) was added to the composition, without changing the kind of monomer, photoinitiator, surfactant, inorganic oxide particle, and compounding ratio used in Example 29, and it carried out similarly to Example 1 To adjust the composition. The adjusted composition was spin-coated to a film thickness of 4 µm on a glass substrate, and 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. The mold pressure is 10 kN / cm ² , the vacuum degree during exposure is 0.2 Torr, and the mold is made of polydimethylsiloxane having a 5 mm square pattern (hardened SILPOT 184 manufactured by Toray Dow Corning Inc. at 80 ° C. for 60 minutes). It exposed on the conditions of 500mJ / cm <^2> from the back surface, and after exposure, the mold was peeled off and the residual film ratio, transmittance | permeability, and imaging resistance of the pattern part of the photocurable resin before and after heating were measured. Thereafter, solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 43 was excellent in residual film rate, transmittance | permeability, imaging resistance, and solvent resistance, and was also excellent in the characteristic as a permanent film.

Example 44

2 mass% of antioxidant (made by ADEKA, Adecastabu AO503) was added to the composition, without changing the kind and compounding ratio of the monomer, photoinitiator, surfactant, and inorganic oxide particles used in Example 31, in the same manner as in Example 1. To adjust the composition. The adjusted composition was spin-coated to a film thickness of 4 µm on a glass substrate, and 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. The mold pressure is 10 kN / cm ² , the vacuum degree during exposure is 0.2 Torr, and the mold is made of polydimethylsiloxane having a 5 mm square pattern (hardened SILPOT 184 manufactured by Toray Dow Corning Inc. at 80 ° C. for 60 minutes). It exposed on the conditions of 500mJ / cm <^2> from the back surface, and after exposure, the mold was peeled off and the residual film ratio, transmittance | permeability, and imaging resistance of the pattern part of the photocurable resin before and after heating were measured. Thereafter, solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 44 was excellent in residual film rate, transmittance | permeability, imaging resistance, and solvent resistance, and was also excellent in the characteristic as a permanent film.

Example 45

2 mass% of antioxidant (made by Adeka, Adeka stop AO503) was added to the composition, without changing the kind of monomer, photoinitiator, surfactant, inorganic oxide particle, and compounding ratio used in Example 36, and it carried out similarly to Example 1 To adjust the composition. The adjusted composition was spin-coated to a film thickness of 4 µm on a glass substrate, and 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. The mold back pressure is 10 kN / cm ² , the vacuum degree during exposure is 0.2 Torr, and the back side of the mold made of polydimethylsiloxane (cured SILPOT184 manufactured by Toray Dow Corning Inc. at 80 ° C. for 60 minutes) having a square pattern of 5 mm. It exposed on 500 mJ / cm <^2> conditions, and after exposure, the mold was peeled off and the residual film rate, transmittance | permeability, and imaging resistance of the pattern part of the photocurable resin before and after heating were measured. Thereafter, solvent resistance of the photocured film was examined. The results are shown in Table 7. The composition of Example 45 was excellent in residual film rate, transmittance | permeability, imaging resistance, and solvent resistance, and was also excellent in the characteristic as a permanent film.

Comparative Example 14

The composition used in Comparative Example 1 and patterned was adjusted in the same manner as in Example 36, and the properties of the composition were examined. The results are shown in Table 7. In addition, the antioxidant added to Example 36 is no addition. The composition of Comparative Example 14 tended to have a somewhat poor residual film ratio, permeability, and solvent resistance (NMP), and was also poor overall.

Comparative Example 15

The composition used in Comparative Example 2 was patterned in the same manner as in Example 36, and the properties of the composition were examined. The results are shown in Table 7. The composition of Comparative Example 12 tended to have a somewhat poor residual film ratio and solvent resistance (NMP), poor permeability, and poor overall.

Comparative Example 16

The composition used in the comparative example 3 and adjusted was patterned similarly to Example 36, and the characteristic of the composition was investigated. The results are shown in Table 7. The composition of Comparative Example 12 was poor in residual film rate and transmittance, and also in solvent resistance (NMP, HCl) tended to be somewhat poor, and overall was poor.

Comparative Example 17

The composition used in Comparative Example 4 and adjusted was patterned in the same manner as in Example 36, and the properties of the composition were examined. The results are shown in Table 5. The composition of Comparative Example 13 tended to be somewhat poor in residual film rate, transmittance, and solvent resistance (NMP, HCl), and also poor in permeability and poorly in general.

Comparative Example 18

The composition used in Comparative Example 9 was patterned in the same manner as in Example 36, and the properties of the composition were examined. The results are shown in Table 7. The composition of Comparative Example 18 tended to have a somewhat poor residual film rate, transmittance, and solvent resistance (NaOH), a poor permeability, and a general poor quality.

Examples 1-45

When the viscosity of the photocurable composition of this invention of Examples 1-45 was measured, all were 3-18 mPa * s range.

Comparative Examples 1-7, 9, 12, 13

It was all 20 mPa or more when the viscosity of the photocurable composition of Comparative Examples 1-7, 9, 12, and 13 was measured.

Comparative Example 8, 10, 11

When the viscosity of the photocurable compositions of Comparative Examples 8, 10 and 11 was measured, they were all in the range of 5-15 mPa.

Table 7

Compositions of the present invention include semiconductor integrated circuits, flat screens, microelectromechanical systems (MEMS), sensor elements, optical disks, magnetic recording media such as high density memory disks, optical components such as diffraction gratings and relief holograms, nanodevices, optical devices, Optical film or polarizing element for flat panel display, thin film transistor of liquid crystal display, organic transistor, color filter, overcoat layer, host material, rib material for liquid crystal alignment, micro lens array, immunoassay chip, DNA separation chip, micro In the production of reactors, nano biodevices, optical waveguides, optical filters, photonic liquid crystals and the like, it can be used as an optical nanoimprint resist composition for forming a fine pattern.

Claims (17)

0.00-1-5 mass% and 0.1-50 mass of inorganic oxide fine particles of 35-99 mass% of polymerizable unsaturated monomers, 0.1-15 mass% of photoinitiators, a fluorine-type surfactant, a silicone type surfactant, and a fluorine-type silicone surfactant, It contains%, The curable composition for optical nanoimprint lithography characterized by the above-mentioned. 48-99 mass% of polymerizable unsaturated monomers, 0.1-15 mass% of photoinitiators, 0.001-5 mass% of 1 or more types of fluorine-type surfactant, a silicone type surfactant, and a fluorine-type silicone surfactant, and 0.1-50 mass of inorganic oxide fine particles Containing%; As the polymerizable unsaturated monomer, at least 15% by mass or more of a monofunctional polymerizable unsaturated monomer containing a moiety having an ethylenically unsaturated bond in the molecule and a moiety having at least one of an oxygen atom, a nitrogen atom and a sulfur atom Curable composition for optical nanoimprint lithography characterized by containing. 48-99 mass% of polymerizable unsaturated monomers, 0.1-15 mass% of photoinitiators, 0.001-5 mass% of 1 or more types of fluorine-type surfactant, a silicone type surfactant, and a fluorine-type silicone surfactant, and 0.1-50 mass of inorganic oxide fine particles Containing%; As the polymerizable unsaturated monomer, at least 15% by mass or more of at least one monofunctional polymerizable unsaturated monomer among the compounds selected from the following (a), (b) and (c) is contained in the composition. Curable composition for imprint lithography. (a) a polymerizable unsaturated monomer having a moiety having an ethylenically unsaturated bond in one molecule and an aliphatic cyclic moiety containing a hetero atom (b) a polymerizable unsaturated monomer having a moiety having an ethylenically unsaturated bond in one molecule and a -C (= 0) -bond and an NR bond (R is a hydrogen atom or a methyl group); (c) a polymerizable unsaturated monomer having a moiety having an ethylenically unsaturated bond in one molecule and an alicyclic moiety having 6 to 12 carbon atoms) 0.001-5 mass% and 0.1-50 mass of inorganic oxide fine particles of 48-99 mass% of polymerizable unsaturated monomers, 0.1-15 mass% of photoinitiators, a fluorine-type surfactant, a silicone type surfactant, and a fluorine-type silicone surfactant, Containing%; As the polymerizable unsaturated monomer, (a) at least 15% by mass or more of at least one monofunctional polymerizable unsaturated monomer having a moiety having an ethylenically unsaturated bond in one molecule and an aliphatic cyclic moiety containing a hetero atom in the composition Curable composition for optical nanoimprint lithography, characterized by the above-mentioned. The curable composition for optical nanoimprint lithography according to claim 2, wherein the monofunctional polymerizable unsaturated monomer is at least one selected from the following general formulas (I) to (VIII). Formula (I)

(In General Formula (I), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, and an ethoxy group. represents. n1 is 1 or 2, m1 is 0, 1, represents any one of 2. Z ¹¹ represents a methylene group, an oxygen atom, -NH-, Z ¹¹ is a single 2 may be different from each other. W ¹¹ is -C (= O)-or -SO _2-, R ¹² and R ¹³ , And R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring.) Formula (II)

(In General Formula (II), R ²¹ represents a hydrogen atom or a methyl group, and R ²² , R ²³ , R ^24, and R ²⁵ each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group, Ethoxy group R ²² and R ²³ , And R ²⁴ and R ²⁵ may be bonded to each other to form a ring. n2 is any one of 1, 2, 3, and m2 represents any of 0, 1, 2. Y ²¹ represents a methylene group or an oxygen atom.) General formula (III)

(In Formula (III), R ³² , R ³³ , R ³⁴ and R ³⁵ each represent a hydrogen atom, a methyl group, an ethyl group, an propyl group, a butyl group, a halogen atom, a methoxy group and an ethoxy group. N3 represents 1, 2, 3 and any of one, m3 is 0, 1, represents any one of the 2 X ³¹ is -C (= O) -.. , represents a methylene, ethylene, 2 X ³¹ is Y or different from each other is ^32-methylene Group or oxygen atom.) General formula (IV)

(In General Formula (IV), R ⁴¹ represents a hydrogen atom or a methyl group. R ⁴² and R ⁴³ each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group, an ethoxy group.) ⁴¹ represents a single bond, no bond, or -C (= 0)-n4 represents any of 2, 3 and 4. X ⁴² represents -C (= 0)-, -C = C-,- C = N- or methylene group, and each X ⁴² may be the same or different, M ⁴¹ may represent a hydrocarbon linking group, an oxygen atom or a nitrogen atom having 1 to 4 carbon atoms, and each M ⁴¹ may be the same or different.) General formula (V)

(In formula (V), R ⁵¹ represents a hydrogen atom or a methyl group. Z ⁵² represents an oxygen atom, —CH = N- or a methylene group. W ⁵² represents a methylene group or an oxygen atom. Y ⁵² represents a single bond) Or —C (C═O) — Y ⁵³ represents a single bond or —C (C═O) — R ⁵⁴ and R ⁵⁵ each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen An atom, a methoxy group, an ethoxy group, R ⁵⁴ and R ⁵⁵ may be bonded to each other to form a ring X ⁵¹ may be a single bond or an unbonded m5 is any one of 0, 1, and 2. W ⁵² , At least one of Z ⁵² , R ⁵⁴ and R ⁵⁵ contains an oxygen atom or a nitrogen atom.) General formula (VI)

(In formula (VI), R ⁶¹ is a hydrogen atom or a methyl group, R ⁶² and R ⁶³ are each a hydrogen atom, a methyl group, an ethyl group, a hydroxyethyl group, a propyl group, (CH ₃ ) ₂ N- (CH ₂ ) m _6- (m6 is 1, 2 or 3), CH ₃ CO- (CR ⁶⁴ R ⁶⁵ ) _p6- (R ⁶⁴ and R ⁶⁵ each represent a hydrogen atom or a methyl group, p6 is either 1, 2 or 3), ( CH ₃ ) ₂ -N- (CH ₂ ) _p6- (p6 is either 1, 2 or 3.) provided that -NR ⁶² (R ⁶³ ) in Formula (VI) is -N = C Or a group O. R ⁶² and R ⁶³ are not hydrogen atoms at the same time, and X ⁶ is -CO-, -COCH _2- , -COCH ₂ CH _2- , -COCH ₂ CH ₂ CH ₂ -,- COOCH ₂ CH ₂ -is any one.) Formula (VII)

(In formula (VII), R ⁷¹ and R ⁷² each represent a hydrogen atom or a methyl group, and R ⁷³ represents a hydrogen atom, a methyl group or an ethyl group.) General formula (VIII)

(In formula (VIII), R ⁸¹ represents a hydrogen atom, a methyl group, or a hydroxymethyl group. R ⁸² , R ⁸³ , R ⁸⁴ , and R ⁸⁵ each represent a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, a hydroxymethyl group, or a hydroxyethyl group.) , A propyl group and a butyl group, two or more of R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ may be bonded to each other to form a ring, W ⁸¹ is a methylene group, -NH-, -N (CH ₃ )- , -N (C ₂ H ₅ )-W ⁸² represents a single bond or -C (= O)-When W ⁸² is a single bond, R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ are all hydrogen Not an atom, n7 represents an integer from 0 to 8). The method according to claim 1, wherein the polymerizable unsaturated monomer further contains 0.1% by mass or more of a second polymerizable unsaturated monomer containing at least one ethylenically unsaturated bond and a silicon atom and / or a person atom. Curable composition for optical nanoimprint lithography. The second polymerizable unsaturated monomer containing a site having at least one ethylenically unsaturated bond and a silicon atom and / or a person atom is further contained in an amount of 0.1% by mass or more in the polymerizable unsaturated monomer. Curable composition for optical nanoimprint lithography. The curable composition for photo nanoimprint lithography according to claim 1, wherein the inorganic oxide fine particles are colloidal silica. 3. The curable composition for photo nanoimprint lithography according to claim 2, wherein the inorganic oxide fine particles are colloidal silica. The curable composition for photo nanoimprint lithography according to claim 1, wherein the inorganic oxide particles are colloidal silica surface-treated with a compound having a reactive (meth) acrylate group. 3. The curable composition for photo nanoimprint lithography according to claim 2, wherein the inorganic oxide particles are colloidal silica surface-treated with a compound having a reactive (meth) acrylate group. The curable composition for photo nanoimprint lithography according to claim 1, which contains an antioxidant. The curable composition for photo nanoimprint lithography according to claim 2, which contains an antioxidant. 2. The curable composition for optical nanoimprint lithography according to claim 1, wherein the viscosity at 25 ° C. is 25 mPa · s or less. The curable composition for optical nanoimprint lithography according to claim 2, wherein the viscosity at 25 ° C is 25 mPa · s or less. The process of apply | coating the composition of Claim 1, the process of pressurizing a light-transmissive mold to the resist layer on a board | substrate, and the process of deforming the said apply | coated composition, the light is irradiated from the back surface of a mold or the back surface of a board | substrate, and a coating film is hardened to a desired pattern. A step of forming a tailored resist pattern, and a step of detaching a light-transmissive mold from a coating film. The process of apply | coating the composition of Claim 2, the process of pressurizing a light-transmissive mold to the resist layer on a board | substrate, and the process of deforming the said apply | coated composition, the light is irradiated on the back surface of a mold or a board | substrate, and a coating film is hardened | cured to a desired pattern. A step of forming a tailored resist pattern, and a step of detaching a light-transmissive mold from a coating film.