JP2015012100A - Photocurable composition for nanoimprint, and method for pattern formation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable composition for nanoimprint which is superior in the resistance against etching by a chlorine-based gas and long-term storage stability; and further to provide a photocurable composition for nanoimprint which is easy to transfer a pattern even in the case of pressing a mold against it with a relatively low pressure, exhibits good adhesion of the pattern with a base material, has good nanoimprint pattern transferability, and has good photocurability.SOLUTION: A photocurable composition for nanoimprint comprises (A) a polymerizable monomer having a (meth)acrylic group, (B) a particular metal alkoxide, (C) β-hydroxyketones, and (D) a photopolymerizable initiator.

Description

  The present invention relates to a novel photocurable nanoimprint composition, and further relates to a novel pattern forming method for forming a pattern on a substrate using the photocurable nanoimprint composition. The present invention also relates to a novel nanoimprint replica mold comprising a cured product of the composition.

  In recent years, semiconductor integrated circuits are required to be miniaturized and have high precision, but such microfabrication is not only for high precision semiconductor integrated circuits but also for providing light reflection prevention and light on LED substrates. In various applications such as optical / illumination applications such as taking-out efficiency improvement, energy development of secondary batteries, solar cells, fuel cells, biotechnology, etc., microfabrication by imprint technology has been actively studied.

The imprint technology is a method in which a desired pattern is formed on the surface of a substrate by embossing and peeling a mold having a concavo-convex pattern corresponding to the pattern to be formed on the substrate onto the coating film formed on the substrate surface. It consists of a transfer process and is expected as a fine processing technology that can be mass-produced at low cost.
By using this technique, a nano-order fine pattern can be formed. Among the imprint techniques, a technique for forming an ultrafine pattern of several nanometers to several hundred nanometers (nm) is called a nanoimprint technique.

  The nanoimprint technology is roughly classified into two types depending on the properties of the coating material formed on the substrate surface. One of them is a thermal nanoimprint method in which the pattern is transferred by heating and plastically deforming the coating material to which the pattern is transferred, then pressing the mold, cooling, and curing the coating material. is there. In addition, the other one uses a mold or a substrate in which at least one of the substrates is light transmissive, and forms a coating film by applying a liquid photocurable composition as a coating material on the substrate, In this method, the mold is pressed and brought into contact with the coating film, and then the pattern material is transferred by irradiating light through the mold or the substrate to cure the coating material. Among these, the optical nanoimprint method for transferring a pattern by light irradiation is capable of forming a high-precision pattern, and thus is widely used in nanoimprint technology, and is suitable for use in the method. Development of curable compositions is underway.

In the nanoimprint technology, the adhesion between the substrate surface and the pattern obtained by curing the coating film and the releasability between the pattern and the mold are important. For mold release from the mold, the mold surface is surface treated with a fluorine treatment agent to provide mold release, or fluorine such as pentafluoropropane gas is provided at the interface between the photocurable composition and the mold. A technique for imprinting with a system gas interposed is generally known. On the other hand, the adhesion to the substrate has been attempted to improve by subjecting the surface of the substrate to surface treatment, providing an easy-adhesion layer, or changing the composition of the photocurable composition. Adhesion with the substrate and mold release from the mold are contradictory properties, but further improvement is desired to increase productivity.
In order to give the coating material itself the contradictory characteristics, a proposal has been made to add a fluorine-based surfactant or a silicone compound to the coating material (see Patent Document 1). However, there are problems such as a decrease in adhesion to the substrate and bleeding out of the additive on the surface, and there is still room for improvement in terms of both adhesion to the substrate and releasability from the mold. It was.

  The nanoimprint technique is to form a desired pattern on a substrate based on a coating material (hereinafter sometimes referred to as a cured film) obtained by transferring a pattern with a mold and photocuring. In order to form a pattern on the substrate, dry etching of the cured film and the substrate is performed with oxygen gas, fluorine-based gas, chlorine-based gas, or the like. In such a dry etching process, the patterned cured film that protects the substrate is also etched, so that the etching rate ratio between the substrate and the cured film is important. Therefore, many photocurable compositions have been developed to form a cured film that is difficult to be etched by the above-described gas when performing various patterning. (Hereafter, this characteristic may be regarded as etching resistance).

  In order to improve the light extraction efficiency in the LED substrate, it is considered to suppress the total reflection of light from the element or reduce the crystal defects of the GaN layer stacked on the sapphire substrate by processing the unevenness on the surface of the sapphire substrate. Has been. As a method of processing irregularities on the surface of the sapphire substrate, silica is vapor-deposited using a mask, a resist pattern is formed by photolithography using a silica vapor deposition pattern as a mask, and then by hard mask deposition and lift-off. A method of performing a dry etching process by forming a metal mask is generally used. The substrate obtained by these methods is called Patterned Sapphire Substrates (PSS), and has a micron-order concavo-convex pattern on the sapphire surface. In recent years, for the purpose of further improving the luminous efficiency of LED light sources, it has been studied to provide a concavo-convex pattern of about 100 to 500 nm below the wavelength of visible light on the surface of sapphire to suppress lateral propagation due to total reflection. As such a method, a method of forming a pattern of a cured film on the surface of the sapphire substrate by nanoimprinting and using the mask as a mask to give a concavo-convex pattern to the surface of sapphire by dry etching treatment can be mentioned.

  As a gas used for dry etching of sapphire, a chlorine-based gas is generally used, and a cured film resin of a photocurable composition used for pattern formation is required to have high chlorine etching resistance. Aromatic compounds are considered effective for improving chlorine etching resistance because free carbon sources can be minimized. Thermal nanoimprint method using aromatic polymer is effective, but after the process, the coating material to which the pattern is transferred is heated and plastically deformed, then the mold is pressed, cooled, and the coating film Since the pattern was transferred by curing the material, there was a problem in productivity. From the viewpoint of productivity, photocurable compositions containing a polymerizable monomer or resin having an aryl substituent and an alicyclic compound have been proposed (see Patent Documents 2 to 4). However, in order to improve chlorine etching resistance, it is considered effective to include a monomer having a rigid skeleton such as a polymerizable monomer having an aryl substituent or a resin and an alicyclic compound. In addition, there was room for improvement in terms of adhesion to the sapphire substrate and transferability of the nanoimprint pattern at low pressure because of increased viscosity. In order to solve these problems, the present inventors incorporated a certain amount of water and hydrolyzed the organosilicon compound having a specific structure, a (meth) acrylic group-containing silicon compound, and a metal alkoxide moiety. The composition for photocurable nanoimprint containing a hydrolyzate was proposed (refer patent document 5).

JP 2008-19292 A JP 2009-218550 A JP 2011-157482 A JP 2008-246876 A JP 2012-109551 A

However, according to the study by the present inventors, the photocurable nanoimprint composition described in Patent Document 5 is a highly dispersible composition, excellent in productivity and substrate adhesion, and oxygen gas or fluorine-based gas. However, there is room for improvement in terms of etching resistance to chlorine-based gas and long-term storage stability.
The object of the present invention is to maintain the characteristics as a nanoimprinting composition such as pattern transferability and adhesion between the pattern and the substrate to such an extent that there is no practical problem, while maintaining etching resistance of chlorine-based gas and long-term storage. The object is to provide a photocurable nanoimprint composition having excellent stability.

  The present inventor has made various studies in order to improve the long-term storage stability of the photocurable nanoimprinting composition, which has excellent etching resistance to chlorine gas. As a result, it has been found that the etching resistance to chlorine-based gas is improved by blending a specific metal alkoxide of a type different from that of Patent Document 5.

  On the other hand, when a polymerizable monomer having a (meth) acryl group and a specific metal alkoxide are blended, in a short time, a precipitate or gelled product that is considered to be derived from a hydrolyzate of the metal alkoxide is generated, However, even when stored for a long time, there was a problem that the precipitate / gelatin increased or discolored over time. If a precipitate is generated, it will be used after filtration. Therefore, the etching resistance to chlorine gas deteriorates due to a substantial decrease in metal alkoxide concentration at the time of use, and it remains without being filtered. There is a problem of deterioration of substrate adhesion and transferability due to components. The present inventors have also studied various means for suppressing such precipitates, gelled products, and discoloration. As a result, the combined use of specific metal alkoxides and β-hydroxy ketones suppresses the formation and discoloration of gelated products and precipitates derived from metal alkoxides, and ensures that both chlorine etching resistance and long-term storage stability are compatible. The headline and the present invention were completed.

That is, the present invention
(A) a polymerizable monomer having a (meth) acryl group,
(B) The following formula (1)

(Where
M is tungsten, tin, indium, antimony, molybdenum, niobium, or hafnium;
R ¹ is an alkyl group having 1 to 10 carbon atoms, and may be the same group or different groups,
When M is tungsten, p is 6 or 5;
When M is molybdenum or niobium, p is 5,
When M is tin or hafnium, p is 4,
When M is indium or antimony, p is 3. )
A metal alkoxide represented by
A photocurable nanoimprinting composition containing (C) β-hydroxy ketones and (D) a photopolymerization initiator.

The second invention is
Applying the photocurable nanoimprint composition onto a substrate and then drying to form a coating film comprising the composition;
Contacting the pattern forming surface of the mold on which the pattern is formed with the coating film, and irradiating light in that state to cure the coating film;
Separating the mold from the cured coating film, and forming a pattern corresponding to the pattern formed on the pattern forming surface of the mold on the substrate. is there.

The third invention is
A method of manufacturing a surface-processed sapphire substrate, wherein the substrate is a sapphire substrate, and the substrate surface is processed by dry etching with a chlorine-based gas using the pattern formed on the substrate by the pattern formation method as a mask. is there.

  In the present invention, the (meth) acryl group means a methacryl group or an acryl group.

  The photocurable nanoimprint composition of the present invention is a chlorine-based gas etching while maintaining the characteristics of the nanoimprint composition such as pattern transferability and adhesion between the pattern and the substrate to such an extent that there is no practical problem. It is a composition excellent in resistance and long-term storage stability.

The present invention relates to a photocurable nanoimprint composition,
(A) a polymerizable monomer having a (meth) acryl group,
(B) The following formula (1)

(Where
M is tungsten, tin, indium, antimony, molybdenum, niobium, or hafnium;
R ¹ is an alkyl group having 1 to 10 carbon atoms, and may be the same group or different groups,
When M is tungsten, p is 6 or 5;
When M is molybdenum or niobium, p is 5,
When M is tin or hafnium, p is 4,
When M is indium or antimony, p is 3. )
A metal alkoxide represented by
(C) β-hydroxy ketones and (D) a photopolymerization initiator are included.

  In the present invention, nanoimprint refers to a pattern that can favorably form a pattern of 5 nm to 100 μm, and a fine pattern of 5 nm to 500 nm. However, as a matter of course, the photocurable nanoimprinting composition of the present invention can be used to form a pattern exceeding 100 μm.

In the following, description will be given in order. First, the polymerizable monomer (A) having a (meth) acryl group will be described.
(Polymerizable monomer having (meth) acrylic group (A))
In the present invention, the polymerizable monomer (A) having a (meth) acryl group (hereinafter also simply referred to as “polymerizable monomer (A)”) is not particularly limited, and is used for photopolymerization. A known polymerizable monomer having a (meth) acryl group can be used. In addition, in the composition for photocurable nanoimprint of the present invention, in addition to the polymerizable monomer (A) having a (meth) acryl group, other than the (meth) acryl group, as long as the effects of the present invention are not impaired. A polymerizable monomer having a polymerizable functional group may be included. This polymerizable monomer (A) does not contain an organosilicon compound (E) having a (meth) acryl group described later. A preferable compound includes a polymerizable monomer having a (meth) acryl group and containing no silicon atom in the molecule. These polymerizable monomers (A) may be monofunctional polymerizable monomers having one (meth) acrylic group in one molecule, or two or more (meth) acrylic in one molecule. It may be a polyfunctional polymerizable monomer having a group. Furthermore, these monofunctional polymerizable monomers and polyfunctional polymerizable monomers can also be used in combination.

  If the example of a polymerizable monomer (A) is specifically illustrated, as a monofunctional polymerizable monomer which has one (meth) acryl group in 1 molecule, for example, methyl (meth) acrylate, ethyl (Meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, isoamyl (meth) ) Acrylate, isomyristyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, long chain alkyl (meth) acrylate, n-butoxyethyl (meth) acrylate, Butoxydiethylene glycol (meth) Chrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, 2-ethylhexyl-diglycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) Acrylate, dicyclopentanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, hydroxyethyl (meth) acrylamide, 2- (2- Vinyloxyethoxy) ethyl (meth) acrylate, glycidyl (meth) acrylate, methoxyethylene glycol modified (meth) acrylate, ethoxyethylene glycol modified (meth) acrylate Relate, propoxyethylene glycol modified (meth) acrylate, methoxypropylene glycol modified (meth) acrylate, ethoxypropylene glycol modified (meth) acrylate, propoxypropylene glycol modified (meth) acrylate, isobornyl (meth) acrylate, adamantane (meth) acrylate derivative Aliphatic acrylates such as acryloylmorpholine; benzyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethylene glycol modified (meth) acrylate, phenoxypropylene glycol modified (meth) acrylate, hydroxyphenoxyethyl (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate Hydro phenolate Kishikishi ethylene glycol-modified (meth) acrylate, hydroxyphenoxy propylene glycol-modified (meth) acrylate, alkyl phenol ethylene glycol-modified (meth) acrylate, alkyl phenol propylene glycol-modified (meth) acrylate, the following formula (4)

(Where
R ¹⁰ is a hydrogen atom or a methyl group,
R ¹¹ is an alkylene group having 1 to 10 carbon atoms or a hydroxyalkylene group having 1 to 10 carbon atoms, and q is an integer of 1 to 6. And (meth) acrylate having an aromatic ring such as a monomer having an o-phenylphenol group in the molecule.

  As a polyfunctional polymerizable monomer (bifunctional polymerizable monomer) having two (meth) acryl groups in one molecule, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Polyolefin glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-hydroxy-1,3-dimethacryloxypropane, dioxane glycol di (meth) acrylate , Tricyclodecane dimethanol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, glycerin di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (Meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, butyl Aliphatic di (meth) acrylates such as ethylpropanediol di (meth) acrylate and 3-methyl-1,5-pentanediol di (meth) acrylate; ethoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A Di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, formula (5)

(Where
R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group,
R ¹⁴ and R ¹⁵ are an alkylene group having 1 to 10 carbon atoms, a hydroxyalkylene group having 1 to 10 carbon atoms, or a group represented by the following formula (6). Also good. )

(In the formula, R ¹⁶ and R ¹⁷ are an ethylene group or a propylene group, and n is an integer of 1 to 3.)
And di (meth) acrylate having an aromatic ring such as di (meth) acrylate having a fluorene structure represented by

  Furthermore, in this polyfunctional polymerizable monomer, as the polymerizable monomer having three or more (meth) acrylate groups in one molecule, ethoxylated glycerin tri (meth) acrylate, trimethylolpropane tri (meta) ) Acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, Examples include ethoxylated pentaerythritol tetra (meth) acrylate and dipentaerythritol polyacrylate.

  Among the polymerizable monomers (A), it is preferable to include a polymerizable monomer having an aromatic ring from the viewpoint that the etching resistance of chlorine-based gas can be improved. , A monomer having a fluorene structure in the molecule, a (meth) acrylate having an o-phenylphenol group in the molecule represented by the formula (4), and a fluorene represented by the formula (5) Examples thereof include di (meth) acrylate having a structure.

  In addition, the polymerizable monomer (A) may be used alone or in combination of a plurality of types depending on the intended use and the shape of the pattern to be formed.

  The (meth) acrylate having an o-phenylphenol group in the molecule represented by the formula (4) will be described.

  Following formula (4)

(Where
R ¹⁰ is a hydrogen atom or a methyl group,
R ¹¹ is an alkylene group having 1 to 10 carbon atoms or a hydroxyalkylene group having 1 to 10 carbon atoms, and q is an integer of 1 to 6. )
In the formula, R ¹⁰ is a hydrogen atom or a methyl group. Among these, a hydrogen atom is preferable because the photocuring speed when curing the photocurable nanoimprinting composition is high.
R ¹¹ is an alkylene group having 1 to 10 carbon atoms or a hydroxyalkylene group having 1 to 10 carbon atoms. Specifically, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, 2,2-dimethylpropylene group, 2-methylbutylene group, 2- Methyl-2-butylene group, 3-methylbutylene group, 3-methyl-2-butylene group, pentylene group, 2-pentylene group, 3-pentylene group, 3-dimethyl-2-butylene group, 3,3-dimethylbutylene Group, 3,3-dimethyl-2-butylene group, 2-ethylbutylene group, hexylene group, 2-hexylene group, 3-hexylene group, 2-methylpentylene group, 2-methyl-2-pentylene group, 2- Methyl-3-pentylene group, 3-methylpentylene group, 3-methyl-2-pentylene group, 3-methyl-3-pentylene group, 4-methylpentylene Group, 4-methyl-2-pentylene group, 2,2-dimethyl-3-pentylene group, 2,3-dimethyl-3-pentylene group, 2,4-dimethyl-3-pentylene group, 4,4-dimethyl 2-pentylene group, 3-ethyl-3-pentylene group, heptylene group, 2-heptylene group, 3-heptylene group, 2-methyl-2-hexylene group, 2-methyl-3-hexylene group, 5-methylhexene Xylene group, 5-methyl-2-hexylene group, 2-ethylhexylene group, 6-methyl-2-heptylene group, 4-methyl-3-heptylene group, octylene group, 2-octylene group, 3-octylene group, Alkylene groups such as 2-propylpentylene group and 2,4,4-trimethylpentylene group; 1-hydroxyethylene group, 2-hydroxyethylene group, 1-hydroxypropylene group 2-hydroxypropylene group, 3-hydroxypropylene group, 1-hydroxyisopropylene group, 2-hydroxyisopropylene group, 3-hydroxyisopropylene group, 1-hydroxybutylene group, 2-hydroxybutylene group, 3-hydroxybutylene group 4-hydroxybutylene group, 1-hydroxyisobutylene group, 2-hydroxyisobutylene group, 3-hydroxyisobutylene group, 1-hydroxysec-butylene group, 2-hydroxysec-butylene group, 3-hydroxysec-butylene group, 4 -Hydroxy sec-butylene group, 1-hydroxy-2,2-dimethylpropylene group, 3-hydroxy-2,2-dimethylpropylene group, 1-hydroxy-2-methylbutylene group, 2-hydroxy-2-methylbutylene group , 3-hydroxy- 2-methylbutylene group, 4-hydroxy-2-methylbutylene group, 1-hydroxy-2-methyl-2-butylene group, 3-hydroxy-2-methyl-2-butylene group, 4-hydroxy-2-methyl-2-butylene Group, 1-hydroxy-3-methylbutylene group, 2-hydroxy-3-methylbutylene group, 3-hydroxy-3-methylbutylene group, 4-hydroxy-3-methylbutylene group, 1-hydroxy-3-methyl- 2-butylene group, 2-hydroxy-3-methyl-2-butylene group, 3-hydroxy-3-methyl-2-butylene group, 4-hydroxy-3-methyl-2-butylene group, 1-hydroxypentylene group 2-hydroxypentylene group, 3-hydroxypentylene group, 4-hydroxypentylene group, 5-hydroxypentylene group, 1-hydroxy 2-pentylene group, 2-hydroxy-2-pentylene group, 3-hydroxy-2-pentylene group, 4-hydroxy-2-pentylene group, 5-hydroxy-2-pentylene group, 1-hydroxy-3-pentylene group 2-hydroxy-3-pentylene group, 3-hydroxy-3-pentylene group, 4-hydroxy-3-pentylene group, 5-hydroxy-3-pentylene group, 1-hydroxy-3-dimethyl-2-butylene group, 2-hydroxy-3-dimethyl-2-butylene group, 3-hydroxy-3-dimethyl-2-butylene group, 4-hydroxy-3-dimethyl-2-butylene group, 1-hydroxy-3,3-dimethylbutylene group 2-hydroxy-3,3-dimethylbutylene group, 4-hydroxy-3,3-dimethylbutylene group, 1-hydroxy-3,3 Dimethyl-2-butylene group, 2-hydroxy-3,3-dimethyl-2-butylene group, 4-hydroxy-3,3-dimethyl-2-butylene group, 1-hydroxy-2-ethylbutylene group, 2-hydroxy 2-ethylbutylene group, 3-hydroxy-2-ethylbutylene group, 4-hydroxy-2-ethylbutylene group, 1-hydroxy-hexylene group, 2-hydroxy-hexylene group, 3-hydroxy-hexylene group, 4- Hydroxy-hexylene group, 5-hydroxy-hexylene group, 6-hydroxy-hexylene group, 1-hydroxy-2-hexylene group, 2-hydroxy-2-hexylene group, 3-hydroxy-2-hexylene group, 4-hydroxy- 2-hexylene group, 5-hydroxy-2-hexylene group, 6-hydroxy-2-hexylene group, 1- Hydroxy-3-hexylene group, 2-hydroxy-3-hexylene group, 3-hydroxy-3-hexylene group, 4-hydroxy-3-hexylene group, 5-hydroxy-3-hexylene group, 6-hydroxy-3-hexylene Group, 1-hydroxy-2-methylpentylene group, 2-hydroxy-2-methylpentylene group, 3-hydroxy-2-methylpentylene group, 4-hydroxy-2-methylpentylene group, 5-hydroxy- 2-methylpentylene group, 1-hydroxy-2-methyl-2-pentylene group, 2-hydroxy-2-methyl-2-pentylene group, 3-hydroxy-2-methyl-2-pentylene group, 4-hydroxy- 2-methyl-2-pentylene group, 5-hydroxy-2-methyl-2-pentylene group, 1-hydroxy-2-methyl-3-pen Len group, 2-hydroxy-2-methyl-3-pentylene group, 3-hydroxy-2-methyl-3-pentylene group, 4-hydroxy-2-methyl-3-pentylene group, 5-hydroxy-2-methyl- 3-pentylene group, 1-hydroxy-3-methylpentylene group, 2-hydroxy-3-methylpentylene group, 3-hydroxy-3-methylpentylene group, 4-hydroxy-3-methylpentylene group, 5 -Hydroxy-3-methylpentylene group, 1-hydroxy-3-methyl-2-pentylene group, 2-hydroxy-3-methyl-2-pentylene group, 3-hydroxy-3-methyl-2-pentylene group, 4 -Hydroxy-3-methyl-2-pentylene group, 5-hydroxy-3-methyl-2-pentylene group, 1-hydroxy-3-methyl-3-pentylene 2-hydroxy-3-methyl-3-pentylene group, 3-hydroxy-3-methyl-3-pentylene group, 4-hydroxy-3-methyl-3-pentylene group, 5-hydroxy-3-methyl-3- Pentylene group, 1-hydroxy-4-methylpentylene group, 2-hydroxy-4-methylpentylene group, 3-hydroxy-4-methylpentylene group, 4-hydroxy-4-methylpentylene group, 5-hydroxy -4-methylpentylene group, 1-hydroxy-4-methyl-2-pentylene group, 2-hydroxy-4-methyl-2-pentylene group, 3-hydroxy-4-methyl-2-pentylene group, 4-hydroxy -4-methyl-2-pentylene group, 5-hydroxy-4-methyl-2-pentylene group, 1-hydroxy-2,2-dimethyl-3-pentylene group 3-hydroxy-2,2-dimethyl-3-pentylene group, 4-hydroxy-2,2-dimethyl-3-pentylene group, 5-hydroxy-2,2-dimethyl-3-pentylene group, 1-hydroxy- 2,3-dimethyl-3-pentylene group, 2-hydroxy-2,3-dimethyl-3-pentylene group, 4-hydroxy-2,3-dimethyl-3-pentylene group, 5-hydroxy-2,3-dimethyl -3-pentylene group, 1-hydroxy-2,4-dimethyl-3-pentylene group, 2-hydroxy-2,4-dimethyl-3-pentylene group, 3-hydroxy-2,4-dimethyl-3-pentylene group 4-hydroxy-2,4-dimethyl-3-pentylene group, 5-hydroxy-2,4-dimethyl-3-pentylene group, 1-hydroxy-4,4-dimethyl-2-pe Tylene group, 2-hydroxy-4,4-dimethyl-2-pentylene group, 3-hydroxy-4,4-dimethyl-2-pentylene group, 5-hydroxy-4,4-dimethyl-2-pentylene group, 1- Hydroxy-3-ethyl-3-pentylene group, 2-hydroxy-3-ethyl-3-pentylene group, 4-hydroxy-3-ethyl-3-pentylene group, 5-hydroxy-3-ethyl-3-pentylene group, 1-hydroxyheptylene group, 2-hydroxyheptylene group, 3-hydroxyheptylene group, 4-hydroxyheptylene group, 5-hydroxyheptylene group, 6-hydroxyheptylene group, 7- Hydroxyheptylene group, 1-hydroxy-2-heptylene group, 2-hydroxy-2-heptylene group, 3-hydroxy-2-heptylene group, 4-hydroxy- -Heptylene group, 5-hydroxy-2-heptylene group, 6-hydroxy-2-heptylene group, 7-hydroxy-2-heptylene group, 1-hydroxy-3-heptylene group, 2-hydroxy-3-heptylene group, 3 -Hydroxy-3-heptylene group, 4-hydroxy-3-heptylene group, 5-hydroxy-3-heptylene group, 6-hydroxy-3-heptylene group, 7-hydroxy-3-heptylene group, 1-hydroxy-2- Methyl-2-hexylene group, 3-hydroxy-2-methyl-2-hexylene group, 4-hydroxy-2-methyl-2-hexylene group, 5-hydroxy-2-methyl-2-hexylene group, 6-hydroxy- 2-methyl-2-hexylene group, 1-hydroxy-2-methyl-3-hexylene group, 2-hydroxy-2-methyl-3-he Xylene group, 3-hydroxy-2-methyl-3-hexylene group, 4-hydroxy-2-methyl-3-hexylene group, 5-hydroxy-2-methyl-3-hexylene group, 6-hydroxy-2-methyl- 3-hexylene group, 1-hydroxy-5-methylhexylene group, 2-hydroxy-5-methylhexylene group, 3-hydroxy-5-methylhexylene group, 4-hydroxy-5-methylhexylene group, 5 -Hydroxy-5-methylhexylene group, 6-hydroxy-5-methylhexylene group, 1-hydroxy-5-methyl-2-hexylene group, 2-hydroxy-5-methyl-2-hexylene group, 3-hydroxy -5-methyl-2-hexylene group, 4-hydroxy-5-methyl-2-hexylene group, 5-hydroxy-5-methyl-2-hexylene group, -Hydroxy-5-methyl-2-hexylene group, 1-hydroxy-2-ethylhexylene group, 2-hydroxy-2-ethylhexylene group, 3-hydroxy-2-ethylhexylene group, 4-hydroxy-2 -Ethylhexylene group, 5-hydroxy-2-ethylhexylene group, 6-hydroxy-2-ethylhexylene group, 1-hydroxy-6-methyl-2-heptylene group, 2-hydroxy-6-methyl-2 -Heptylene group, 3-hydroxy-6-methyl-2-heptylene group, 4-hydroxy-6-methyl-2-heptylene group, 5-hydroxy-6-methyl-2-heptylene group, 6-hydroxy-6-methyl 2-heptylene group, 7-hydroxy-6-methyl-2-heptylene group, 1-hydroxy-4-methyl-3-heptylene group, 2-hydroxyl -4-methyl-3-heptylene group, 3-hydroxy-4-methyl-3-heptylene group, 4-hydroxy-4-methyl-3-heptylene group, 5-hydroxy-4-methyl-3-heptylene group, 6 -Hydroxy-4-methyl-3-heptylene group, 1-hydroxyoctylene group, 2-hydroxyoctylene group, 3-hydroxyoctylene group, 4-hydroxyoctylene group, 5-hydroxyoctylene group, 6-hydroxy Octylene group, 7-hydroxyoctylene group, 8-hydroxyoctylene group, 1-hydroxy-2-octylene group, 2-hydroxy-2-octylene group, 3-hydroxy-2-octylene group, 4-hydroxy-2 -Octylene group, 5-hydroxy-2-octylene group, 6-hydroxy-2-octylene group, 7-hydroxy-2-o Cutylene group, 8-hydroxy-2-octylene group, 1-hydroxy-3-octylene group, 2-hydroxy-3-octylene group, 3-hydroxy-3-octylene group, 4-hydroxy-3-octylene group, 5- Hydroxy-3-octylene group, 6-hydroxy-3-octylene group, 7-hydroxy-3-octylene group, 8-hydroxy-3-octylene group, 1-hydroxy-2-propylpentylene group, 2-hydroxy-2 -Propylpentylene group, 3-hydroxy-2-propylpentylene group, 4-hydroxy-2-propylpentylene group, 5-hydroxy-2-propylpentylene group, 1-hydroxy-2,4,4-trimethyl Pentylene group, 2-hydroxy-2,4,4-trimethylpentylene group, 3-hydroxy-2,4,4-trime Rupenchiren groups include hydroxy alkylene groups such as 5-hydroxy-2,4,4-trimethyl pentylene group.

  Among these, an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group, an isopropylene group, and a butylene group, or a 1-hydroxymethylene group, a 2-hydroxymethylene group, a 1-hydroxypropylene group, 2- Hydroxypropylene group, 3-hydroxypropylene group, 1-hydroxyisopropylene group, 2-hydroxyisopropylene group, 3-hydroxyisopropylene group, 1-hydroxybutylene group, 2-hydroxybutylene group, 3-hydroxybutylene group, 4 A hydroxyalkylene group having 1 to 4 carbon atoms such as a hydroxybutylene group is preferred.

  Examples of the (meth) acrylate having a ο-phenylphenol group in the molecule represented by the formula (4) include, for example, 3-ο-phenylphenolmethyl (meth) acrylate, 3-ο-phenylphenolethyl (meth) acrylate, 3 -Ο-phenylphenol propyl (meth) acrylate, 3-ο-phenylphenol butyl (meth) acrylate, 3-ο-phenylphenol diethoxy (meth) acrylate, 3-ο-phenylphenol triethoxy (meth) acrylate, 3 -Ο-phenylphenol tetraethoxy (meth) acrylate, 2-hydroxy-3-ο-phenylphenolpropyl (meth) acrylate, 2-hydroxy-3-ο-phenylphenolbutyl (meth) acrylate, 3-hydroxy-3- ο-Phenylpheno And rupropyl (meth) acrylate.

  The di (meth) acrylate having a fluorene structure in the molecule represented by the formula (5) will be described.

  Following formula (5)

(Where
R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group,
R ¹⁴ and R ¹⁵ are an alkylene group having 1 to 10 carbon atoms, a hydroxyalkylene group having 1 to 10 carbon atoms, or a group represented by the following formula (6). Also good. )

(In the formula, R ¹⁶ and R ¹⁷ are an ethylene group or a propylene group, and n is an integer of 1 to 3.)
In these, R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group. Among these, a hydrogen atom is preferable because the photocuring speed when curing the photocurable nanoimprinting composition is high.

R ¹⁴ and R ¹⁵ are an alkylene group having 1 to 10 carbon atoms, a hydroxyalkylene group having 1 to 10 carbon atoms, or a group represented by the formula (6). Specifically, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, 2,2-dimethylpropylene group, 2-methylbutylene group, 2- Methyl-2-butylene group, 3-methylbutylene group, 3-methyl-2-butylene group, pentylene group, 2-pentylene group, 3-pentylene group, 3-dimethyl-2-butylene group, 3,3-dimethylbutylene Group, 3,3-dimethyl-2-butylene group, 2-ethylbutylene group, hexylene group, 2-hexylene group, 3-hexylene group, 2-methylpentylene group, 2-methyl-2-pentylene group, 2- Methyl-3-pentylene group, 3-methylpentylene group, 3-methyl-2-pentylene group, 3-methyl-3-pentylene group, 4-methylpentylene Group, 4-methyl-2-pentylene group, 2,2-dimethyl-3-pentylene group, 2,3-dimethyl-3-pentylene group, 2,4-dimethyl-3-pentylene group, 4,4-dimethyl 2-pentylene group, 3-ethyl-3-pentylene group, heptylene group, 2-heptylene group, 3-heptylene group, 2-methyl-2-hexylene group, 2-methyl-3-hexylene group, 5-methylhexene Xylene group, 5-methyl-2-hexylene group, 2-ethylhexylene group, 6-methyl-2-heptylene group, 4-methyl-3-heptylene group, octylene group, 2-octylene group, 3-octylene group, Alkylene groups such as 2-propylpentylene, 2,4,4-trimethylpentylene; trimethylene, tetramethylene, pentamethylene, hexamethylene, heptam Polymethylene groups such as len group, octamethylene group, nonamethylene group, decamethylene group, 1-hydroxyethylene group, 2-hydroxyethylene group, 1-hydroxypropylene group, 2-hydroxypropylene group, 3-hydroxypropylene group, 1-hydroxy Isopropylene group, 2-hydroxyisopropylene group, 3-hydroxyisopropylene group, 1-hydroxybutylene group, 2-hydroxybutylene group, 3-hydroxybutylene group, 4-hydroxybutylene group, 1-hydroxyisobutylene group, 2- Hydroxyisobutylene group, 3-hydroxyisobutylene group, 1-hydroxysec-butylene group, 2-hydroxysec-butylene group, 3-hydroxysec-butylene group, 4-hydroxysec-butylene group, 1-hydroxy-2,2- Jime Tylpropylene group, 3-hydroxy-2,2-dimethylpropylene group, 1-hydroxy-2-methylbutylene group, 2-hydroxy-2-methylbutylene group, 3-hydroxy-2-methylbutylene group, 4-hydroxy- 2-methylbutylene group, 1-hydroxy 2-methyl-2-butylene group, 3-hydroxy 2-methyl-2-butylene group, 4-hydroxy 2-methyl-2-butylene group, 1-hydroxy-3-methylbutylene Group, 2-hydroxy-3-methylbutylene group, 3-hydroxy-3-methylbutylene group, 4-hydroxy-3-methylbutylene group, 1-hydroxy-3-methyl-2-butylene group, 2-hydroxy-3 -Methyl-2-butylene group, 3-hydroxy-3-methyl-2-butylene group, 4-hydroxy-3-methyl-2-butylene 1-hydroxypentylene group, 2-hydroxypentylene group, 3-hydroxypentylene group, 4-hydroxypentylene group, 5-hydroxypentylene group, 1-hydroxy-2-pentylene group, 2-hydroxy-2 -Pentylene group, 3-hydroxy-2-pentylene group, 4-hydroxy-2-pentylene group, 5-hydroxy-2-pentylene group, 1-hydroxy-3-pentylene group, 2-hydroxy-3-pentylene group, 3 -Hydroxy-3-pentylene group, 4-hydroxy-3-pentylene group, 5-hydroxy-3-pentylene group, 1-hydroxy-3-dimethyl-2-butylene group, 2-hydroxy-3-dimethyl-2-butylene Group, 3-hydroxy-3-dimethyl-2-butylene group, 4-hydroxy-3-dimethyl-2-butylene group 1-hydroxy-3,3-dimethylbutylene group, 2-hydroxy-3,3-dimethylbutylene group, 4-hydroxy-3,3-dimethylbutylene group, 1-hydroxy-3,3-dimethyl-2-butylene group 2-hydroxy-3,3-dimethyl-2-butylene group, 4-hydroxy-3,3-dimethyl-2-butylene group, 1-hydroxy-2-ethylbutylene group, 2-hydroxy-2-ethylbutylene group 3-hydroxy-2-ethylbutylene group, 4-hydroxy-2-ethylbutylene group, 1-hydroxy-hexylene group, 2-hydroxy-hexylene group, 3-hydroxy-hexylene group, 4-hydroxy-hexylene group, 5 -Hydroxy-hexylene group, 6-hydroxy-hexylene group, 1-hydroxy-2-hexylene group, 2-hydroxy-2 -Hexylene group, 3-hydroxy-2-hexylene group, 4-hydroxy-2-hexylene group, 5-hydroxy-2-hexylene group, 6-hydroxy-2-hexylene group, 1-hydroxy-3-hexylene group, 2 -Hydroxy-3-hexylene group, 3-hydroxy-3-hexylene group, 4-hydroxy-3-hexylene group, 5-hydroxy-3-hexylene group, 6-hydroxy-3-hexylene group, 1-hydroxy-2- Methylpentylene group, 2-hydroxy-2-methylpentylene group, 3-hydroxy-2-methylpentylene group, 4-hydroxy-2-methylpentylene group, 5-hydroxy-2-methylpentylene group, 1 -Hydroxy-2-methyl-2-pentylene group, 2-hydroxy-2-methyl-2-pentylene group, 3-hydroxy-2 Methyl-2-pentylene group, 4-hydroxy-2-methyl-2-pentylene group, 5-hydroxy-2-methyl-2-pentylene group, 1-hydroxy-2-methyl-3-pentylene group, 2-hydroxy- 2-methyl-3-pentylene group, 3-hydroxy-2-methyl-3-pentylene group, 4-hydroxy-2-methyl-3-pentylene group, 5-hydroxy-2-methyl-3-pentylene group, 1- Hydroxy-3-methylpentylene group, 2-hydroxy-3-methylpentylene group, 3-hydroxy-3-methylpentylene group, 4-hydroxy-3-methylpentylene group, 5-hydroxy-3-methylpentylene Len group, 1-hydroxy-3-methyl-2-pentylene group, 2-hydroxy-3-methyl-2-pentylene group, 3-hydroxy-3-methyl 2-pentylene group, 4-hydroxy-3-methyl-2-pentylene group, 5-hydroxy-3-methyl-2-pentylene group, 1-hydroxy-3-methyl-3-pentylene group, 2-hydroxy-3 -Methyl-3-pentylene group, 3-hydroxy-3-methyl-3-pentylene group, 4-hydroxy-3-methyl-3-pentylene group, 5-hydroxy-3-methyl-3-pentylene group, 1-hydroxy -4-methylpentylene group, 2-hydroxy-4-methylpentylene group, 3-hydroxy-4-methylpentylene group, 4-hydroxy-4-methylpentylene group, 5-hydroxy-4-methylpentylene Group, 1-hydroxy-4-methyl-2-pentylene group, 2-hydroxy-4-methyl-2-pentylene group, 3-hydroxy-4-methyl-2- Pentylene group, 4-hydroxy-4-methyl-2-pentylene group, 5-hydroxy-4-methyl-2-pentylene group, 1-hydroxy-2,2-dimethyl-3-pentylene group, 3-hydroxy-2, 2-dimethyl-3-pentylene group, 4-hydroxy-2,2-dimethyl-3-pentylene group, 5-hydroxy-2,2-dimethyl-3-pentylene group, 1-hydroxy-2,3-dimethyl-3 -Pentylene group, 2-hydroxy-2,3-dimethyl-3-pentylene group, 4-hydroxy-2,3-dimethyl-3-pentylene group, 5-hydroxy-2,3-dimethyl-3-pentylene group, 1 -Hydroxy-2,4-dimethyl-3-pentylene group, 2-hydroxy-2,4-dimethyl-3-pentylene group, 3-hydroxy-2,4-dimethyl-3-pe Tylene group, 4-hydroxy-2,4-dimethyl-3-pentylene group, 5-hydroxy-2,4-dimethyl-3-pentylene group, 1-hydroxy-4,4-dimethyl-2-pentylene group, 2- Hydroxy-4,4-dimethyl-2-pentylene group, 3-hydroxy-4,4-dimethyl-2-pentylene group, 5-hydroxy-4,4-dimethyl-2-pentylene group, 1-hydroxy-3-ethyl -3-pentylene group, 2-hydroxy-3-ethyl-3-pentylene group, 4-hydroxy-3-ethyl-3-pentylene group, 5-hydroxy-3-ethyl-3-pentylene group, 1-hydroxyheptyl Len group, 2-hydroxyheptylene group, 3-hydroxyheptylene group, 4-hydroxyheptylene group, 5-hydroxyheptylene group, 6-hydroxyheptene group Len group, 7-hydroxyheptylene group, 1-hydroxy-2-heptylene group, 2-hydroxy-2-heptylene group, 3-hydroxy-2-heptylene group, 4-hydroxy-2-heptylene group, 5-hydroxy 2-heptylene group, 6-hydroxy-2-heptylene group, 7-hydroxy-2-heptylene group, 1-hydroxy-3-heptylene group, 2-hydroxy-3-heptylene group, 3-hydroxy-3-heptylene group 4-hydroxy-3-heptylene group, 5-hydroxy-3-heptylene group, 6-hydroxy-3-heptylene group, 7-hydroxy-3-heptylene group, 1-hydroxy-2-methyl-2-hexylene group, 3-hydroxy-2-methyl-2-hexylene group, 4-hydroxy-2-methyl-2-hexylene group, 5-hydroxy- 2-methyl-2-hexylene group, 6-hydroxy-2-methyl-2-hexylene group, 1-hydroxy-2-methyl-3-hexylene group, 2-hydroxy-2-methyl-3-hexylene group, 3- Hydroxy-2-methyl-3-hexylene group, 4-hydroxy-2-methyl-3-hexylene group, 5-hydroxy-2-methyl-3-hexylene group, 6-hydroxy-2-methyl-3-hexylene group, 1-hydroxy-5-methylhexylene group, 2-hydroxy-5-methylhexylene group, 3-hydroxy-5-methylhexylene group, 4-hydroxy-5-methylhexylene group, 5-hydroxy-5- Methylhexylene group, 6-hydroxy-5-methylhexylene group, 1-hydroxy-5-methyl-2-hexylene group, 2-hydroxy-5-methyl- -Hexylene group, 3-hydroxy-5-methyl-2-hexylene group, 4-hydroxy-5-methyl-2-hexylene group, 5-hydroxy-5-methyl-2-hexylene group, 6-hydroxy-5-methyl 2-hexylene group, 1-hydroxy-2-ethylhexylene group, 2-hydroxy-2-ethylhexylene group, 3-hydroxy-2-ethylhexylene group, 4-hydroxy-2-ethylhexylene group, 5-hydroxy-2-ethylhexylene group, 6-hydroxy-2-ethylhexylene group, 1-hydroxy-6-methyl-2-heptylene group, 2-hydroxy-6-methyl-2-heptylene group, 3- Hydroxy-6-methyl-2-heptylene group, 4-hydroxy-6-methyl-2-heptylene group, 5-hydroxy-6-methyl-2-heptylene group Group, 6-hydroxy-6-methyl-2-heptylene group, 7-hydroxy-6-methyl-2-heptylene group, 1-hydroxy-4-methyl-3-heptylene group, 2-hydroxy-4-methyl-3 -Heptylene group, 3-hydroxy-4-methyl-3-heptylene group, 4-hydroxy-4-methyl-3-heptylene group, 5-hydroxy-4-methyl-3-heptylene group, 6-hydroxy-4-methyl -3-heptylene group, 1-hydroxyoctylene group, 2-hydroxyoctylene group, 3-hydroxyoctylene group, 4-hydroxyoctylene group, 5-hydroxyoctylene group, 6-hydroxyoctylene group, 7- Hydroxyoctylene group, 8-hydroxyoctylene group, 1-hydroxy-2-octylene group, 2-hydroxy-2-octylene group, 3 -Hydroxy-2-octylene group, 4-hydroxy-2-octylene group, 5-hydroxy-2-octylene group, 6-hydroxy-2-octylene group, 7-hydroxy-2-octylene group, 8-hydroxy-2- Octylene group, 1-hydroxy-3-octylene group, 2-hydroxy-3-octylene group, 3-hydroxy-3-octylene group, 4-hydroxy-3-octylene group, 5-hydroxy-3-octylene group, 6- Hydroxy-3-octylene group, 7-hydroxy-3-octylene group, 8-hydroxy-3-octylene group, 1-hydroxy-2-propylpentylene group, 2-hydroxy-2-propylpentylene group, 3-hydroxy 2-propylpentylene group, 4-hydroxy-2-propylpentylene group, 5-hydroxy-2-pro Rupentylene group, 1-hydroxy-2,4,4-trimethylpentylene group, 2-hydroxy-2,4,4-trimethylpentylene group, 3-hydroxy-2,4,4-trimethylpentylene group, 5- Examples include hydroxyalkylene groups such as hydroxy-2,4,4-trimethylpentylene group.

Among these, an alkylene group having 1 to 4 carbon atoms such as methylene group, ethylene group, propylene group, isopropylene group, butylene group, 1-hydroxyethylene group, 2-hydroxyethylene group, 1-hydroxypropylene group, 2 -Hydroxypropylene group, 3-hydroxypropylene group, 1-hydroxyisopropylene group, 2-hydroxyisopropylene group, 3-hydroxyisopropylene group, 1-hydroxybutylene group, 2-hydroxybutylene group, 3-hydroxybutylene group, A hydroxyalkylene group having 1 to 4 carbon atoms such as 4-hydroxybutylene group and 1-hydroxyisobutylene group, or a group of formula (6), wherein R ¹⁶ and R ¹⁷ are ethylene groups, and n is 1 to 2 or R ¹⁶ and R ¹⁷ are propylene groups, and n is preferably 1 or 2 groups. Good.

Examples of the di (meth) acrylate having a fluorene structure in the molecule represented by the formula (5) include 9,9-bis [4- (2- (meth) acryloyloxymethoxy) phenyl] fluorene, 9,9-bis. [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxypropyloxy) phenyl] fluorene, 9,9-bis [4- (2 -(Meth) acryloyloxyisopropyloxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxybutyloxy) phenyl] fluorene, 9,9-bis [4- (2- (meth)) Acryloyloxyhydroxyethylethoxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxy) Roxypropyloxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxyhydroxyisopropyloxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxyhydroxybutyl) Oxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxyethyleneglycoxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxypropyleneglycoxy) Phenyl] fluorene and the like.
(Metal alkoxide (B))
In the present invention, the following formula (1)

(Where
M is tungsten, tin, indium, antimony, molybdenum, niobium, or hafnium;
R ¹ is an alkyl group having 1 to 10 carbon atoms, and may be the same group or different groups,
When M is tungsten, p is 6 or 5;
When M is molybdenum or niobium, p is 5,
When M is tin or hafnium, p is 4,
When M is indium or antimony, p is 3. )
The metal alkoxide shown below (hereinafter also simply referred to as “metal alkoxide”) is used. The metal alkoxide may be used alone or a mixture of the metal alkoxides.

  By using the metal alkoxide, etching resistance to chlorine-based gas, oxygen-based gas, fluorine-based gas and the like is improved, and a cured film having particularly excellent etching resistance to chlorine-based gas can be formed. And the etching rate of chlorine gas can also be adjusted with the usage-amount of a metal alkoxide.

  In the above formula (1), M is preferably tungsten in order to further improve the etching resistance against chlorine gas.

  Further, tungsten oxide alkoxides such as tungsten oxide alkoxide (IV) may be included within a range not impairing the effects of the present invention.

  In the present invention, water is not actively added as a method for producing a photocurable nanoimprinting composition, but (B) a metal alkoxide and water described later (E ) (Meth) acrylic group-containing organosilicon compound, (F) a mixture of the hydrolyzate obtained by hydrolyzing a part of the alkoxy group of the organosilicon compound, and a polycondensate of the hydrolysates of the present invention. You may include in the range which does not injure an effect.

The metal alkoxide of the formula (1) may generate an alcohol by reaction with water or water contained in a solvent or a β-hydroxyketone described later, but can be easily mixed with other components. In particular, R ¹ is a methyl group, an ethyl group, or a propyl group. And an alkyl group having 1 to 4 carbon atoms such as isopropyl group and butyl group.

Examples of suitable metal alkoxides include hexamethyl tungsten alkoxide, hexaethyl tungsten alkoxide, hexaisopropyl tungsten alkoxide, hexapropyl tungsten alkoxide, hexaisobutyl tungsten alkoxide, hexabutyl tungsten alkoxide, hexapentyl tungsten alkoxide, hexahexyl tungsten alkoxide, hexa Heptyl tungsten alkoxide, hexaoctyl tungsten alkoxide, hexanonyl tungsten alkoxide, hexadecyl tungsten alkoxide, pentamethyl tungsten alkoxide, pentaethyl tungsten alkoxide, pentaisopropyl tungsten alkoxide, pentapropyl tungsten alkoxide Pentapentyl tungsten alkoxide, pentabutyl tungsten alkoxide, pentapentyl tungsten alkoxide, pentahexyl tungsten alkoxide, pentaheptyl tungsten alkoxide, pentaoctyl tungsten alkoxide, pentanonyl tungsten alkoxide, pentadecyl tungsten alkoxide; pentamethyl molybdenum alkoxide, pentaethyl molybdenum Alkoxide, pentaisopropyl molybdenum alkoxide, pentapropyl molybdenum alkoxide, pentaisobutyl molybdenum alkoxide, pentabutyl molybdenum alkoxide, pentapentyl molybdenum alkoxide, pentahexyl molybdenum alkoxide, pentaheptyl molybdenum alkoxide, Taoctyl molybdenum alkoxide, pentanonyl molybdenum alkoxide, pentadecyl molybdenum alkoxide; pentamethyl niobium alkoxide, pentaethyl niobium alkoxide, pentaisopropyl niobium alkoxide, pentapropyl niobium alkoxide, pentaisobutyl niobium alkoxide, pentabutyl niobium alkoxide, pentapentyl niobium alkoxide, Pentahexyl niobium alkoxide, pentaheptyl niobium alkoxide, pentaoctyl niobium alkoxide, pentanonyl niobium alkoxide, pentadecyl niobium alkoxide; tetramethyltin alkoxide, tetraethyltin alkoxide, tetraisopropyltin alkoxide, tetrapropyltin alkoxide, tetraisobutyltin alkoxide Sid, tetrabutyltin alkoxide, tetrapentyltin alkoxide, tetraheptyltin alkoxide, tetrahexyltin alkoxide, tetraheptyltin alkoxide, tetraoctyltin alkoxide, tetranonyltin alkoxide, tetradecyltin alkoxide; tetramethylhafnium alkoxide, tetraethylhafnium alkoxide , Tetraisopropyl hafnium alkoxide, tetrapropyl hafnium alkoxide, tetraisobutyl hafnium alkoxide, tetrabutyl hafnium alkoxide, tetrapentyl hafnium alkoxide, tetraheptyl hafnium alkoxide, tetrahexyl hafnium alkoxide, tetraheptyl hafnium alkoxide, tetraoctyl hafnium alkoxy , Tetranonyl hafnium alkoxide, tetradecyl hafnium alkoxide; trimethyl indium alkoxide, triethyl indium alkoxide, triisopropyl indium alkoxide, tripropyl indium alkoxide, triisobutyl indium alkoxide, tributyl indium alkoxide, tripentyl indium alkoxide, trihexyl indium alkoxide, triheptyl Indium alkoxide, trioctyl indium alkoxide, trinonyl indium alkoxide, tridecyl indium alkoxide; trimethylantimony alkoxide, triethylantimony alkoxide, triisopropylantimony alkoxide, tripropylantimony alkoxide, triisobutylan Mon alkoxides, tributyl antimony alkoxides, tripentyl antimony alkoxides, trihexyl antimony alkoxides, triheptyl antimony alkoxides, trioctyl antimony alkoxides, trinonylamine antimony alkoxides include tridecyl antimony alkoxides. Among these, pentaethyl tungsten alkoxide, pentaisopropyl tungsten alkoxide, pentapropyl tungsten alkoxide, pentaisobutyl tungsten alkoxide, and pentabutyl tungsten alkoxide are preferable.
(Β-hydroxy ketones (C))
In the present invention, by using a metal alkoxide and a β-hydroxyketone in combination, when a mixture of a polymerizable monomer having a meth) acrylic group is produced, the occurrence of precipitation that is thought to be derived from the hydrolysis of the metal alkoxide As a result, etching of chlorine-based gas while maintaining the characteristics of nanoimprinting compositions such as pattern transferability and adhesion between the pattern and the substrate to such a level that there is no practical problem. The composition for photocurable nanoimprinting of the present invention having improved resistance and excellent long-term storage stability can be obtained. When α-diketones having a structure similar to β-hydroxyketone are used, stability in a short time is good, but long-term storage stability has room for improvement. The short-term stability in the present specification means the stability within 7 days at 50 ° C. after adjusting the composition, and the long-term stability is 21 at 50 ° C. after adjusting the composition. Means long-term stability over a day.

When the metal alkoxide of the present invention is contained in a polymerizable monomer having a (meth) acryl group, a precipitate and a gelled product are formed in a short time, and the precipitate is described later in the composition (meth). This is particularly noticeable when there is no organosilicon compound or organosilicon compound having an acrylic group.
The β-hydroxy ketones used in the present invention mean a compound having a β-hydroxy ketone skeleton (O = CCC-OH), and among them, β-hydroxy ketones represented by the following formula (7) are preferable. It is.

(In the formula, R ¹⁸ is an optionally substituted alkyl group or an optionally substituted aryl group, and R ^{19 to} R ²² are hydrogen or an optionally substituted alkyl group or a substituted group. And may be the same or different groups.
The alkyl group which may be substituted in the formula (7) is preferably an alkyl group having 1 to 6 carbon atoms. Examples of the substituent include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a diethylene glycol group, a triethylene glycol group, a hydroxyl group, and a halogen. Among them, a methoxy group and an ethoxy group are preferable. The aryl group which may be substituted in the formula (7) is preferably an aryl group having 6 to 12 carbon atoms. Examples of the substituent include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a diethylene glycol group, a triethylene glycol group, a phenyl group, a hydroxyl group, and a halogen. Among them, a methoxy group and an ethoxy group are preferable.
The β-hydroxy ketones may be used alone or may be a mixture of the β-hydroxy ketones. Specific examples of β-hydroxyketones used in the present invention include, for example, 4-hydroxy-2-butanone, 4-hydroxy-5,5-dimethyl-2-hexanone, 3-methyl-4-hydroxy-2. -Butanone, 3,3'-dimethyl-4-hydroxy-2-butanone, 4-hydroxy-4-methyl-2-pentanone, 4-hydroxy-4-methyl-5-phenyl-2-pentanone, 3-hydroxy- 1,3-diphenyl-1-propanone, 3-hydroxy-1-phenyl-3- (4-methoxyphenyl) -1-propanone, 3-hydroxy-1- (3,4,5-trimethoxyphenyl) -3 -Phenyl-1-propanone, 3-hydroxy-1- (3,4-methylenedioxyphenyl) -3-phenyl-1-propanone, 3-hydroxy- -(4-Methylphenyl) -3-phenyl-1-propanone, 3-hydroxy-1- (3-methoxyphenyl) -3-phenyl-1-propanone, 4- (2-methylphenyl) -4-hydroxy- Examples include 2-butanone, 4-phenyl-4-hydroxy-3-methyl-2-butanone, 4- (4-fluorophenyl) -4-hydroxy-3-methyl-2-butanone, and the like. Among them, 4-hydroxy-2-butanone, 4-hydroxy-5,5-dimethyl-2-hexanone, 3-methyl-4-hydroxy-2-butanone, 3,3′-dimethyl-4-hydroxy-2- Butanone and 4-hydroxy-4-methyl-2-pentanone are preferred.

  The reason why the long-term storage stability is improved by blending β-hydroxy ketones is estimated as follows. That is, by replacing a part of the alkoxy group and performing chelate coordination, in addition to the effect of reducing the positive polarization of the central metal of the metal alkoxide, the OH group of β-hydroxy ketones is substituted or coordinated with the alkoxy group. It is presumed that the hydrolysis effect of the metal alkoxide was suppressed in the (meth) acrylic group-containing polymerizable monomer due to the increased induction effect.

(Organic silicon compound having (meth) acrylic group)
In the present invention, (E) the following formula (2)

(Where
R ² is a hydrogen atom or a methyl group,
R ³ is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or an alkylene ether having 2 to 20 carbon atoms,
R ⁴ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms,
R ⁵ is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 4 carbon atoms,
R3 or R4 may be substituted with an alkyl group, an aryl group, a halogen, or a hydroxyl group. l is an integer of 1 to 3, m is an integer of 0 to 2, k is an integer of 1 to 3,
l + m + k is 4,
R ^{2, R} 3, ^{R 4} and ^{R 5} are each, when there are a plurality, the plurality of ^{R 2,} R 3, ^{R 4} and ^{R 5} may each be the same or different groups. )
And an organosilicon compound having a (meth) acryl group (hereinafter also referred to simply as “organosilicon compound having a (meth) acryl group”).

  By using this organosilicon compound having a (meth) acrylic group, a photocurable nanoimprinting composition with good dispersibility can be obtained, which facilitates purification by filtration and improves productivity. Moreover, in the fine structure of the cured film obtained by photocuring, the inorganic component and the organic component are dispersed in a relatively homogeneous state (the dispersed state is not such that the inorganic component is extremely aggregated). Adhesion with the material is also improved. As a result, it is estimated that a uniform transfer pattern and a uniform residual film can be formed. In addition, the organosilicon compound having a (meth) acryl group is a precipitate that is considered to be derived from the metal alkoxide when coexisting with a metal alkoxide in a polymerizable monomer having a (meth) acryl group. Generation can be suppressed. This is presumed to be because the solubility of the reaction product by the hydrolysis reaction between the metal alkoxide and the organosilicon compound having a (meth) acrylic group in the (meth) acrylate polymerizable monomer is high.

In the formula (2), R ² is a hydrogen atom or a methyl group. Among these, a hydrogen atom is preferable because the photocuring speed when curing the photocurable nanoimprinting composition is high.

R ³ is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or an alkylene ether group having 2 to 20 carbon atoms. The alkylene ether group is represented by —R _X —O—R _Y — (R _X and R _Y represent an alkylene group), and refers to a group in which two alkylene groups are bonded to an oxygen atom. The carbon number of represents the total number of carbon atoms of the two alkylene groups. Specific examples of R ³ include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, 2,2-dimethylpropylene group, and 2-methylbutylene group. 2-methyl-2-butylene group, 3-methylbutylene group, 3-methyl-2-butylene group, pentylene group, 2-pentylene group, 3-pentylene group, 3-dimethyl-2-butylene group, 3, 3 -Dimethylbutylene group, 3,3-dimethyl-2-butylene group, 2-ethylbutylene group, hexylene group, 2-hexylene group, 3-hexylene group, 2-methylpentylene group, 2-methyl-2-pentylene group 2-methyl-3-pentylene group, 3-methylpentylene group, 3-methyl-2-pentylene group, 3-methyl-3-pentylene group, 4-methyl Tylpentylene group, 4-methyl-2-pentylene group, 2,2-dimethyl-3-pentylene group, 2,3-dimethyl-3-pentylene group, 2,4-dimethyl-3-pentylene group, 4,4-dimethyl 2-pentylene group, 3-ethyl-3-pentylene group, heptylene group, 2-heptylene group, 3-heptylene group, 2-methyl-2-hexylene group, 2-methyl-3-hexylene group, 5-methylhexene Xylene group, 5-methyl-2-hexylene group, 2-ethylhexylene group, 6-methyl-2-heptylene group, 4-methyl-3-heptylene group, octylene group, 2-octylene group, 3-octylene group, Alkylene groups such as 2-propylpentylene group, 2,4,4-trimethylpentylene group, decaoctylene group; cyclopropylene group, cyclobutylene group, cyclopropylene Cycloalkylene groups such as methylene group, cyclopentylylene group, cyclohexylene group, cyclooctylene group; dimethylene ether group, trimethylene ether group, diethylene ether group, triethylene ether group, dipropylene ether group, diisopropylene ether And alkylene ether groups such as a group, a dibutylene ether group and a dioctylene ether group.

  Among these, C1-C4 alkylene groups, such as a methylene group, ethylene group, propylene group, isopropylene group, butylene group, and C3-C4 cycloalkylene groups, such as a cyclopropylene group and a cyclobutylene group, are preferable. .

R ⁴ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group; cyclopropyl group, cyclobutyl group, cyclopropylmethyl group, etc. Cycloalkyl group; aryl groups such as phenyl group, benzyl group, 1-naphthyl group, 2-naphthyl group and o-methylnaphthyl group can be exemplified. Of these, a methyl group and an ethyl group are preferable.

R ⁵ is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 4 carbon atoms. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group; cyclopropyl group, cyclobutyl group, cyclopropylmethyl group, etc. A cycloalkyl group is mentioned.

The alkoxy group represented by —OR ⁵ generates an alcohol derived from R ⁵ upon hydrolysis, but the photocurable nanoimprinting composition of the present invention may contain this alcohol. Therefore, considering that it becomes an alcohol that can be easily mixed with other components, and that it becomes an alcohol that can be easily removed after forming a coating film on the substrate, specifically, R ⁵ represents a methyl group, an ethyl group, It is preferably an alkyl group having 1 to 4 carbon atoms such as a group, a propyl group, an isopropyl group, or a butyl group.

  L is preferably 1, m is preferably 0 to 2, and k is preferably 1 to 3. However, the sum of l, m, and k, that is, l + m + k is 4.

  Specific examples of such (meth) acrylic group-containing silicon compounds include trimethoxysilylmethylene (meth) acrylate, trimethoxysilyldimethylene (meth) acrylate, trimethoxysilyltrimethylene (meth) acrylate, triethoxy Silylmethylene (meth) acrylate, triethoxysilyldimethylene (meth) acrylate, triethoxysilyltrimethylene (meth) acrylate, tripropoxysilylmethylene (meth) acrylate, tripropoxysilylethylene (meth) acrylate, tripropoxysilyl trimethylene (Meth) acrylate, Tributoxysilylmethylene (meth) acrylate, Tributoxysilyldimethylene (meth) acrylate, Tributoxysilyltrimethylene (meth) acrylate Triisopropoxysilylmethylene (meth) acrylate, triisopropoxysilyldimethylene (meth) acrylate, triisopropoxysilyltrimethylene (meth) acrylate, dimethoxymethylsilylmethylene (meth) acrylate, dimethoxymethylsilyldimethylene (meth) acrylate , Dimethoxymethylsilyltrimethylene (meth) acrylate, diethoxymethylsilylmethylene (meth) acrylate, diethoxymethylsilyldimethylene (meth) acrylate, diethoxymethylsilyltrimethylene (meth) acrylate, dimethoxyethylsilylmethylene (meth) Acrylate, dimethoxyethylsilyldimethylene (meth) acrylate, dimethoxyethylsilyltrimethylene (meth) acrylate, diethoxy Tylsilylmethylene (meth) acrylate, diethoxyethylsilyldimethylene (meth) acrylate, diethoxyethylsilyltrimethylene (meth) acrylate, methoxydimethylsilylmethylene (meth) acrylate, methoxydimethylsilyldimethylene (meth) acrylate, methoxy Dimethylsilyltrimethylene (meth) acrylate, ethoxydimethylsilylmethylene (meth) acrylate, ethoxydimethylsilyldimethylene (meth) acrylate, ethoxydimethylsilyltrimethylene (meth) acrylate, methoxydiethylsilylmethylene (meth) acrylate, methoxydiethylsilyl Dimethylene (meth) acrylate, methoxydiethylsilyltrimethylene (meth) acrylate, ethoxydiethylsilylmethylene (Meth) acrylate, ethoxydiethylsilyldimethylene (meth) acrylate, ethoxydiethylsilyltrimethylene (meth) acrylate and the like can be mentioned. Of these, trimethoxysilyltrimethylene (meth) acrylate and triethoxysilyltrimethylene (meth) acrylate are preferable.

(Organic silicon compound)
In the present invention, (F) the following formula (3)

(Where
R ⁶ and R ⁷ are the same or different alkyl group having 1 to 4 carbon atoms or hydrogen,
R ⁸ is an aryl group, R ⁹ is an aryl group or an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 1 to 10. )
(Hereinafter also referred to simply as “organosilicon compound”). By using this organosilicon compound, etching resistance to fluorine, oxygen and chlorine can be improved, and in particular, etching resistance to chlorine-based gas can be effectively improved. In particular, the organosilicon compound has a structure having an aromatic ring as shown in the formula (3). In order to further improve the dispersibility of the photocurable nanoimprint composition of the present invention, a combination of a polymerizable monomer having an aromatic ring and an organosilicon compound in the polymerizable monomer (A) described above. Are preferably used. Such a combination is preferable because etching resistance and transferability are further improved.
In addition, the organosilicon compound also has an effect of suppressing the formation of a precipitate considered to be derived from the metal alkoxide when coexisting with the metal alkoxide in the polymerizable monomer having a (meth) acryl group. is there. This is presumed to be because the solubility of the reaction product resulting from the hydrolysis reaction between the metal alkoxide and the organosilicon compound in the (meth) acrylate polymerizable monomer is high.

In the formula (3), R ⁶ and R ⁷ are hydrogen, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, isobutyl group, and tert-butyl group. Group, ethyl group, propyl group, isopropyl group and butyl group are preferred. -OR ^6, alkoxy group represented by -OR ⁷ is ^-OR 6 upon hydrolysis, but produces an alcohol derived from -OR ^7, photocurable composition for imprints of the invention, contain the alcohol Also good. Therefore, considering that the alcohol can be easily mixed with other components and that the alcohol can be easily removed after forming a coating film on the substrate, specifically, R ⁶ and R ⁷ are methyl. An alkyl group having 1 to 4 carbon atoms such as a group, an ethyl group, a propyl group, an isopropyl group and a butyl group is preferable.

In R ⁸ and R ⁹ , the aryl group is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, and a naphthyl group, and among them, a phenyl group is preferable.

R ⁹ represents an alkoxy group such as a methyl alkoxy group, an ethyl alkoxy group, a propyl alkoxy group, an isopropyl alkoxy group, a butyl alkoxy group, a sec-butyl alkoxy group, an isobutyl alkoxy group, a tert-butyl alkoxy group, and the like. Can do. As the alkoxy group, a methyl alkoxy group, an ethyl alkoxy group, a propyl alkoxy group, an isopropyl alkoxy group, and a butyl alkoxy group are particularly preferable. Alkoxy group represented by the R ⁹ is to produce an alcohol derived from R ⁹ upon hydrolysis, photocurable composition for imprints of the invention may contain the alcohol. Therefore, considering that it becomes an alcohol that can be easily mixed with other components, and that it becomes an alcohol that can be easily removed after forming a coating film on the substrate, specifically, a methyl alkoxy group, an ethyl alkoxy group, An alkoxy group having 1 to 4 carbon atoms such as propylalkoxy group, isopropylalkoxy group, butylalkoxy group, sec-butylalkoxy group, isobutylalkoxy group, tert-butylalkoxy group and the like is preferable. The aryl group and alkoxy group may have a substituent such as an alkyl group, an ether group, a glycol ether group, a hydroxyl group, or a halogen.

Among these, R ⁸ and R ⁹ are preferably aryl groups having 6 to 20 carbon atoms from the viewpoint of forming a cured film having good etching resistance, in particular, chlorine gas etching resistance.

  The organosilicon compound may be a single compound or a plurality of organosilicons having different values of n as long as n satisfies the integer of 1 to 10 in the formula (3). It may be a mixture of compounds. In the case of using a single compound, the value of n is preferably 1 or more and 7 or less in consideration of transferability of a pattern at a relatively low pressure and transfer of a fine pattern such as 100 nm or less. Further, when a mixture of a plurality of organosilicon compounds is used, the average value of n is preferably 1 or more and 10 or less, and further, the pattern transferability at a relatively lower pressure, 100 nm or less, etc. Considering the transfer of the fine pattern, it is more preferably 1 or more and 7 or less.

Specific examples of these organosilicon compounds include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldibutoxysilane. And polycondensates thereof. Among them, the alcohol produced during hydrolysis is an alcohol that can be easily removed after forming a coating film, and for reasons such as reactivity, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldioxydioxide. Ethoxysilanes and their polycondensates are preferred.
In the present invention, the metal alkoxide (B) and the β-hydroxyketone (C) maintain the properties as a nanoimprinting composition such as pattern transferability and adhesion between the pattern and the substrate to such an extent that there is no practical problem. However, the following blending amounts are preferable from the viewpoint of achieving both etching resistance of chlorine-based gas and long-term storage stability. That is, with respect to 100 parts by mass of the polymerizable monomer (A), the metal alkoxide (B) is 0.1 part by mass to 150 parts by mass, and the β-hydroxy ketones (C) are 10 parts by mass to 10,000 parts by mass. Part. Addition of β-hydroxy ketones (C) within the above range can contribute not only to ensuring storage stability but also to etching resistance of chlorine-based gas as a result of not causing precipitation. Considering the etching resistance of chlorine-based gas and long-term storage stability, the metal alkoxide (B) is used in an amount of 0.5 to 100 parts by mass with respect to 100 parts by mass of the polymerizable monomer (A). It is more preferable that it is a mass part, and it is more preferable that the usage-amount of (beta) -hydroxy ketone (C) is 20 mass parts-5,000 mass parts. Furthermore, it is preferable that the usage-amount of a metal alkoxide (B) is 1 mass part-80 mass parts, and the usage-amount of (beta) -hydroxy ketone (C) is 25 mass parts-2,000 mass parts. It is preferable. In particular, the amount of metal alkoxide (B) used is particularly preferably 3 to 50 parts by mass, and the amount of β-hydroxy ketones (C) used is 30 to 1,000 parts by mass. It is particularly preferred.
In using the photocurable nanoimprint composition of the present invention, the photocurable nanoimprint composition is applied on a substrate and used. In this case, the content of β-hydroxy ketones (C) is set to the above-mentioned content. By adjusting to a preferable range, the coating film which consists of the photocurable nanoimprint composition of this invention mentioned later can be formed.

The photocurable nanoimprinting composition of the present invention can further contain an organosilicon compound (E) having a (meth) acryl group. By including the organosilicon compound (E) having a (meth) acrylic group, a highly dispersible photocurable nanoimprinting composition is obtained, and purification by filtration is facilitated and productivity is improved. In the fine structure of the resulting cured film, the inorganic and organic components are dispersed in a relatively homogeneous state (the dispersed state does not result in the inorganic component being extremely agglomerated), and adhesion to the substrate Can also be preferably added. The amount of the metal alkoxide (B) is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the polymerizable monomer (A), and the β-hydroxy ketones (C) 10 to 10 parts by mass, It is preferable that it is 000 mass parts, and it is preferable that the organosilicon compound (E) which has a (meth) acryl group is 3 mass parts-300 mass parts. In consideration of dispersibility and adhesion to the substrate, the amount of metal alkoxide (B) used is more preferably 0.5 to 100 parts by weight, and the amount of β-hydroxy ketones (C) used. Is more preferably 20 parts by mass to 5,000 parts by mass,
As for the usage-amount of the organosilicon compound (E) which has a (meth) acryl group, it is more preferable that they are 5 mass parts-250 mass parts. Furthermore, it is preferable that the usage-amount of a metal alkoxide (B) is 1 mass part-80 mass parts, and the usage-amount of (beta) -hydroxy ketone (C) is 25 mass parts-2,000 mass parts. It is preferable that the amount of the organosilicon compound (E) having a (meth) acryl group be 10 to 200 parts by mass. In particular, the amount of metal alkoxide (B) used is particularly preferably 3 to 50 parts by mass, and the amount of β-hydroxy ketones (C) used is 30 to 1,000 parts by mass. It is particularly preferable that the amount of the organosilicon compound (E) having a (meth) acrylic group be 15 to 180 parts by mass.

  The photocurable nanoimprint composition of the present invention can further contain an organosilicon compound (F) in addition to the organosilicon compound (E) having a (meth) acryl group. By including the organosilicon compound (F), etching resistance, particularly etching resistance to chlorine-based gas can be improved, and nanoimprint pattern transferability at a lower pressure is also improved, so that it can be preferably added. It is preferable that it is 0.1-150 mass parts of metal alkoxides (B) with respect to 100 mass parts of the said polymerizable monomer (A), (beta) -hydroxy ketones (C) 10 mass parts-10, The organic silicon compound (E) having a (meth) acryl group is preferably 3 parts by mass to 300 parts by mass, and the organosilicon compound (F) is 10 parts by mass to 400 parts. It is preferable that it is a mass part. In consideration of dispersibility and adhesion to the substrate, the amount of metal alkoxide (B) used is more preferably 0.5 to 100 parts by weight, and the amount of β-hydroxy ketones (C) used. Is more preferably 20 parts by mass to 5,000 parts by mass, and the amount of the organosilicon compound (E) having a (meth) acryl group is more preferably 5 parts by mass to 250 parts by mass, The organosilicon compound (F) is more preferably 30 parts by mass to 300 parts by mass. Furthermore, it is preferable that the usage-amount of a metal alkoxide (B) is 1 mass part-80 mass parts, and the usage-amount of (beta) -hydroxy ketone (C) is 25 mass parts-2,000 mass parts. The amount of the organosilicon compound (E) having a (meth) acryl group is preferably 10 parts by mass to 200 parts by mass, and the amount of the organosilicon compound (F) used is 50 parts by mass to It is preferably 250 parts by mass. In particular, the amount of metal alkoxide (B) used is particularly preferably 3 to 50 parts by mass, and the amount of β-hydroxy ketones (C) used is 30 to 1,000 parts by mass. It is particularly preferable that the amount of the organosilicon compound (E) having a (meth) acryl group is particularly preferably 15 to 180 parts by mass, and the amount of the organosilicon compound (F) used is 80 masses. It is particularly preferable that the amount is from 200 parts by mass to 200 parts by mass.

  Next, the photopolymerization initiator (D) will be described.

(Photopolymerization initiator (D))
In the present invention, the photopolymerization initiator (D) is not particularly limited, and any photopolymerization initiator can be used as long as it can photopolymerize the polymerizable monomer (A).

  Specific examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy- 2-methylpropionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methylben) Acetophenone derivatives such as (zyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2, 6-dichlorobenzoyldiphenylphosphine oxide, 2,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide Bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide Bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis- (2,5,6-trimethylbenzoyl)- Acylphosphine oxide derivatives such as 2,4,4-trimethylpentylphosphine oxide; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, O-acyloxime derivatives such as 1- (O-acetyloxime); diacetyl, acetylbenzoyl, benzyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, 4,4′-oxybenzyl Α-diketones such as camphorquinone, 9,10-phenanthrenequinone, and acenaphthenequinone; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin propyl ether; 2,4-diethoxythioxanthone, 2 -Thioxanthone derivatives such as chlorothioxanthone and methylthioxanthone; benzophenone derivatives such as benzophenone, p, p'-dimethylaminobenzophenone and p, p'-methoxybenzophenone; bis (η5-2,4-cyclopentadiene-1- Il) -bis (2,6 A titanocene derivative such as -difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium is preferably used.

  These photopolymerization initiators are used alone or in combination of two or more.

  When α-diketone is used, it is preferably used in combination with a tertiary amine compound. Tertiary amine compounds that can be used in combination with α-diketone include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline. N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N- Dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylanthranic acid methyl Ester, N, N-dihydroxyethylaniline, N, N-dihydroxyethyl-p-toluidine, p Dimethylaminophenethyl alcohol, p-dimethylaminostilbene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine, tri Butylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate N, N-diethylaminoethyl methacrylate, 2,2 ′-(n-butylimino) diethanol, and the like.

  In the present invention, it is preferable to use an acetophenone derivative, an acylphosphine oxide derivative, an O-acyloxime derivative, or an α-diketone.

  In this invention, it is preferable that the usage-amount of the said photoinitiator is 0.1 mass part-10 mass parts with respect to 100 mass parts of said polymerizable monomers (A), 0.1 mass part It is more preferable that it is ˜5 parts by mass from the viewpoint of etching resistance.

(Other additive components in photocurable nanoimprint composition)
The photocurable nanoimprint composition of the present invention may contain other components within a range that does not impair the effects of the present invention.

The photocurable nanoimprinting composition of the present invention can be used in combination with a solvent in addition to (C) β-hydroxy ketones. As the solvent used, any solvent that can dissolve the composition for photocurable nanoimprinting of the present invention can be used without any limitation. For example, acetonitrile, tetrahydrofuran, toluene, chloroform, acetic acid ethyl ester, methyl ethyl ketone, dimethylformamide, Cyclohexanone, ethylene glycol, ethylene glycol isopropyl ether, propylene glycol, propylene glycol methyl ether, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethylene glycol monoethyl ether acetate, ethyl lactate, ethyl-3-ethoxypropio Butyl acetate, 2-heptanone, methyl isobutyl ketone, acetylacetone, t-butyl alcohol, poly When a solvent is used which may be mentioned Ji glycol, other alcohols, the amount is not particularly limited, depending on the thickness of the coating of interest is properly selected. In particular, when the total amount of the solvent and the photocurable nanoimprint composition is 100% by mass, the concentration of the solvent is preferably in the range of 10% by mass to 99% by mass.

  Other well-known additives can be mix | blended with the composition for photocurable nanoimprint of this invention. Specifically, a surfactant, a polymerization inhibitor, a reactive diluent and the like can be blended. From the viewpoint of the uniformity of the coating film, the surfactant is added to stabilize the polymerization inhibitor so that it does not polymerize during storage.

  When the surfactant is blended, 0.0001 parts by mass to 1 part by mass, preferably 0.001 parts by mass to 0.1 parts by mass with respect to 100 parts by mass of the polymerizable monomer (A). It can mix | blend in a ratio.

  As the surfactant, a fluorine-containing surfactant, a silicone-containing surfactant, and an aliphatic surfactant can be used. Among these, in the case where the photocurable nanoimprint composition is applied to a substrate such as a silicon wafer, an aliphatic surfactant may be used from the viewpoint that the composition can be uniformly applied without causing repelling. More preferred.

  Examples of surfactants include metal salts of higher alcohol sulfates such as sodium decyl sulfate and sodium lauryl sulfate, aliphatic carboxylic acid metal salts such as sodium laurate, sodium stearate and sodium oleate, lauryl alcohol and ethylene oxide. Anionic activity such as metal salts of higher alkyl ether sulfates such as sodium lauryl ether sulfate esterified with adducts with sodium, sulfosuccinic diesters such as sodium sulfosuccinate, phosphate esters of higher alcohol ethylene oxide adducts, etc. Agents; Cationic surfactants such as alkylamine salts such as dodecylammonium chloride and quaternary ammonium salts such as trimethyldodecylammonium bromide; such as dodecyldimethylamine oxide Zwitterionic surfactants such as alkyl dimethyl betaines such as alkyl dimethyl amine oxides, alkyl carboxy betaines such as dodecyl carboxy betaine, alkyl sulfo betaines such as dodecyl sulfo betaine, and amide amino acid salts such as lauramido propyl amine oxide; Polyoxyethylene alkyl ethers, polyoxyalkylene alkyl ethers, polyoxyethylene distyrenated phenyl ethers, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene lauryl phenyl ether, polyoxyethylene tribenzylphenyl ethers, Fatty acid polyoxyethylene esters such as fatty acid polyoxyethylene lauryl ester, polio such as polyoxyethylene sorbitan lauryl ester It can be mentioned non-ionic surfactants such as polyoxyethylene sorbitan esters. Surfactants can be used not only independently but also in combination of a plurality of types as required.

  When blending a polymerization inhibitor, 0.01 parts by weight to 1.0 parts by weight, preferably 0.1 parts by weight to 0.5 parts by weight with respect to 100 parts by weight of the polymerizable monomer (A). It can mix | blend in the ratio of a part.

  Examples of the polymerization inhibitor include known ones. For example, the most typical ones include hydroquinone monomethyl ether, hydroquinone, butylhydroxytoluene and the like.

  Examples of the reactive diluent include known ones such as N-vinylpyrrolidone.

  The addition amount of the reactive diluent is not particularly limited and is appropriately selected within a range not affecting the formation of the pattern from the mold, and is usually 1 mass per 100 mass parts of the polymerizable monomer (A). Part to 100 parts by mass. Among these, it is preferable that it is 5-50 mass parts when the viscosity reduction of the composition for photocurable nanoimprint, the mechanical strength of a pattern, etc. are taken into consideration.

  In addition, as another additive component, the releasability from the mold (pattern forming surface) is improved, and thus a pattern having a shape with excellent reproducibility can be formed on the substrate. Spherical fine particles can also be added. In this case, it is preferable to blend a spherical hyperbranched polymer having a diameter of 1 to 10 nm and a molecular weight of 10,000 to 100,000. The blending amount is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer (A).

  The composition for photocurable nanoimprint of the present invention comprises a polymerizable monomer (A), a metal alkoxide (B), a β-hydroxyketone (C), a photopolymerization initiator (D), and if necessary. It is prepared by mixing other additive ingredients. The order of addition of these components is not particularly limited.

  Next, a method for forming a pattern on a substrate using this photocurable nanoimprint composition will be described.

(Pattern formation method using photocurable imprinting composition)
A pattern forming method using the photocurable nanoimprinting composition of the present invention will be described.

  First, the coating film is formed by apply | coating the composition for photocurable nanoimprint prepared according to the said method on a base material according to a well-known method.

  The form and material of the substrate are not particularly limited, and substrates, sheets, and films can be used. Specifically, silicon wafer, quartz, glass, sapphire, various metal materials, ceramics such as alumina / aluminum nitride / silicon carbide / silicon nitride, polyethylene terephthalate film, polypropylene film, polycarbonate film, triacetyl cellulose film, cycloolefin resin A known substrate such as a film, a sheet, or a film can be used. In addition, these base materials can also surface-treat in order to improve adhesiveness with the cured film which consists of a composition for photocurable nanoimprint of this invention more.

  On these substrates, the photocurable nanoimprint composition of the present invention is applied by a known method such as a spin coating method, a dipping method, a dispensing method, an ink jet method, a spray coating method, or a roll-to-roll method, followed by drying. By doing so, a coating film may be formed. The thickness of the coating film is not particularly limited and may be appropriately determined according to the intended use, but is usually 0.1 μm to 5 μm, and the photocurable nanoimprint composition of the present invention is 0 The present invention can also be suitably applied to the formation of a coating film having a thickness of 0.01 μm to 0.1 μm.

  The drying temperature is not particularly limited as long as it is a temperature at which the coating film dries, but can be usually selected from the range of 40 ° C. to 200 ° C. in consideration of removing volatile components in the air. Considering productivity and suppression of oxidative degradation, the temperature is preferably selected from the range of 60 ° C to 190 ° C, more preferably from 80 ° C to 180 ° C.

  The drying time is not particularly limited as long as it is a time for drying the coating film, but can be usually selected from the range of 10 seconds to 10 minutes in consideration of suppression of oxidative deterioration in the air.

  In order to apply thinly, it can be applied by adjusting the content with β-hydroxy ketones (C) and optionally a solvent used together. When using a solvent together, the boiling point and volatilization of the solvent used. What is necessary is just to determine a drying temperature and drying time suitably according to property.

  Next, the pattern forming surface of the mold on which a desired pattern is formed is brought into contact with the coating film. At this time, the mold may be formed of a transparent material such as quartz or a transparent resin film so that a cured film can be formed by curing the applied composition through light irradiation. preferable. The photocurable nanoimprinting composition of the present invention can transfer a pattern at a relatively low pressure when pressing a mold. The pressure at this time is not particularly limited, but the pattern can be transferred at a pressure of 0.01 MPa to 1 MPa. As a matter of course, the pattern can be transferred even at a pressure higher than the upper limit of the pressure.

  Thereafter, the coating film is cured by irradiating light while keeping the pattern forming surface of the mold in contact with the coating film. The light to be irradiated has a wavelength of 500 nm or less, and the light irradiation time is selected from the range of 0.1 seconds to 300 seconds. Although it depends on the thickness of the coating film, etc., it is usually 1 second to 60 seconds.

  The atmosphere during photopolymerization can be polymerized even in the air, but in order to promote the photopolymerization reaction, photopolymerization in an atmosphere with little oxygen inhibition is preferred. For example, a nitrogen gas atmosphere, an inert gas atmosphere, a fluorine gas atmosphere, a vacuum atmosphere, or the like is preferable.

  After photocuring, a laminate in which a pattern is formed by a cured coating film (cured film) on the substrate is obtained by separating the mold from the cured coating film.

(Pattern formation on the substrate: Etching of the laminate with the pattern formed by the cured film)
In the photocurable nanoimprint composition of the present invention, the formed cured film exhibits excellent etching resistance. Therefore, the pattern formed from the cured film has very good etching resistance with oxygen gas, fluorine-based gas, chlorine-based gas, etc., and nanoscale irregularities are formed by etching with oxygen gas, fluorine-based gas, chlorine-based gas, etc. It can be suitably used as a mask for producing a substrate having a structure. In particular, the cured film obtained from the photocurable nanoimprinting composition of the present invention is excellent in etching resistance to chlorine-based gas for processing a sapphire substrate, and is therefore used as a mask for surface processing of a sapphire substrate. Suitable for As the chlorine-based gas, a known gas used for reactive ion etching can be used. Specific examples include chlorine, boron trichloride, and carbon tetrachloride. If necessary, oxygen gas, fluorine-based gas, and the like can be mixed and used.

As a method of forming a pattern based on the pattern of the cured film on the substrate (laminate formed with the pattern by the cured film) having a cured film having a pattern transferred by a mold on the surface obtained as described above, First, the thin part (residual film) of the cured film is removed by dry etching to expose the substrate surface. Further, dry etching is performed on the substrate from which the residual film has been removed. The substrate covered with the thick part of the cured film is not dry-etched entirely using the thick part of the cured film as a mask. By removing the thick part of the cured film remaining at the end, a substrate obtained by dry etching the substrate surface can be obtained. As a method for removing the thick portion of the cured film, it can be removed by dry etching or wet etching. In particular, in the case of pattern formation on a sapphire substrate, dry etching with a fluorine-based gas is preferably used.
After the thin part (residual film) of the cured film is removed by dry etching, metal can be deposited on the substrate surface where the residual film has been removed.

  Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.

(1) Evaluation of substrate adhesion of cured film The obtained composition for photocurable nanoimprint was applied on a sapphire substrate (single mirror surface, thickness 430 μm, surface roughness Ra ≦ 0.1 nm, plane orientation C surface). After spin coating at 3000 rpm for 30 seconds and drying at 160 ° C. for 2 minutes, UV irradiation was performed to prepare a cured film of the photocurable nanoimprinting composition, and a 15 mm wide cellophane tape 405 manufactured by Nichiban Co., Ltd. was used ( 5cm long), peeled after 3 reciprocal contact with finger pressure,
The cured film was not removed at all: 5
The peeled area is less than 10%: 4
Exfoliation area of 10% or more and less than 50%: 3
Exfoliation area 50% or more and less than 100%: 2
With peeling area of 100% (full peeling): 1
As evaluated.

(2) Evaluation of transferability (Application of photocurable nanoimprint composition)
The obtained photocurable nanoimprint composition was spin-coated on a silicon wafer (P-type, single mirror surface, no oxide film) at 3000 rpm for 30 seconds, and dried at 160 ° C. for 2 minutes. A silicon wafer coated with a coating film of the composition was obtained.

(Pattern formation: Manufacture of laminate)
Using a 200 nm line / space quartz mold, in a nanoimprint apparatus (ImpFlex-Essential, manufactured by Sanmei Electronics Co., Ltd.), a silicon wafer having a coating film of the photocurable nanoimprint composition obtained as described above Then, light nanoimprinting was performed by applying a pressure of 1 MPa and irradiating light from an LED 365 nm light source for 60 seconds. The quartz mold used was previously subjected to a mold release treatment by a fluorine-based surface treatment (manufactured by Daikin Industries, Ltd., OPTOOL HD-1100TH).

  The shape transferability of the pattern formed on the sapphire substrate using the photocurable nanoimprint composition was evaluated by observation with a scanning electron microscope (SEM). In the evaluation of transferability, “100” indicates that all 100 lines with a width of 200 nm have been transferred, and “△” indicates that some of the pattern shapes are defective, and all patterns cannot be transferred. Was evaluated as “×”.

(3) Evaluation of etching resistance (etching of sapphire substrate)
A sapphire substrate (single mirror surface, thickness 430 μm, surface roughness Ra ≦ 0.1 nm, plane orientation C plane) is dry-etched with chlorine gas under the following conditions using a reactive ion etching apparatus, and is performed for a certain period of time. The etching amount (reduced thickness of the sapphire substrate) was measured with a stylus type step difference measuring device.
<Dry etching conditions with chlorine gas>
Chlorine gas flow rate: 20sccm
Antenna power: 400W
Bias power: 80W
Substrate cooling temperature: 5 ° C
(Etching cured film)
The obtained photocurable nanoimprint composition was spin-coated on a silicon wafer (P-type, single mirror surface, no oxide film) at 3000 rpm for 30 seconds, dried at 160 ° C. for 2 minutes, and then irradiated with UV. A silicon wafer coated with a cured film of the photocurable nanoimprinting composition was obtained. The thickness of the obtained cured film was observed with an electron microscope (SEM). The silicon wafer coated with the resulting cured film is dry etched under the same conditions as dry etching with chlorine gas on a sapphire substrate, and the thickness of the cured film that has decreased over a certain period of time is measured with a stylus type step gauge. It was measured.

(Calculation of sapphire selectivity)
Ratio of etching amount of sapphire substrate only for sapphire substrate in a certain time (reduced thickness of sapphire substrate) and reduced coating thickness of cured film in a certain time of cured film of photocurable nanoimprint composition (sapphire Calculate the etching amount of the substrate in a certain time (reduced thickness of the sapphire substrate) / the cured film thickness of the cured film of the composition for photocurable nanoimprinting that has decreased in a certain time), and calculate this photocurable nanoimprint It was set as the sapphire selectivity of the cured film of the composition for use. The higher the sapphire selectivity value, the harder the cured film of the photocurable nanoimprinting composition is to be less susceptible to etching by chlorine gas than the sapphire substrate, and the better the chlorine etching resistance when using a sapphire substrate. .

(4) Evaluation of long-term storage stability The obtained photocurable nanoimprint composition was put in a sample bottle, sealed with a lid, and placed in a constant temperature oven maintained at 50 ° C. to evaluate long-term storage stability. Went.
If no change in fluidity or appearance (precipitation, gelation, color) was observed for 21 consecutive days or more, “○” was given, and fluidity and appearance (precipitation, gelation, color) were observed in 8 to 20 days. A change was observed as “Δ”, and a change in fluidity and appearance (precipitation, gelation, color) was observed as “x” from 0 to 7 days.

Example 1
(Production of photocurable nanoimprint composition)
As a polymerizable monomer (A) having a (meth) acryl group, hydroxyethylated o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-LEN-10) 5.0 g, 9,9 5.0 g of -bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-BPEF) was used.

  As the metal alkoxide (B), 0.2 g of tungsten (V) ethoxide (manufactured by Alfa Aesar) was used.

  As β-hydroxy ketones (C), 9.8 g of 4-hydroxy-4-methyl-2-pentanone was used.

  As a photopolymerization initiator (D), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (BASF Japan K.K.) 0.2 g of IRGACURE (registered trademark) 379 EG).

  As the polymerization inhibitor, 0.015 g of hydroquinone monomethyl ether and 0.002 g of butylhydroxytoluene were used.

The metal alkoxide (B) and β-hydroxy ketones (C) were uniformly mixed to obtain a mixed solution composed of the metal alkoxide (B) and β-hydroxy ketones (C).
The polymerizable monomer (A) having the (meth) acryl group, the photopolymerization initiator (D), and the polymerization inhibitor were uniformly mixed to obtain a mixture. 2.0 g of a mixture consisting of the polymerizable monomer (A) having a (meth) acrylic group, a photopolymerization initiator (D) and a polymerization inhibitor was collected, and the metal alkoxide (B) and β obtained above were collected. -The composition for photocurable nanoimprint was obtained by adding 2.0 g of mixed solutions which consist of hydroxy ketones (C), and stirring for 15 minutes at room temperature.
The obtained composition for photocurable nanoimprint was filtered with a syringe filter having a 0.2 μmφ hole diameter. The blending ratio of this photocurable nanoimprint composition is shown in Table 1.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion of the cured film, transferability, cured film thickness, sapphire selectivity, and long-term storage stability. The results are shown in Tables 2-4.

Example 2
(Production of photocurable nanoimprint composition)
As a polymerizable monomer (A) having a (meth) acryl group, hydroxyethylated o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-LEN-10) 5.0 g, 9,9 5.0 g of -bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-BPEF) was used.

  As the metal alkoxide (B), 0.2 g of tungsten (V) ethoxide (manufactured by Alfa Aesar) was used.

  As β-hydroxy ketones (C), 4.8 g of 4-hydroxy-4-methyl-2-pentanone was used.

  As a photopolymerization initiator (D), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (BASF Japan K.K.) 0.2 g of IRGACURE (registered trademark) 379 EG).

  As the polymerization inhibitor, 0.015 g of hydroquinone monomethyl ether and 0.002 g of butylhydroxytoluene were used.

The metal alkoxide (B) and β-hydroxy ketones (C) were uniformly mixed to obtain a mixed solution composed of the metal alkoxide (B) and β-hydroxy ketones (C).
The polymerizable monomer (A) having the (meth) acryl group, the photopolymerization initiator (D), and the polymerization inhibitor were uniformly mixed to obtain a mixture. 2.0 g of a mixture consisting of the polymerizable monomer (A) having a (meth) acrylic group, a photopolymerization initiator (D) and a polymerization inhibitor was collected, and the metal alkoxide (B) and β obtained above were collected. -1.0 g of mixed solution which consists of hydroxy ketones (C) and 1.0 g of acetylacetone as a solvent were added, and the composition for photocurable nanoimprint was obtained by stirring for 15 minutes at room temperature.
The obtained composition for photocurable nanoimprint was filtered with a syringe filter having a 0.2 μmφ hole diameter. The blending ratio of this photocurable nanoimprint composition is shown in Table 1.
The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion of the cured film, transferability, cured film thickness, sapphire selectivity, and long-term storage stability. The results are shown in Tables 2-4.

Example 3
(Production of photocurable nanoimprint composition)
As a polymerizable monomer (A) having a (meth) acryl group, hydroxyethylated o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-LEN-10) 5.0 g, 9,9 5.0 g of -bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-BPEF) was used.

  As the metal alkoxide (B), 0.2 g of tungsten (V) ethoxide (manufactured by Alfa Aesar) was used.

  As β-hydroxy ketones (C), 9.8 g of 4-hydroxy-4-methyl-2-pentanone was used.

  As a photopolymerization initiator (D), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (BASF Japan K.K.) 0.2 g of IRGACURE (registered trademark) 379 EG).

  As the polymerization inhibitor, 0.015 g of hydroquinone monomethyl ether and 0.002 g of butylhydroxytoluene were used.

  As the organosilicon compound (E) having a (meth) acryl group, 1.5 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

The metal alkoxide (B), the β-hydroxy ketones (C), and the organosilicon compound (E) having a (meth) acryl group are uniformly mixed, and the metal alkoxide (B), the β-hydroxy ketones (C) and A mixed solution comprising an organosilicon compound (E) having a (meth) acryl group was obtained.
The polymerizable monomer (A) having the (meth) acryl group, the photopolymerization initiator (D), and the polymerization inhibitor were uniformly mixed to obtain a mixture. 2.0 g of a mixture consisting of the polymerizable monomer (A) having a (meth) acrylic group, a photopolymerization initiator (D) and a polymerization inhibitor was collected, and the metal alkoxide (B) and β obtained above were collected. -A photocurable nanoimprinting composition was obtained by adding 2.0 g of a mixed solution composed of hydroxy ketones (C) and an organosilicon compound (E) having a (meth) acrylic group and stirring at room temperature for 15 minutes. .
The obtained composition for photocurable nanoimprint was filtered with a syringe filter having a 0.2 μmφ hole diameter. The blending ratio of this photocurable nanoimprint composition is shown in Table 1.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion of the cured film, transferability, cured film thickness, sapphire selectivity, and long-term storage stability. The results are shown in Tables 2-4.

Example 4
(Production of photocurable nanoimprint composition)
As a polymerizable monomer (A) having a (meth) acryl group, hydroxyethylated o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-LEN-10) 5.0 g, 9,9 5.0 g of -bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-BPEF) was used.

  As the metal alkoxide (B), 0.2 g of tungsten (V) ethoxide (manufactured by Alfa Aesar) was used.

  As β-hydroxy ketones (C), 9.8 g of 4-hydroxy-4-methyl-2-pentanone was used.

  As a photopolymerization initiator (D), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (BASF Japan K.K.) 0.2 g of IRGACURE (registered trademark) 379 EG).

  As the polymerization inhibitor, 0.015 g of hydroquinone monomethyl ether and 0.002 g of butylhydroxytoluene were used.

  As the organosilicon compound (E) having a (meth) acryl group, 1.5 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

  As the organosilicon compound (F), 5.4 g of diphenyldimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

The above metal alkoxide (B), β-hydroxyketone (C), organosilicon compound (E) having (meth) acrylic group and organosilicon compound (F) are uniformly mixed, and the metal alkoxide (B) and β- A mixed solution consisting of hydroxy ketones (C), an organosilicon compound (E) having a (meth) acryl group and an organosilicon compound (F) was obtained.
The polymerizable monomer (A) having the (meth) acryl group, the photopolymerization initiator (D), and the polymerization inhibitor were uniformly mixed to obtain a mixture. 2.0 g of a mixture consisting of the polymerizable monomer (A) having a (meth) acrylic group, a photopolymerization initiator (D) and a polymerization inhibitor was collected, and the metal alkoxide (B) and β obtained above were collected. -Photocurability by adding 2.0 g of a mixed solution composed of hydroxyketone (C), organosilicon compound (E) having (meth) acrylic group and organosilicon compound (F) and stirring at room temperature for 15 minutes A composition for nanoimprinting was obtained.
The obtained composition for photocurable nanoimprint was filtered with a syringe filter having a 0.2 μmφ hole diameter. The blending ratio of this photocurable nanoimprint composition is shown in Table 1.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion of the cured film, transferability, cured film thickness, sapphire selectivity, and long-term storage stability. The results are shown in Tables 2-4.

Example 5
(Production of photocurable nanoimprint composition)
As metal alkoxide (B), 0.1 g of tungsten (V) ethoxide (manufactured by Alfa Aesar) is used, and 19.9 g of 4-hydroxy-4-methyl-2-pentanone is used as β-hydroxy ketones (C). did. 2.0 g of a mixture of the polymerizable monomer (A) having a (meth) acrylic group obtained in Example 1, a photopolymerization initiator (D), and a polymerization inhibitor was collected, and the metal obtained above was collected. A photocurable nanoimprinting composition was obtained in the same manner as in Example 1 except that 4.0 g of a mixed solution composed of alkoxide (B) and β-hydroxyketone (C) was added.
The obtained composition for photocurable nanoimprint was filtered with a syringe filter having a 0.2 μmφ hole diameter. The blending ratio of this photocurable nanoimprint composition is shown in Table 1.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion of the cured film, transferability, cured film thickness, sapphire selectivity, and long-term storage stability. The results are shown in Tables 2-4.

Example 6
(Production of photocurable nanoimprint composition)
As the polymerizable monomer (A) having a (meth) acrylic group, 5.0 g of polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-200), tricyclodecane dimethanol diacrylate (new) 5.0 g of Nakamura Chemical Co., Ltd. (NK ester A-DCP) was used. In the same manner as in Example 1, except that 2.0 g of a mixture composed of the polymerizable monomer (A) having the (meth) acrylic group, the photopolymerization initiator (D), and the polymerization inhibitor was collected. A curable nanoimprinting composition was obtained.
The obtained composition for photocurable nanoimprint was filtered with a syringe filter having a 0.2 μmφ hole diameter. The blending ratio of this photocurable nanoimprint composition is shown in Table 1.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion of the cured film, transferability, cured film thickness, sapphire selectivity, and long-term storage stability. The results are shown in Tables 2-4.

Example 7
(Production of photocurable nanoimprint composition)
As a polymerizable monomer (A) having a (meth) acryl group, hydroxyethylated o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-LEN-10) 5.0 g, 9,9 5.0 g of -bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-BPEF) was used.

  As the metal alkoxide (B), 1.2 g of tungsten (V) ethoxide (manufactured by Alfa Aesar) was used.

  As the β-hydroxy ketones (C), 38.8 g of 4-hydroxy-4-methyl-2-pentanone was used.

  As a photopolymerization initiator (D), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (BASF Japan K.K.) 0.2 g of IRGACURE (registered trademark) 379 EG).

  As the polymerization inhibitor, 0.015 g of hydroquinone monomethyl ether and 0.002 g of butylhydroxytoluene were used.

The metal alkoxide (B) and β-hydroxy ketones (C) were uniformly mixed to obtain a mixed solution composed of the metal alkoxide (B) and β-hydroxy ketones (C).
The polymerizable monomer (A) having the (meth) acryl group, the photopolymerization initiator (D), and the polymerization inhibitor were uniformly mixed to obtain a mixture. 2.0 g of a mixture consisting of the polymerizable monomer (A) having a (meth) acrylic group, a photopolymerization initiator (D) and a polymerization inhibitor was collected, and the metal alkoxide (B) and β obtained above were collected. -8.0 g of mixed solution which consists of hydroxy ketones (C) was added, and the composition for photocurable nanoimprint was obtained by stirring for 15 minutes at room temperature.
The obtained composition for photocurable nanoimprint was filtered with a syringe filter having a 0.2 μmφ hole diameter. The blending ratio of this photocurable nanoimprint composition is shown in Table 1.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion of the cured film, transferability, cured film thickness, sapphire selectivity, and long-term storage stability. The results are shown in Tables 2-4.

Comparative Example 1
(Production of photocurable nanoimprint composition)
As a polymerizable monomer (A) having a (meth) acryl group, hydroxyethylated o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-LEN-10) 5.0 g, 9,9 5.0 g of -bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-BPEF) was used.

  As the metal alkoxide (B), tungsten (V) ethoxide (manufactured by Alfa Aesar) was used.

  As a photopolymerization initiator (D), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (BASF Japan K.K.) 0.2 g of IRGACURE (registered trademark) 379 EG).

  As the polymerization inhibitor, 0.015 g of hydroquinone monomethyl ether and 0.002 g of butylhydroxytoluene were used.

The polymerizable monomer (A) having the (meth) acryl group, the photopolymerization initiator (D), and the polymerization inhibitor were uniformly mixed to obtain a mixture. 5.0 g of a mixture composed of the polymerizable monomer (A) having a (meth) acrylic group, a photopolymerization initiator (D) and a polymerization inhibitor was sampled, and 0.1 g of the metal alkoxide (B) was added. When the mixture was stirred at room temperature for 15 minutes, a white precipitate was deposited. A photocurable nanoimprinting composition was obtained. The blending ratio of this photocurable nanoimprint composition is shown in Table 1.
As a solvent, 5.0 g of acetylacetone was added as a solvent to the resulting photocurable nanoimprinting composition on which the white precipitate was deposited, followed by filtration through a 0.2 μmφ hole diameter syringe filter.

  Using the filtered composition for photo-curable nanoimprint, the substrate adhesion of the cured film, transferability, cured film thickness, sapphire selectivity, and long-term storage stability were evaluated. The results are shown in Tables 2-4.

Comparative Example 2
(Production of photocurable nanoimprint composition)
As a polymerizable monomer (A) having a (meth) acryl group, hydroxyethylated o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-LEN-10) 5.0 g, 9,9 5.0 g of -bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-BPEF) was used.

  As the metal alkoxide (B), tungsten (V) ethoxide (manufactured by Alfa Aesar) was used.

  As a photopolymerization initiator (D), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (BASF Japan K.K.) 0.2 g of IRGACURE (registered trademark) 379 EG).

  As the polymerization inhibitor, 0.015 g of hydroquinone monomethyl ether and 0.002 g of butylhydroxytoluene were used.

  0.1 g of the metal alkoxide (B) and 4.9 g of acetylacetone as a solvent were uniformly mixed to obtain a mixed solution composed of the metal alkoxide (B) and acetylacetone.

The polymerizable monomer (A) having the (meth) acryl group, the photopolymerization initiator (D), and the polymerization inhibitor were uniformly mixed to obtain a mixture. A mixture of the polymerizable monomer (A) having the (meth) acrylic group (A), the photopolymerization initiator (D), and a polymerization inhibitor is mixed with the metal alkoxide (B) obtained above and acetylacetone. It added to the mixed solution and stirred for 15 minutes at room temperature to obtain a photocurable nanoimprinting composition.
The obtained composition for photocurable nanoimprint was filtered with a syringe filter having a 0.2 μmφ hole diameter. The blending ratio of this photocurable nanoimprint composition is shown in Table 1.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion of the cured film, transferability, cured film thickness, sapphire selectivity, and long-term storage stability. The results are shown in Tables 2-4.

Comparative Example 3
(Production of photocurable nanoimprint composition)
As a polymerizable monomer (A) having a (meth) acryl group, hydroxyethylated o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-LEN-10) 5.0 g, 9,9 5.0 g of -bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-BPEF) was used.

  As the metal alkoxide (B), tungsten (V) ethoxide (manufactured by Alfa Aesar) was used.

  As a photopolymerization initiator (D), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (BASF Japan K.K.) 0.2 g of IRGACURE (registered trademark) 379 EG).

  As the polymerization inhibitor, 0.015 g of hydroquinone monomethyl ether and 0.002 g of butylhydroxytoluene were used.

The polymerizable monomer (A) having the (meth) acryl group, the photopolymerization initiator (D), and the polymerization inhibitor were uniformly mixed to obtain a mixture. 5.0 g of a mixture consisting of the polymerizable monomer (A) having a (meth) acrylic group, a photopolymerization initiator (D) and a polymerization inhibitor was collected, and 0.1 g of the metal alkoxide (B) and a solvent were used. When 4.9 g of propylene glycol monomethyl ether was added and stirred for 15 minutes at room temperature, a photocurable nanoimprinting composition with a white precipitate was obtained. The blending ratio of this photocurable nanoimprint composition is shown in Table 1.
The resulting photocurable nanoimprinting composition on which the white precipitate was deposited was filtered through a 0.2 μmφ hole diameter syringe filter.

  Using the filtered composition for photo-curable nanoimprint, the substrate adhesion of the cured film, transferability, cured film thickness, sapphire selectivity, and long-term storage stability were evaluated. The results are shown in Tables 2-4.

Comparative Example 4
(Production of photocurable nanoimprint composition)
As the polymerizable monomer (A) having a (meth) acrylic group, 5.0 g of polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-200), tricyclodecane dimethanol diacrylate (new) 5.0 g of Nakamura Chemical Co., Ltd. (NK ester A-DCP) was used.

  As a photopolymerization initiator (D), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (BASF Japan K.K.) 0.2 g of IRGACURE (registered trademark) 379 EG).

  As the polymerization inhibitor, 0.015 g of hydroquinone monomethyl ether and 0.002 g of butylhydroxytoluene were used.

  The polymerizable monomer (A) having the (meth) acryl group, the photopolymerization initiator (D), and the polymerization inhibitor were uniformly mixed to obtain a mixture. The mixture of the polymerizable monomer (A) having the (meth) acrylic group, the photopolymerization initiator (D), and a polymerization inhibitor is diluted with 2.0 g of acetylacetone as a solvent, and the diluted mixture is diluted. It filtered with the syringe filter of 0.2 micrometer (phi) hole diameter. The blending ratio of this photocurable nanoimprint composition is shown in Table 1.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion of the cured film, transferability, cured film thickness, sapphire selectivity, and long-term storage stability. The results are shown in Tables 2-4.

Comparative Example 5
(Production of photocurable nanoimprint composition)
As a polymerizable monomer (A) having a (meth) acryl group, hydroxyethylated o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-LEN-10) 5.0 g, 9,9 5.0 g of -bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-BPEF) was used.

  As a metal alkoxide, 0.3 g of 1-butanol solution of 85% by mass zirconium butoxide (tetrabutylzirconium alkoxide) was used.

  As β-hydroxy ketones (C), 9.7 g of 4-hydroxy-4-methyl-2-pentanone was used.

  As a photopolymerization initiator (D), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (BASF Japan K.K.) 0.2 g of IRGACURE (registered trademark) 379 EG).

  As the polymerization inhibitor, 0.015 g of hydroquinone monomethyl ether and 0.002 g of butylhydroxytoluene were used.

The metal alkoxide and β-hydroxy ketone (C) were uniformly mixed to obtain a mixed solution consisting of the metal alkoxide and β-hydroxy ketone (C).
The polymerizable monomer (A) having the (meth) acryl group, the photopolymerization initiator (D), and the polymerization inhibitor were uniformly mixed to obtain a mixture. 2.0 g of a mixture comprising the polymerizable monomer (A) having a (meth) acrylic group, a photopolymerization initiator (D) and a polymerization inhibitor was collected, and the metal alkoxide and β-hydroxyketone obtained above were collected. A mixed solution 2.0 g of the mixture (C) was added and stirred at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition.
The obtained composition for photocurable nanoimprint was filtered with a syringe filter having a 0.2 μmφ hole diameter. The blending ratio of this photocurable nanoimprint composition is shown in Table 1.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion of the cured film, transferability, cured film thickness, sapphire selectivity, and long-term storage stability. The results are shown in Tables 2-4.

Example 8
(Manufacture of surface processed sapphire substrates)
The photocurable nanoimprint composition obtained in Example 7 was spin-coated on a sapphire substrate (single mirror surface, thickness 430 μm, surface roughness Ra ≦ 0.1 nm, plane orientation C plane) at 3000 rpm for 30 seconds. And dried at 160 ° C. for 2 minutes to obtain a sapphire substrate on which the coating film of the photocurable nanoimprinting composition was coated with a thickness of about 0.2 μm.

  A photocurable nanoimprint obtained as described above using a resin mold having a hole pattern with a diameter of 230 nm and a depth of 200 nm and a vacuum pressure UV curing apparatus (VS005-200C-UV) manufactured by Mikado Technos Co., Ltd. An optical nanoimprint was performed by applying a pressure of 3 MPa to a sapphire substrate having a coating film of the composition for irradiation and irradiating light with a metal halide lamp for 60 seconds. The resin mold was peeled off to obtain a sample in which the pillar pattern was transferred onto the sapphire substrate.

  Using a reactive ion etching apparatus, surface treatment of the sapphire substrate was performed by dry etching of the sapphire substrate, using the above sample as a mask under dry etching conditions using chlorine gas. When the obtained sample was observed by SEM, it was confirmed that the surface of the sapphire substrate was etched and the surface was processed.

Claims (8)

(A) a polymerizable monomer having a (meth) acryl group,
(B) The following formula (1)

(Where
M is tungsten, tin, indium, antimony, molybdenum, niobium, or hafnium;
R ¹ is an alkyl group having 1 to 10 carbon atoms, and may be the same group or different groups,
When M is tungsten, p is 6 or 5;
When M is molybdenum or niobium, p is 5,
When M is tin or hafnium, p is 4,
When M is indium or antimony, p is 3. )
A metal alkoxide represented by
A photocurable nanoimprinting composition comprising (C) β-hydroxyketones and (D) a photopolymerization initiator.   2. The photocuring according to claim 1, wherein the polymerizable monomer having the (A) (meth) acrylic group includes a polymerizable monomer having (a) a (meth) acrylic group and an aromatic ring. Nanoimprint composition. Furthermore, (E) The organosilicon compound which has a (meth) acryl group shown by following formula (2) is included, The composition for photocurable nanoimprint of Claim 1 or 2 characterized by the above-mentioned.

(Where
R ² is a hydrogen atom or a methyl group,
R ³ is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or an alkylene ether having 2 to 20 carbon atoms,
R ⁴ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms,
R ⁵ is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 4 carbon atoms,
R ³ or R ⁴ may be substituted with an alkyl group, an aryl group, a halogen, or a hydroxyl group. l is an integer of 1 to 3, m is an integer of 0 to 2, k is an integer of 1 to 3,
l + m + k is 4,
R ^{2, R} 3, ^{R 4} and ^{R 5} are each, when there are a plurality, the plurality of ^{R 2,} R 3, ^{R 4} and ^{R 5} may each be the same or different groups. ) Furthermore, (F) the organosilicon compound shown by following formula (3) is included, The composition for photocurable nanoimprint in any one of Claims 1-3 characterized by the above-mentioned.

(Where
R ⁶ and R ⁷ are the same or different alkyl group having 1 to 4 carbon atoms or hydrogen, R ⁸ is an aryl group, R ⁹ is an aryl group or an alkoxy group having 1 to 4 carbon atoms, and n is It is an integer of 1-10. )   It is for sapphire substrate surface processing, The composition for photocurable nanoimprints in any one of Claims 1-4. A photocurable nanoimprint composition comprising at least the following components (A) to (D):
(A) a polymerizable monomer having a (meth) acryl group,
(B) The following formula (1)

(Where
M is tungsten, tin, indium, antimony, molybdenum, niobium, or hafnium;
R ¹ is an alkyl group having 1 to 10 carbon atoms, and may be the same group or different groups,
When M is tungsten, p is 6 or 5;
When M is molybdenum or niobium, p is 5,
When M is tin or hafnium, p is 4,
When M is indium or antimony, p is 3. )
A metal alkoxide represented by
(C) β-hydroxy ketones and (D) photopolymerization initiator The process of apply | coating the composition for photocurable nanoimprint of any one of Claims 1-6 on a board | substrate, and drying after that, and forming the coating film which consists of this composition,
Contacting the pattern forming surface of the mold on which the pattern is formed with the coating film, and irradiating light in that state to cure the coating film;
A method for forming a pattern, comprising: separating the mold from a cured coating film, and forming a pattern corresponding to a pattern formed on a pattern forming surface of the mold on a substrate. 8. A surface-processed sapphire substrate, characterized in that the substrate surface is processed by dry etching with chlorine-based gas using the pattern formed on the substrate by the pattern forming method according to claim 7 as a mask. Manufacturing method.