JP2014065853A - Composition for photocurable nanoimprint and method of forming pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for photocurable nanoimprint excellent in etching resistance of chlorine-based gas, productivity and long term storage stability, and further capable of easily transferring patterns even in the case of pushing a mold at relatively low pressure, and good in nanoimprint pattern transferring properties such as good in adhesion with base materials of the patterns and good in releasability from a mold.SOLUTION: A composition for photocurable nanoimprint contains (A) an organosilicon compound having a (meth)acrylic group, (B) heteropolyacid, (C) a polymerizable monomer having a (meth)acrylic group, and (D) a photoinitiator. (E) an organosilicon compound and/or (F) a fluorinated organosilicon compound may be contained.

Description

  The present invention relates to a novel photocurable nanoimprint composition, and further relates to a novel pattern formation 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 blended an organosilicon compound having a specific structure, a (meth) acrylic group-containing silicon compound, and a partial hydrolyzate obtained by hydrolyzing a metal alkoxide with a specific amount of water. A photocurable nanoimprint composition was proposed (see 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, substrate adhesion and transferability, oxygen gas and Although etching resistance to fluorine-based gas is good, there is room for improvement in etching resistance to chlorine-based gas.

  Moreover, since the composition for photocurable nanoimprint described in Patent Document 5 stores the metal alkoxide in the presence of water, a gelled product and a precipitate are generated based on the hydrolysis reaction of the metal alkoxide, and is stable for long-term storage. There was room for improvement in sex. As described above, the metal alkoxide is an effective component for improving the etching resistance, but has been one factor that deteriorates the long-term storage stability. From such a point of view, there has been a demand for a photocurable nanoimprint composition that has good long-term storage stability, and at the same time has high etching resistance, particularly etching resistance to chlorine.

  The purpose of the present invention is a photo-curable nanoimprint that is excellent in etching resistance of chlorine-based gas and has excellent long-term storage stability while maintaining the physical properties of the prior art such as good adhesion and transferability between the pattern and the substrate. It is to provide a composition for use.

  The present inventor has made various studies in order to improve etching resistance of chlorine-based gas and long-term storage stability and to improve nanoimprint pattern transferability. As a result, it has been found that by using a heteropolyacid, the etching resistance to a chlorine-based gas can be improved while maintaining good storage stability for a long period of time, and the present invention has been completed.

That is, the present invention
(A) The following formula (1)

(Where
R ¹ is a hydrogen atom or a methyl group,
R ² is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms,
R ³ 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 ⁴ is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 4 carbon atoms,
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 ^{1, R} 2, ^{R 3} and ^{R 4} respectively, when there are a plurality, the plurality of ^{R 1,} R 2, ^{R 3} and ^{R 4,} respectively, may be the same or different groups) An organosilicon compound having the (meth) acrylic group shown,
(B) a heteropolyacid,
(C) a polymerizable monomer having a (meth) acryl group, and (D) a photocurable nanoimprint composition containing a photopolymerization initiator,
further,
(E) The following formula (2)

(Where
R ⁵ and R ⁶ are the same or different alkyl group having 1 to 4 carbon atoms or hydrogen,
R ⁷ is an aryl group, R ⁸ is an aryl group or an alkoxy group having 1 to 4 carbon atoms,
n is an integer of 1-10. )
It is preferable to contain an organosilicon compound represented by
(F) Formula (3) below

(Where
R ⁹ and R ¹¹ are each an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms; R ¹⁰ is a fluorine-containing alkyl group having 1 to 100 carbon atoms or a fluorine-containing cyclo group. An alkyl group or a fluorine-containing alkoxy ether group; a is an integer of 1 to 3, b is an integer of 0 to 2, provided that a + b = 1 to 3; R ⁹ , R ¹⁰ and R ^{When a} plurality of ¹¹ are present, the plurality of R ⁹ , R ¹⁰ and R ¹¹ may be the same or different. You may contain the fluorinated organosilane compound shown by this.

The second invention is
Applying the photocurable nanoimprint composition onto a substrate 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 for producing 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 has good dispersibility, and maintains the physical properties of the prior art that the cured film has a base film adhesion and transferability after being cured as a coating film. On the other hand, the composition is suitable for forming a cured film having excellent etching resistance to chlorine gas and is excellent in long-term storage stability. Furthermore, by containing a fluorinated organosilane compound, in addition to the above effects, a composition having excellent releasability from the mold is obtained.

The present invention relates to a photocurable nanoimprint composition,
(A) The following formula (1)

(Where
R ¹ is a hydrogen atom or a methyl group,
R ² is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms,
R ³ 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 ⁴ is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 4 carbon atoms,
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 ^{1, R} 2, ^{R 3} and ^{R 4} respectively, when there are a plurality, the plurality of ^{R 1,} R 2, ^{R 3} and ^{R 4,} respectively, may be the same or different groups) (B) heteropolyacid, (C) polymerizable monomer having (meth) acrylic group (hereinafter, also simply referred to as (C) polymerizable monomer) And (D) a photopolymerization initiator.

  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 organosilicon compound (A) having a (meth) acryl group will be described.

(Organic silicon compound having (meth) acrylic group)
In the present invention, the following formula (1)
(A) The following formula (1)

(Where
R ¹ is a hydrogen atom or a methyl group,
R ² is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms,
R ³ 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 ⁴ is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 4 carbon atoms,
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 ^{1, R} 2, ^{R 3} and ^{R 4} respectively, when there are a plurality, the plurality of ^{R 1,} R 2, ^{R 3} and ^{R 4} may each be the same or different groups)
The organosilicon compound having a (meth) acryl group (hereinafter also referred to simply as “organosilicon compound having a (meth) acryl group”) (A) is used.

  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, in addition to good adhesion to the substrate, the inorganic component and the organic component are dispersed in a relatively homogeneous state (the inorganic component is It will not be in a dispersed state that is extremely agglomerated). As a result, it is estimated that a uniform transfer pattern and a uniform residual film can be formed.

In the formula (1), R ¹ 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 ² is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 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, 2,4,4-trimethylpentylene group, decaoctylene group; cyclopropylene group, cyclobutylene group, cyclopropylmethylene , Cyclopentyl alkylene group, cyclohexylene group, and a cycloalkylene group such as a cyclooctylene 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 ³ 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 ⁴ 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 ⁴ generates an alcohol derived from R ⁴ 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 ⁴ 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, and 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.

(Heteropoly acid)
The composition for photocurable nanoimprinting of the present invention can improve etching resistance to chlorine gas by blending a heteropolyacid. As described above, the metal alkoxide such as zirconium alkoxide used in Patent Document 5 is one factor that deteriorates the long-term storage stability although it has an effect of improving etching resistance. In the present invention, even when a metal alkoxide is not used, it is possible to maintain good etching resistance. Therefore, in the case where a metal alkoxide is not included, in addition to the effect of excellent etching resistance against chlorine gas, long-term storage stability Can be improved. Of course, the present invention does not exclude the use of a metal alkoxide in addition to the heteropolyacid.

  The (B) heteropolyacid of the present invention is a general term for compounds in which another kind of oxo acid is polymerized around one kind of oxo acid. Further, the heteropolyacid may be an anhydride or a hydrate containing crystal water. In addition, in the present invention, when simply expressed as heteropolyacid, it is a concept including heteropolyacid anhydride and heteropolyacid hydrate, and similarly, for example, when expressed as silicotungstic acid, which is a subordinate concept of heteropolyacid. Includes silicotungstic acid anhydride and silicotungstic acid hydrate.

In the present invention, the (B) heteropolyacid is preferably a compound represented by the following general formula (4).
_{H x [M m · M '} n O r] · yH 2 O (4)
(In the formula, M represents a hetero element composed of one or two elements selected from silicon, phosphorus, and boron, M ′ represents one or more poly elements selected from tungsten, molybdenum, niobium, and vanadium; (An integer of 10-100, m is an integer of 1-10, n is an integer of 6-40, x is an integer of 1-10, y represents an integer of 0-50.)
In Formula (4), H represents a hydrogen atom, O represents an oxygen atom, and H ₂ O represents a water molecule. M represents a hetero element composed of one or two elements selected from silicon, phosphorus and boron. That is, if m is 1, it consists of a kind of heteroelement M, but if m is 2 or more, it consists of one or two kinds of heteroelement M. For example, if m is 2, both of the two Ms may be silicon, one of the two Ms may be silicon, and the remaining one M may be phosphorus or boron. .

  M ′ represents one or more poly elements selected from tungsten, molybdenum, niobium, and vanadium. For example, if n is 12, all of the 12 M ′ may be tungsten, or a part of the 12 M ′ may be molybdenum, niobium or vanadium.

  Examples of suitable heteropolyacids include silicotungstic acid, phosphotungstic acid, silicomolybdic acid, phosphomolybdic acid, phosphomolybdotungstic acid, phosphomolybdotungstic acid, phosphovanadotungstic acid, caivanadotungstic acid, and caivanadomolybdenum. Acid, borotungstic acid, boromolybdic acid, and boromolybdotungstic acid are preferred.

  Among these, silicotungstic acid is more preferable in consideration of the dispersibility of the composition of the present invention and the etching resistance to chlorine-based gas.

  In the above formula (4), x is preferably an integer of 2 to 6, and more preferably 3 or 4. M is preferably 1 to 3, and more preferably 1. n is preferably an integer of 8 to 12, and more preferably 12. r is preferably 20 to 60, more preferably 35 to 45, and particularly preferably 40. y is preferably an integer of 10 to 40, and more preferably an integer of 20 to 30.

Examples of preferred heteropolyacids based on the above formula (4) are H ₃ [PW _(n) Mo _(12-n) O ₄₀ ] yH ₂ O, H ₃ [PV _(12-n) W _(n) O _{40] yH 2 O, H 4} [SiW (n) Mo (12-n) O 40] yH 2 O, H 4 [SiV (12-n) W (n) O 40] yH 2 O, H 4 [SiW ₁₂ O ₄₀ ] yH ₂ O (where n is an integer of 8-12 or less, y is an integer of 20-30, H is a hydrogen atom, P is a phosphorus atom, Si is a silicon atom, Mo is a molybdenum atom) , V represents a vanadium atom, W represents a tungsten atom, and O represents an oxygen atom), and a silicotungstic acid represented by H ₄ [SiW ₁₂ O ₄₀ ] 24H ₂ O is particularly preferable.

In particular, silicotungstic acid represented by H ₄ [SiW ₁₂ O ₄₀ ] 24H ₂ O (another notation is SiO ₂ · 12WO ₃ · 26H ₂ O; silicotungstic acid 26 water) is a photocurable nanoimprinting composition. From the viewpoint of improving the dispersibility of the metal and the etching resistance to chlorine-based gas.

  In addition, from the viewpoint of improving the dispersibility of the photocurable nanoimprinting composition of the present invention and the etching resistance to chlorine gas, the heteropolyacid is a polymerizable monomer (C) having a (meth) acryl group of 100 mass. It is preferable to set it as 0.1-50 mass parts with respect to a part, It is more preferable to set it as 0.2-40 mass parts, It is especially preferable to set it as 1-20 mass parts.

Next, the polymerizable monomer (C) having a (meth) acryl group will be described.
(Polymerizable monomer having (meth) acrylic group (C))
In the present invention, the polymerizable monomer (C) having a (meth) acryl group (hereinafter also simply referred to as “polymerizable monomer (C)”) 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 nanoimprints of the present invention, in addition to the polymerizable monomer (C) 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 (C) does not contain an organosilicon compound having a (meth) acryl group represented by the formula (1). A preferable compound includes a polymerizable monomer having a (meth) acryl group and containing no silicon atom in the molecule. These polymerizable monomers (C) 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 (C) 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, hydrophenoxyethylene glycol modified (meth) acrylate, hydroxyphenoxypropylene glycol modified (meth) acrylate, alkylphenol ethylene glycol modified (meth) acrylate, alkylphenol propylene glycol modified (meth) acrylate, the following formula (5)

(Where
R ¹² is a hydrogen atom or a methyl group,
R ¹³ 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 (6)

(Where
R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or a methyl group,
R ¹⁶ and R ¹⁷ 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 (7). Also good.

(In the formula, R ¹⁸ and R ¹⁹ 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 (C), a monomer having a ο-phenylphenol group in the molecule and a monomer having a fluorene structure in the molecule can improve the etching resistance of chlorine gas. A dimer is preferable, and a (meth) acrylate having an o-phenylphenol group in the molecule represented by the formula (5) and a di (meth) acrylate having a fluorene structure represented by the formula (6) are preferable.

  Moreover, the said polymerizable monomer (C) may be individual according to the use to be used and the shape of the pattern to form, and may be used combining several types.

  The (meth) acrylate having an o-phenylphenol group in the molecule represented by the formula (5) will be described.

  Following formula (5)

(Where
R ¹² is a hydrogen atom or a methyl group,
R ¹³ 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 ¹² 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 ¹³ 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 (5) include 3-ο-phenylphenol methyl (meth) acrylate, 3-ο-phenylphenol ethyl (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 (6) will be described.

  Following formula (6)

(Where
R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or a methyl group,
R ¹⁶ and R ¹⁷ 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 (7). Also good. )

(In the formula, R ¹⁸ and R ¹⁹ are an ethylene group or a propylene group, and n is an integer of 1 to 3.)
, R ¹⁴ and R ¹⁵ 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 ¹⁶ and R ¹⁷ 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 (7). 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- Hydroxyalkylene group such as hydroxy-2,4,4-trimethylpentylene group, etc., ethylene glycol group, diethylene glycol group, triethylene glycol group, tetraethylene glycol group, polyethylene glycol group such as pentaethylene glycol group, propylene glycol group, Examples thereof include polypropylene glycol groups such as dipropylene glycol group, tripropylene glycol group, and tetrapropylene glycol 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 (7) wherein R ¹⁸ and R ¹⁹ are ethylene groups and n is 1 to 2; or ^{R 18, R 19} is a propylene group, and the group of n is 1-2 Masui.
Examples of the di (meth) acrylate having a fluorene structure in the molecule represented by the formula (6) 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.

  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 (C).

  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 0.1-10 mass parts with respect to 100 mass parts of said polymerizable monomers (C), and 0.1-5 mass parts It is more preferable from the viewpoint of etching resistance.

(Organic silicon compound)
In the present invention, the following formula (2)
(E) The following formula (2)

(Where
R ⁵ and R ⁶ are the same or different alkyl group having 1 to 4 carbon atoms or hydrogen,
R ⁷ is an aryl group, R ⁸ is an aryl group or an alkoxy group having 1 to 4 carbon atoms,
n is an integer of 1-10. ) (E) is preferably contained, and by using this organosilicon compound, a chlorine-based gas, an oxygen-based gas, a fluorine-based gas is contained. Etching resistance with respect to etc. improves, and especially etching resistance with respect to chlorine gas can be improved.

  The presence or absence of water is not particularly limited in the photocurable nanoimprint composition of the present invention. When water is not blended, there is an effect in terms of long-term storage stability, but there are cases where the transferability is inferior to some extent. However, even when water is not added, the transferability can be improved by using the organosilicon compound of the formula (2).

In the formula (2), R ⁵ and R ⁶ 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. The photocurable nanoimprinting composition of the present invention may contain an 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 and R ⁶ are methyl. It is preferably an alkyl group having 1 to 4 carbon atoms such as a group, an ethyl group, a propyl group, an isopropyl group, or a butyl group.

In R ⁷ and R ⁸ , examples of the aryl group include aryl groups such as a phenyl group, a biphenyl group, and a naphthyl group, and among them, a phenyl group is preferable.

R ⁸ represents an alkoxy group such as methyl alkoxy group, ethyl alkoxy group, propyl alkoxy group, isopropyl alkoxy group, butyl alkoxy group, sec-butyl alkoxy group, isobutyl alkoxy group, 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. Considering that the alkoxy group represented by R ⁸ 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, It is preferably an alkoxy group having 1 to 4 carbon atoms 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, or a tert-butyl alkoxy group. . 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 ⁷ and R ⁸ are preferably aryl groups from the viewpoint of forming a cured film having good etching resistance, in particular, etching resistance to chlorine gas.

  The organosilicon compound may be a single compound or a plurality of organosilicons having different values of n as long as n satisfies an integer of 1 to 10 in the formula (2). 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.

(Fluorinated organosilane compound)
In the present invention, the following formula (3)
(F) Formula (3) below

(Where
R ⁹ and R ¹¹ are each an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms; R ¹⁰ is a fluorine-containing alkyl group having 1 to 100 carbon atoms or a fluorine-containing cyclo group. An alkyl group or a fluorine-containing alkoxy ether group; a is an integer of 1 to 3, b is an integer of 0 to 2, provided that a + b = 1 to 3; R ⁹ , R ¹⁰ and R ^{When a} plurality of ¹¹ are present, the plurality of R ⁹ , R ¹⁰ and R ¹¹ may be the same or different. ) (F) can be further included (hereinafter also referred to simply as “fluorinated organosilane compound”). By using this fluorinated organosilane compound, the releasability from the mold can be improved without impairing the adhesion of the pattern to the substrate.

In the formula (3), R ⁹ and R ¹¹ are an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group. C1-C4 alkyl groups, such as butyl group, sec-butyl group, isobutyl group, ter-butyl group. In consideration of the fact that the alkoxy group composed of —OR ^{9 in the} formula (3) becomes an alcohol that can be easily mixed with other components, specifically, R ⁹ is a methyl group, an ethyl group, or a propyl group. Is more preferable.
R ¹⁰ is a fluorine-containing alkyl group, a fluorine-containing cycloalkyl group, or a fluorine-containing alkoxy ether group. Here, the fluorine-containing alkyl group means one in which one or more hydrogen atoms of the alkyl group are substituted with fluorine atoms, and other fluorine-containing cycloalkyl groups or fluorine-containing alkoxy ether groups are each similarly cycloalkyl. Group, an alkoxy ether group in which one or more hydrogen atoms are substituted with fluorine atoms. The fluorine-containing alkyl group preferably has 1 to 10 carbon atoms, and the fluorine-containing cycloalkyl group preferably has 3 to 10 carbon atoms. In addition, the fluorine-containing alkoxy ether group in the present invention is obtained by substituting one or more hydrogen atoms with fluorine atoms in the alkoxy ether group represented by the following formula (8).

(In the formula, X is an integer of 1 or more, and Y is an integer of 2 or more)
In the above formula (8), X is preferably 1 to 6, and Y is preferably 5 to 50.
^Also, if ^R 9, R ^10, and ^{the R 11} are present in plural, the plurality of ^{R 9, R 10,} and ^{R 11} are identical or may be different groups.

Specific examples of these fluorinated organosilane compounds are (heptadecafluoro-1,1,2,2-tetrahydrodecyl) -triethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl). ) -Trimethoxysilane, nonafluorohexyltriethoxysilane, nonafluorohexyltrimethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) -triethoxysilane, (tridecafluoro-1,1, 2,2-tetrahydrooctyl) -trimethoxysilane, pentafluoro-1,1,2,2-tetrahydropentyltriethoxysilane, pentafluoro-1,1,2,2-tetrahydropentyltrimethoxysilane, (3,3 , 3-trifluoropropyl) dimethylethoxysilane, (3,3, -Trifluoropropyl) dimethylmethoxysilane, (3,3,3-trifluoropropyl) methyldiethoxysilane, (3,3,3-trifluoropropyl) methyldimethoxysilane, (3,3,3-trifluoropropyl) ) Triethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, perfluoropropyltriethoxysilane, perfluoropropyltrimethoxysilane, 5,5,6,6,7,7,8,8, 9,9,10,10,10-tridecafluoro-2- (tridecafluorohexyl) decyltriethoxysilane, 5,5,6,6,7,7,8,8,9,9,10,10 , 10-tridecafluoro-2- (tridecafluorohexyl) decyltrimethoxysilane, perfluorododecyl-1H, 1H, 2 , 2H-triethoxysilane, perfluorododecyl-1H, 1H, 2H, 2H-trimethoxysilane, perfluorotetradecyl-1H, 1H, 2H, 2H-triethoxysilane, perfluorotetradecyl-1H, 1H, 2H , 2H-trimethoxysilane, 3- (perfluorocyclohexyloxy) propyltrimethoxysilane and the like, and in the alkoxy ether group represented by the above formula (8), one or more hydrogen atoms are substituted with fluorine atoms. As an example of a fluorinated organosilane compound having a fluorine-containing alkoxy ether group, a trade name includes, for example, OPTOOL HD-1100TH manufactured by Daikin Industries, Ltd. Among these, the interaction between molecules is relatively weak, and the disorder of the molecular arrangement structure seems to be advantageous for surface releasability, and the ease of hydrolysis of the alkoxy group consisting of —OR ^{9 in the} above formula (3). In consideration, (tridecafluoro-1,1,2,2-tetrahydrooctyl) -trimethoxysilane and (3,3,3-trifluoropropyl) trimethoxysilane are preferable.

(Method for producing photocurable nanoimprint composition)
The composition for photocurable nanoimprint of the present invention is obtained by mixing the components (A) to (D) and, in addition to the components (E) and (F), other additives and the like as necessary. Is.

  In the present invention, the organosilicon compound (A) having a (meth) acryl group and the heteropolyacid (B) constituting the photocurable nanoimprint composition are preferably blended in the following amounts. That is, the composition for photocurable nanoimprint is used in an amount of 3 to 300 parts by mass of the organosilicon compound (A) having the (meth) acrylic group, 100 parts by mass of the polymerizable monomer (C), the heteropolyacid ( B) It is preferable that 0.1-50 mass parts and the said photoinitiator (D) 0.1-10 mass parts are included.

  When the blending amount of the organosilicon compound (A) having a (meth) acrylic group and the heteropolyacid (B) satisfies the above range, the composition for photo-curable nanoimprint having good dispersibility and good coating appearance is obtained. Purification by filtration is easy and productivity can be improved. Furthermore, chlorine etching resistance and substrate adhesion are particularly good. Moreover, since nanoimprinting at a relatively low pressure is possible, the life of the mold to be used can be extended. In consideration of dispersibility and nanoimprint at a relatively low pressure, the blending amount of the organosilicon compound (A) having a (meth) acrylic group is 5 to 250 masses with respect to 100 mass parts of the polymerizable monomer (C). The amount of the heteropolyacid (B) is more preferably 0.2 to 40 parts by mass.

  Furthermore, the blending amount (A) of the organosilicon compound having a (meth) acryl group is particularly preferably 8 to 200 parts by weight, and the blending amount of the heteropolyacid (B) is 0.5 to 30 parts by weight. It is particularly preferred that The amount of the organosilicon compound (A) having a (meth) acryl group is most preferably 10 to 180 parts by mass, and the amount of the heteropolyacid (B) is most preferably 1 to 20 parts by mass. preferable.

In the present invention, the organosilicon compound (A) having a (meth) acryl group and the heteropolyacid (B) constituting the photocurable nanoimprint composition may further contain an organosilicon compound (E). By including the organosilicon compound (E), it is possible to improve etching resistance, particularly etching resistance against chlorine-based gas.
The amount of the organosilicon compound (E) used is preferably 10 to 400 parts by mass of the organosilicon compound (E) with respect to 100 parts by mass of the polymerizable monomer (C) described in detail below.
The amount of the organosilicon compound (E) used is more preferably 20 to 350 parts by mass with respect to 100 parts by mass of the polymerizable monomer (C) described in detail below. The amount of E) used is particularly preferably 30 to 300 parts by mass, and the amount of the organosilicon compound (E) used is most preferably 40 to 250 parts by mass.

In the present invention, the organosilicon compound (A) having a (meth) acryl group constituting the photocurable nanoimprint composition and the heteropolyacid (B) may further contain a fluorinated organosilane compound (F). it can. By including the fluorinated organic silane compound (F), the releasability from the mold can be improved without impairing the adhesion of the pattern to the substrate. The usage-amount of a fluorinated organosilane compound (F) shall be 0.001-4 mass parts of fluorinated organosilane compounds (F) with respect to 100 mass parts of polymerizable monomers (B) explained in full detail below. It is preferable.
The amount of the fluorinated organosilane compound (F) used is more preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the polymerizable monomer (B) described in detail below. The amount of the fluorinated organosilane compound (F) used is particularly preferably 0.03 to 2 parts by mass, and the amount of the fluorinated organosilane compound (F) used is 0.05 to 1 part by mass. Most preferred.

(Method for producing photocurable nanoimprint composition: water used and its amount)
In the present invention, the organosilicon compound (A) having a (meth) acryl group constituting the photocurable nanoimprinting composition, the organosilicon compound (E), and / or the fluorinated organosilane compound (F) The presence or absence of hydrolysis is not particularly limited, but from the viewpoint of solubility in the composition of the heteropolyacid and transferability, a state in which a part of the alkoxy group is partially hydrolyzed by hydrolysis is preferable.

  The amount of water newly added to the hydrolysis is preferably a constant amount in consideration of long-term storage stability. That is, the amount of water to be added can be preferably selected from 0-fold mol to less than 2.0-fold mol with respect to the number of moles of all alkoxy groups, and more preferably 0-fold with respect to the number of moles of all alkoxy groups. It is more than mol and less than 1.2 times mol. The number of moles of all alkoxy groups means the number of moles of the organosilicon compound (A) having a (meth) acryl group and the alkoxy present in one molecule of the organosilicon compound (A) having the (meth) acryl group. When the product of the number of groups and the organosilicon compound (E) are used, the number of moles of the organosilicon compound (E) used and the number of alkoxy groups present in one molecule of the organosilicon compound (E) Product, the product of the number of moles of the fluorinated organic silane compound (F) used and the number of alkoxy groups present in one molecule of the fluorinated organic silane compound. Is added.

  In the present invention, the heteropolyacid (B) is an acid used for hydrolysis, but an acid may be used in addition to the heteropolyacid (B). Acids used include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, organic phosphoric acid, formic acid, acetic acid, acetic anhydride, chloroacetic acid, propionic acid, butyric acid, valeric acid, citric acid, gluconic acid, Examples thereof include organic acids such as succinic acid, tartaric acid, lactic acid, fumaric acid, malic acid, itaconic acid, oxalic acid, mucinic acid, uric acid, barbituric acid, and p-toluenesulfonic acid, and acidic cation exchange resins. When an acid is used, it is not particularly limited, but the amount used is an amount such that the amount of hydrogen ions is 0.0001 times to 0.01 times mol relative to the number of moles of all alkoxy groups. It is preferable that The acid can be used as it is, but it is preferable to use an acid aqueous solution or a solution dispersed in water. In this case, it is preferable to use one having a concentration of 0.1 to 6N. In this case, the used water is included in the amount of water used.

In the present invention, the photocurable nanoimprinting composition comprises an organosilicon compound (A) having a (meth) acryl group (organosilicon in the case of using an organosilicon compound (E) and / or a fluorinated organosilane compound (F)). Compound (E) and / or fluorinated organosilane compound (F) are also mixed with polyheteroacid.
Examples of the method for adding an acid other than polyheteroacid or water include, for example, adding a predetermined amount of acid or water to an organosilicon compound (A) having a (meth) acrylic group and hydrolyzing, or (meth) A predetermined amount of acid or water is added to the mixture of the organic silicon compound (A) having the acrylic group and the organic silicon compound (E) for hydrolysis, or the organic silicon compound (A) having the (meth) acryl group and the organic Hydrolysis by adding a predetermined amount of acid or water to a mixture of the silicon compound (E) and the fluorinated organosilane compound (F), or an organosilicon compound (A) having a (meth) acryl group and the fluorinated organosilane After adding a predetermined amount of water or acid to the mixture of the compound (F) for hydrolysis, an organosilicon compound (E) is further added, and a predetermined amount of acid or water is added for hydrolysis.

  Moreover, what is necessary is just to implement mixing of the component to hydrolyze and water at the temperature of 5 to 60 degreeC. At this time, a diluting solvent may be used to facilitate the hydrolysis. As a dilution solvent, a C1-C4 alcohol is preferable and it is preferable to use ethanol especially. Although the usage-amount of a dilution solvent should just be suitably determined with the kind of component to hydrolyze, it is preferable that it is 50-400 mass parts with respect to 100 mass parts of mixtures of the component to hydrolyze.

(Production method of photocurable nanoimprint composition: hydrolysis conditions)
In the present invention, the reaction temperature in the hydrolysis is not particularly limited, but is usually selected from the range of 5 ° C to 60 ° C. The reaction time may be appropriately selected in consideration of the reaction temperature, and is usually selected from the range of 10 minutes to 12 hours.

(Usage and physical properties of photocurable nanoimprint composition)
According to said method, the composition for photocurable nanoimprint can be prepared. An alcohol derived from an alkoxy group is produced during hydrolysis. The composition for photocurable nanoimprinting of the present invention can also contain alcohol produced as a by-product during hydrolysis and water used for hydrolysis. Furthermore, the diluent solvent used in order to advance a hydrolysis easily can also be included.

  In consideration of ease of mixing with other components, productivity of the photocurable nanoimprint composition, etc., the photocurable nanoimprint composition has a viscosity at 25 ° C. of 0.1 to 100 mPa · sec. Is preferred. This viscosity value is a value measured with a tuning fork viscometer: AND VIBRO VISCOMETER SV-1A. When used in a condition containing by-produced alcohol, water used, and dilution solvent used for dilution. Is a value obtained by measuring those including these.

(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.

  In use of the photocurable nanoimprint composition of the present invention, the photocurable nanoimprint composition is used by being applied onto a substrate. In this case, the photocurable nanoimprint composition is diluted with a solvent and used. You can also Moreover, a solvent, a stabilizer, and other well-known additives can also be mix | blended for the objective of stabilizing the composition for photocurable nanoimprint of this invention, or another objective. 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 Nate, butyl acetate, 2-heptanone, methyl isobutyl ketone, diacetone alcohol, acetylacetone, t- Chill alcohol, and polyethylene glycol, other alcohols. When using a solvent, the amount used is not particularly limited and is appropriately selected according to the thickness of the target coating film. 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 to 99% by mass.

  The stabilizer used can be used without any limitation as long as it is generally known as a stabilizer for sol-gel components. For example, α-hydroxycarboxylic acid alkyl ether such as methoxyacetic acid; glycolic acid Α-hydroxycarboxylic acids such as lactic acid, oxalic acid, mandelic acid, 2-hydroxyisobutyric acid; ethanolamines such as diethanolamine; diketones such as diacetyl, 2,5-hexanedione, acetylacetone, methylpropyl diketone, and dimedone Can be mentioned. When a stabilizer is used, the amount used is not particularly limited, but it is preferable to adjust the amount used according to the amount of the sol-gel component.

  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 blending the surfactant, the proportion of 0.0001 to 0.1 parts by weight, preferably 0.0005 to 0.01 parts by weight, with respect to 100 parts by weight of the polymerizable monomer (C). Can be blended.

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 lauryl ether, etc. 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, it is 0.01 to 1.0 part by weight, preferably 0.1 to 0.5 part by weight with respect to 100 parts by weight of the polymerizable monomer (C). Can be blended.

  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, is appropriately selected within a range that does not affect the formation of the pattern from the mold, and is usually 1 to 100 parts by mass of the polymerizable monomer (C). It is suitably selected from the range of 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 (C).

  The composition for photocurable nanoimprinting of the present invention is an organosilicon compound (A) having a (meth) acryl group, a heteropolyacid (B), a polymerizable monomer (C), a photopolymerization initiator (D), and necessary. It is obtained by mixing the organosilicon compound (E) blended as needed, the fluorinated organosilane compound (F) blended as needed, and other additive components. 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 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 to 0.1 μm.

  What is necessary is just to determine a drying temperature suitably as temperature which a coating film dries, and it can select normally from the range of 40 to 150 degreeC. In order to apply thinly, it is also possible to apply the photocurable nanoimprinting composition of the present invention diluted with an organic solvent, in which case the drying temperature depends on the boiling point and volatility of the organic solvent used. May be determined as appropriate.

  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 to 300 seconds. Although it depends on the thickness of the coating film, etc., it is usually 1 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.

  By processing the surface of the sapphire substrate, improvement of LED light extraction efficiency, homogeneous GaN growth with little crystal transition, and prevention of cracks in the GaN layer are expected.

(Use of laminates with patterns formed from cured films (used as replica molds))
Although a pattern can be formed on a substrate by etching by the above method, the photocurable nanoimprint composition of the present invention has excellent performance and can be used for other applications. For example, a cured film made of the photocurable nanoimprint composition has excellent hardness because the inorganic component is well dispersed. Therefore, the laminated body in which the pattern which consists of a cured film was formed on the board | substrate can also be used as a replica metal mold | die for nanoimprint.

  When used as this nanoimprint replica mold, it is preferable to react a fluorine-containing silane coupling agent on the surface of the laminate. By reacting the silane coupling agent, the releasability between the laminate surface and another substance can be improved. It is considered that alkoxy groups remain in the cured film and can be chemically bonded to the silane coupling agent. Therefore, the laminate obtained by reacting the silane coupling agent is further excellent in releasability.

  As the silane coupling agent, a known silane coupling agent can be used as long as it is a silane coupling agent containing a fluorine atom capable of improving releasability. Specific examples include those in which part or all of hydrogen in the alkyl chain of a trihalogenated organosilane molecule or trialkoxyorganosilane molecule is substituted with fluorine.

  The reaction between the silane coupling agent and the laminate is not particularly limited, but is preferably performed under humidified conditions. Specifically, the reaction is preferably performed under conditions of a relative humidity of 40 to 100%. Both can be made to react by making a silane coupling agent and a laminated body contact under the said humidity. Although the temperature at the time of making it react is not restrict | limited in particular, It is preferable that it is 40-80 degreeC. In addition, in the case of a liquid silane coupling agent, the surface on which the pattern is formed may be immersed in the liquid, or applied to the surface by a known method such as dip coating, spin coating, or splatte. . The time for the reaction can be appropriately selected depending on the temperature and relative humidity.

  The laminated body reacted with the silane coupling agent by such a method may be dried after washing with a fluorine-based solvent such as hydrofluoroether or alcohol. The obtained laminate has excellent mold release performance and can be used as a replica mold for nanoimprint.

  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 photocurable nanoimprint composition was diluted with acetylacetone, and a sapphire substrate (single mirror surface, thickness 430 μm, surface roughness Ra ≦ 0.1 nm, plane orientation) C surface) was spin-coated at 3000 rpm for 30 seconds, dried at 120 ° C. for 2 minutes, and then irradiated with UV to prepare a cured film of a photocurable nanoimprint composition having a thickness of about 1 μm. ) Using 15 mm wide cellophane tape 405 (length: 5 cm), peeled after 3 reciprocations 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 releasability from molds The obtained photocurable composition for nanoimprinting was diluted with acetylacetone, and on a silicon wafer (P-type, one mirror surface, no oxide film) at 3000 rpm for 30 seconds. It spin-coated and dried at 120 degreeC for 2 minute (s), and the silicon wafer with which the coating film of the photocurable nanoimprinting composition about 1 micrometer thick was coated was obtained. Using a 20 mm long and 20 mm wide flat quartz plate as a mold, a nanoimprinting device (ImpFlex Essential, manufactured by Sanmei Electronics Co., Ltd.) applies a pressure of 0.25 MPa to the obtained silicon wafer to produce an LED light source. Photoimprinting was performed by irradiation with 365 nm light for 10 seconds. The stress (release force) at the time of peeling the quartz plate from the cured film was measured, and the release property from the mold was evaluated.

(3) Evaluation of transferability (application of photocurable nanoimprint composition)
The obtained photocurable nanoimprint composition was diluted with acetylacetone, and the diluted photocurable nanoimprint composition was applied to a silicon wafer (P-type, single mirror surface, no oxide film) at 3000 rpm for 30 seconds. It spin-coated and dried at 120 degreeC for 2 minute (s), and the silicon wafer with which the coating film of the photocurable nanoimprinting composition was coated with the thickness of about 1 micrometer 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 10 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 “×”.

(4) 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 level difference measuring instrument.
<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 nanoimprinting composition was diluted with acetylacetone, spin-coated on a silicon wafer (P-type, single mirror surface, no oxide film) at 3000 rpm for 30 seconds, and dried at 120 ° C. for 2 minutes. Thereafter, UV irradiation was performed to obtain a silicon wafer coated with a cured film of a photocurable nanoimprinting composition having a thickness of about 1 μm. The silicon wafer coated with the obtained cured film was subjected to dry etching under the same conditions as dry etching with chlorine gas on a sapphire substrate, and the thickness of the coating film with the reduced cured film in a certain time was measured with a level difference measuring instrument.

(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. .

(5) Evaluation of long-term storage stability The obtained photocurable nanoimprinting 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.
A change in fluidity and appearance (precipitation, transparency) was observed from 8 to 20 days when no change in fluidity or appearance (precipitation, transparency) was observed for 21 consecutive days or more. “Δ” was defined as “Δ”, and “x” was defined as a change in fluidity and appearance (precipitation, transparency) from 0 to 7 days.

(6) Used compounds and their abbreviations <Organic silicon compound having a methacrylic group (A)>
Trimethoxysilyl trimethylene acrylate; KBM-5103
<Heteropolyacid (B)>
H ₄ [SiW ₁₂ O ₄₀ ] 24H ₂ O (another notation is SiO ₂ · 12WO ₃ · 26H ₂ O; silicotungstic acid 26 water)
<Polymerizable monomer (C) having (meth) acrylic group>
Hydroxyethylated o-phenylphenol acrylate; A-LEN-10
9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene; A-BPEF
Polyethylene glycol diacrylate; A-200
Trimethylolpropane triacrylate; A-TMPT
Tricyclodecane dimethanol diacrylate; A-DCP
<Photopolymerization initiator (D)>
2-Dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one; 379EG
<Organic silicon compound (E)>
Diphenyldimethoxysilane; DPDMS
Diphenylsilanediol; DPSDO
Trimethoxyphenylsilane; TMPS
Tetraethoxysilane; TEOS
<Fluorinated organosilane compound (F)>
(3,3,3, -trifluoropropyl) trimethoxysilane; TFPS
<Metal alkoxide>
Zirconium butoxide

Example 1
(Production of photocurable nanoimprint composition)
In a glove box substituted with nitrogen gas, 9.6 g of ethanol, 1.5 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as the organosilicon compound (A) having a (meth) acryl group Then, silicotungstic acid 26 water (manufactured by Wako Pure Chemical Industries, Ltd.) 0.5 g was mixed as the heteropolyacid (B). This mixture was stirred at room temperature for 1 hour in an air atmosphere to obtain a mixture of an organosilicon compound (A) having a (meth) acrylic group and a heteropolyacid (B).

  As a polymerizable monomer (C) 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 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 (C) having the (meth) acryl group, the photopolymerization initiator (D), and the polymerization inhibitor were uniformly mixed, and 1.0 g of the mixture was collected. To 1.0 g of the mixture, 1.0 g of the mixture of the organosilicon compound (A) having the (meth) acrylic group and the heteropolyacid (B) and 2.5 g of acetylacetone are added, and the mixture is stirred for 15 minutes at room temperature. 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. Tables 1 and 2 show the compositions and blending ratios of the photocurable nanoimprint composition.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion, release property, transferability, sapphire selectivity, and long-term storage stability of the cured film. The results are shown in Table 3.

Example 2
(Production of photocurable nanoimprint composition)
In a glove box substituted with nitrogen gas, 9.6 g of ethanol, 1.5 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as the organosilicon compound (A) having a (meth) acryl group Then, 0.5 g of silicotungstic acid 26 water (manufactured by Wako Pure Chemical Industries, Ltd.) as heteropolyacid (B) and 5.8 g of diphenyldimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) as organic silicon compound (E) were mixed. This mixture was stirred at room temperature for 1 hour in an air atmosphere to obtain a mixture of an organosilicon compound (A) having a (meth) acryl group, a heteropolyacid (B), and an organosilicon compound (E).

  After mixing the same type, the same amount of the polymerizable monomer (C), the photopolymerization initiator (D), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 1.2 g of the mixture of the organosilicon compound (A) having the (meth) acrylic group, the heteropolyacid (B) and the organosilicon compound (E) and 2.8 g of acetylacetone, the mixture is stirred and mixed at room temperature for 15 minutes, A photocurable nanoimprinting composition was obtained. The obtained composition for photocurable nanoimprint was filtered with a syringe filter having a 0.2 μmφ hole diameter. Tables 1 and 2 show the compositions and blending ratios of the photocurable nanoimprint composition.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion, release property, transferability, sapphire selectivity, and long-term storage stability of the cured film. The results are shown in Table 3.

Example 3
(Production of photocurable nanoimprint composition)
In a glove box substituted with nitrogen gas, 8.5 g of ethanol, 1.5 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as the organosilicon compound (A) having a (meth) acryl group Then, 0.5 g of silicotungstic acid 26 water (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed as the heteropolyacid (B), and 5.8 g of diphenyldimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed as the organosilicon compound (E).
While stirring and mixing the mixture, a 2.0N ethanol / water 0.6g / 2N-HCl 0.03 g 2N-HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. Further, an ethanol aqueous solution of 0.5 g of ethanol / 0.1 g of water was gradually added dropwise and stirred at room temperature for 1 hour. And a hydrolyzate of organosilicon compound (E) was obtained.

  After mixing the same type, the same amount of the polymerizable monomer (C), the photopolymerization initiator (D), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) 4.6 g of a mixture containing the hydrolyzate of the organosilicon compound (A) having the (meth) acrylic group and the heteropolyacid (B) and the organosilicon compound (E) is added to The mixture was stirred and mixed to obtain a photocurable nanoimprint composition. The obtained composition for photocurable nanoimprint was filtered with a syringe filter having a 0.2 μmφ hole diameter. Tables 1 and 2 show the compositions and blending ratios of the photocurable nanoimprint composition.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion, release property, transferability, sapphire selectivity, and long-term storage stability of the cured film. The results are shown in Table 3.

Example 4
As the polymerizable monomer (C) 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 photopolymerization initiator (D), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (BASF Japan K.K.) Manufactured by IRGACURE (registered trademark) 379 EG) 0.05 g was used.

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

  The polymerizable monomer (C) having the (meth) acryl group, the photopolymerization initiator (D), and the polymerization inhibitor were uniformly mixed, and 1.0 g of the mixture was collected. The hydrolyzate of the organosilicon compound (A) having a (meth) acrylic group obtained in Example 3 and the hydrolyzate of the heteropolyacid (B) and the organosilicon compound (E) obtained in Example 3 are included in 1.0 g of the mixture. 4.6 g of the mixture 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. Tables 1 and 2 show the compositions and blending ratios of the photocurable nanoimprint composition.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion, release property, transferability, sapphire selectivity, and long-term storage stability of the cured film. The results are shown in Table 3.

Example 5
As the polymerizable monomer (C) 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 photopolymerization initiator (D), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (BASF Japan K.K.) Manufactured by IRGACURE (registered trademark) 379 EG) 0.4 g was used.

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

  The polymerizable monomer (C) having the (meth) acryl group, the photopolymerization initiator (D), and the polymerization inhibitor were uniformly mixed, and 1.0 g of the mixture was collected. The hydrolyzate of the organosilicon compound (A) having a (meth) acrylic group obtained in Example 3 and the hydrolyzate of the heteropolyacid (B) and the organosilicon compound (E) obtained in Example 3 are included in 1.0 g of the mixture. 4.6 g of the mixture 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. Tables 1 and 2 show the compositions and blending ratios of the photocurable nanoimprint composition.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion, release property, transferability, sapphire selectivity, and long-term storage stability of the cured film. The results are shown in Table 3.

Example 6
(Production of photocurable nanoimprint composition)
In a glove box substituted with nitrogen gas, 0.14 g of a solution obtained by diluting (3,3,3, -trifluoropropyl) trimethoxysilane with ethanol to a solid content of 1% as the fluorinated organosilane compound (F) , 2.0 g of ethanol, 1.5 g of trimethoxysilyltrimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) is mixed as the organosilicon compound (A) having a (meth) acrylic group, and this mixture is mixed by stirring. Then, a 2N-HCl / ethanol mixed aqueous solution of ethanol 0.6 g / water 0.2 g / 2N-HCl 0.03 g was gradually added dropwise at room temperature. Furthermore, 0.5 g of silicotungstic acid 26 water (manufactured by Wako Pure Chemical Industries, Ltd.) as a heteropolyacid (B) is mixed, and a hydrolyzate of the fluorinated organosilane compound (F) and an organosilicon compound having a (meth) acryl group A mixture containing the hydrolyzate of (A) and the heteropolyacid (B) was obtained.

  After mixing the same type, the same amount of the polymerizable monomer (C), the photopolymerization initiator (D), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) 5.0 g of a mixture containing the hydrolyzate of the fluorinated organosilane compound (F), the hydrolyzate of the organosilicon compound (A) having a (meth) acrylic group and the heteropolyacid (B) is added at room temperature. The mixture was stirred and mixed 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. Tables 1 and 2 show the compositions and blending ratios of the photocurable nanoimprint composition.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion, release property, transferability, sapphire selectivity, and long-term storage stability of the cured film. The results are shown in Table 3.

Example 7
(Production of photocurable nanoimprint composition)
In a glove box substituted with nitrogen gas, 0.14 g of a solution obtained by diluting (3,3,3, -trifluoropropyl) trimethoxysilane with ethanol to a solid content of 1% as the fluorinated organosilane compound (F) 6.5 g of ethanol, 1.5 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as an organosilicon compound (A) having a (meth) acrylic group, and this mixture is stirred and mixed While stirring, a 2.0N ethanol / water 0.2g / 2N-HCl 0.03 g 2N-HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. Furthermore, silicotungstic acid 26 water (manufactured by Wako Pure Chemical Industries) 0.5 g was mixed as the heteropolyacid (B), and diphenyldimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.8 g was mixed as the organosilicon compound (E).
While stirring and mixing this mixture, an ethanol mixed aqueous solution of ethanol 2.0 g / water 0.4 g was gradually added dropwise at room temperature. Further, an ethanol aqueous solution of 0.5 g of ethanol / 0.1 g of water is gradually added dropwise and stirred at room temperature for 1 hour to hydrolyze the fluorinated organosilane compound (F) and an organosilicon compound having a (meth) acryl group. A mixture containing the hydrolyzate of (A) and the hydrolyzate of heteropolyacid (B) and organosilicon compound (E) was obtained.

  After mixing the same type, the same amount of the polymerizable monomer (C), the photopolymerization initiator (D), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) The hydrolyzate of the fluorinated organosilane compound (F), the hydrolyzate of the organosilicon compound (A) having a (meth) acryl group, the hydrolyzate of the heteropolyacid (B) and the organosilicon compound (E) After adding 4.7 g of the mixture, the mixture was stirred and mixed 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. Tables 1 and 2 show the compositions and blending ratios of the photocurable nanoimprint composition.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion, release property, transferability, sapphire selectivity, and long-term storage stability of the cured film. The results are shown in Table 3.

Example 8
In a glove box substituted with nitrogen gas, 8.5 g of ethanol and 7.8 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as the organosilicon compound (A) having a (meth) acryl group In addition, 0.1 g of silicotungstic acid 26 water (manufactured by Wako Pure Chemical Industries, Ltd.) as heteropoly acid (B) and 2.2 g of diphenyldimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) as organic silicon compound (E) were mixed.
While stirring and mixing the mixture, a 2.0N ethanol / water 0.6g / 2N-HCl 0.03 g 2N-HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. Further, an ethanol aqueous solution of 0.5 g of ethanol / 0.1 g of water was gradually added dropwise and stirred at room temperature for 1 hour. And a hydrolyzate of organosilicon compound (E) was obtained.

  After mixing the same type, the same amount of the polymerizable monomer (C), the photopolymerization initiator (D), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) 4.6 g of a mixture containing the hydrolyzate of the organosilicon compound (A) having the (meth) acrylic group and the heteropolyacid (B) and the organosilicon compound (E) is added to The mixture was stirred and mixed to obtain a photocurable nanoimprint composition. The obtained composition for photocurable nanoimprint was filtered with a syringe filter having a 0.2 μmφ hole diameter. Tables 1 and 2 show the compositions and blending ratios of the photocurable nanoimprint composition.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion, release property, transferability, sapphire selectivity, and long-term storage stability of the cured film. The results are shown in Table 3.

Example 9
(Production of photocurable nanoimprint composition)
As the polymerizable monomer (C) having a (meth) acrylic group, 5.0 g of polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-200), trimethylolpropane triacrylate (Shin-Nakamura Chemical) Industrial Co., Ltd., NK ester A-TMPT (5.0 g) and tricyclodecane dimethanol diacrylate (Shin Nakamura Chemical Co., Ltd., NK ester A-DCP) 15.0 g were used.

  As a photopolymerization initiator (D), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (manufactured by BASF Japan Ltd.) , IRGACURE (registered trademark) 379 EG) 0.5 g was used.

  As a polymerization inhibitor, hydroquinone monomethyl ether 0.0375 g and butylhydroxytoluene 0.005 g were used.

Said (C), (D), and the polymerization inhibitor were mixed uniformly, and 1.0g of the mixture was fractionated. The hydrolyzate of the organosilicon compound (A) having a (meth) acrylic group obtained in Example 3 and the hydrolyzate of the heteropolyacid (B) and the organosilicon compound (E) obtained in Example 3 are included in 1.0 g of the mixture. 8.2 g of the mixture 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. Tables 1 and 2 show the compositions and blending ratios of the photocurable nanoimprint composition.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion, release property, transferability, sapphire selectivity, and long-term storage stability of the cured film. The results are shown in Table 3.

Example 10
In a glove box substituted with nitrogen gas, 0.14 g of a solution obtained by diluting (3,3,3, -trifluoropropyl) trimethoxysilane with ethanol to a solid content of 1% as the fluorinated organosilane compound (F) 6.5 g of ethanol, 1.5 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as an organosilicon compound (A) having a (meth) acrylic group, and this mixture is stirred and mixed Then, a 2N-HCl / ethanol mixed aqueous solution of ethanol 2.2 g / water 0.1 g / 2N-HCl 0.03 g was gradually added dropwise at room temperature. Furthermore, silicotungstic acid 26 water (manufactured by Wako Pure Chemical Industries, Ltd.) 0.5 g was mixed as the heteropolyacid (B), and diphenylsilanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.2 g was mixed as the organosilicon compound (E). .
This mixture is stirred at room temperature for 1 hour, hydrolyzate of fluorinated organosilane compound (F), hydrolyzate of organosilicon compound (A) having (meth) acrylic group, heteropolyacid (B) and organosilicon compound. A mixture containing (E) was obtained.

After mixing the same type, the same amount of the polymerizable monomer (C), the photopolymerization initiator (D), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) 2. A mixture comprising a hydrolyzate of the fluorinated organosilane compound (F), a hydrolyzate of an organosilicon compound (A) having a (meth) acrylic group, a heteropolyacid (B), and an organosilicon compound (E). After adding 8 g and 5.0 g of acetylacetone, the mixture was stirred and mixed 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. Tables 1 and 2 show the compositions and blending ratios of the photocurable nanoimprint composition.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion, release property, transferability, sapphire selectivity, and long-term storage stability of the cured film. The results are shown in Table 3.

Example 11
(Production of photocurable nanoimprint composition)
In a glove box substituted with nitrogen gas, 6.8 g of ethanol, 1.5 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as the organosilicon compound (A) having a (meth) acryl group , 0.5 g of silicotungstic acid 26 water (manufactured by Wako Pure Chemical Industries) as heteropoly acid (B) and 4.7 g of trimethoxyphenylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) as organic silicon compound (E) were mixed. .
While this mixture was stirred and mixed, a 1.6 N ethanol / 0.6 g water / 2 0.03 g 2N HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. Further, an ethanol aqueous solution of 0.8 g of ethanol / 0.1 g of water was gradually added dropwise and stirred at room temperature for 1 hour to hydrolyze the organosilicon compound (A) having a (meth) acrylic group and the heteropolyacid (B). And a hydrolyzate of organosilicon compound (E) was obtained.

  After mixing the same type, the same amount of the polymerizable monomer (C), the photopolymerization initiator (D), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) 3.9 g of a mixture containing the hydrolyzate of the organosilicon compound (A) having the (meth) acrylic group and the heteropolyacid (B) and the organosilicon compound (E) is added to The mixture was stirred and mixed to obtain a photocurable nanoimprint composition. The obtained composition for photocurable nanoimprint was filtered with a syringe filter having a 0.2 μmφ hole diameter. Tables 1 and 2 show the compositions and blending ratios of the photocurable nanoimprint composition.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion, release property, transferability, sapphire selectivity, and long-term storage stability of the cured film. The results are shown in Table 3.

Comparative Example 1
(Production of photocurable nanoimprint composition)
In a glove box substituted with nitrogen gas, 8.5 g of ethanol, 1.5 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as the organosilicon compound (A) having a (meth) acryl group Then, 5.8 g of diphenyldimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed as the organosilicon compound (E).
While stirring and mixing the mixture, a 2.0N ethanol / water 0.6g / 2N-HCl 0.03 g 2N-HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. Further, an ethanol aqueous solution of 0.5 g of ethanol / 0.1 g of water was gradually added dropwise and stirred at room temperature for 1 hour to hydrolyze an organosilicon compound (A) having a (meth) acryl group and an organosilicon compound (E ) Was obtained.

  After mixing the same type, the same amount of the polymerizable monomer (C), the photopolymerization initiator (D), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) 4.5 g of the mixture containing the hydrolyzate of the organosilicon compound (A) having the (meth) acrylic group and the hydrolyzate of the organosilicon compound (E) is added to the mixture, followed by stirring and mixing at room temperature for 15 minutes, and photocuring A nano-imprinting composition was obtained. The obtained composition for photocurable nanoimprint was filtered with a syringe filter having a 0.2 μmφ hole diameter. Tables 1 and 2 show the compositions and blending ratios of the photocurable nanoimprint composition.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion, release property, transferability, sapphire selectivity, and long-term storage stability of the cured film. The results are shown in Table 3.

Comparative Example 2
(Production of photocurable nanoimprint composition)
In a glove box substituted with nitrogen gas, ethanol 6.8 g, silicotungstic acid 26 water (manufactured by Wako Pure Chemical Industries) 0.5 g as heteropolyacid (B), diphenyldimethoxysilane (Tokyo Kasei) as organosilicon compound (E) 5.8 g (manufactured by Kogyo Co., Ltd.) was mixed.
While this mixture was stirred and mixed, a 1.6 N ethanol / 0.6 g water / 2 0.03 g 2N HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. Furthermore, ethanol aqueous solution of ethanol 0.4g / water 0.1g was dripped gradually, and it stirred at room temperature for 1 hour, and obtained the mixture containing the hydrolyzate of heteropoly acid (B) and organosilicon compound (E).

  After mixing the same type, the same amount of the polymerizable monomer (C), the photopolymerization initiator (D), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) 4.8 g of a mixture containing a hydrolyzate of the heteropolyacid (B) and the organosilicon compound (E) was added to the mixture, followed by stirring and mixing at room temperature for 15 minutes to obtain a photocurable nanoimprint composition. The obtained composition for photocurable nanoimprint was filtered with a syringe filter having a 0.2 μmφ hole diameter. Tables 1 and 2 show the compositions and blending ratios of the photocurable nanoimprint composition.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion, release property, transferability, sapphire selectivity, and long-term storage stability of the cured film. The results are shown in Table 3.

Comparative Example 3
(Production of photocurable nanoimprint composition)
13.6 g of ethanol, 3.0 g of trimethoxysilylpropyl acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as the organosilicon compound (A) having a (meth) acryl group, and ethyl silicate 40 (corcol ( Co., Ltd. Tetraethoxysilane average pentamer) 6.8 g, and 1-butanol solution of 85 mass% zirconium butoxide (tetrabutylzirconium alkoxide) as metal alkoxide was mixed with stirring, and this mixture was stirred and mixed. Then, ethanol 4.25g / water 0.85g / 2N-HCl 0.16g 2N-HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. Further, an ethanol aqueous solution of ethanol 1 g / water 0.46 g was gradually dropped and stirred at room temperature for 1 hour, and a hydrolyzate of an organosilicon compound (A) having a (meth) acryl group, an organosilicon compound, and a metal alkoxide was added. A mixture containing was obtained.

  After mixing the same type, the same amount of the polymerizable monomer (C), the photopolymerization initiator (D), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 3.6 g of the mixture containing the organomethanoic compound (A) having the (meth) acrylic group and the hydrolyzate of the organosilicon compound and the metal alkoxide, the mixture is stirred and mixed at room temperature for 15 minutes to form a photocurable nanoimprint composition. I got a thing. The obtained composition for photocurable nanoimprint was filtered with a syringe filter having a 0.2 μmφ hole diameter. Tables 1 and 2 show the compositions and blending ratios of the photocurable nanoimprint composition.

  The obtained photocurable nanoimprint composition was used to evaluate the substrate adhesion, release property, transferability, sapphire selectivity, and long-term storage stability of the cured film. The results are shown in Table 3.

Example 12
(Manufacture of surface processed sapphire substrates)
The photocurable nanoimprinting composition obtained in Example 3 was diluted with acetylacetone to 10% by weight. The diluted photocurable nanoimprint composition 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 at 120 ° C. It dried for 2 minutes and the sapphire board | substrate with which the coating film of the composition for photocurable nanoimprint was coated with the thickness of about 100 nm was obtained.

  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 1 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.

Example 13
(Replica mold for Nanon print)
0.5 ml of the photocurable nanoimprinting composition obtained in Example 3 was dropped on a 188 μm-thick polyethylene terephthalate film that had been subjected to easy adhesion surface treatment, and dried at 300 mPa and 70 ° C. for 3 minutes to evaporate volatile components. It was. On a polyethylene terephthalate film having the obtained photocurable nanoimprint composition, a quartz mold (NTT-AT nano) with a minimum pattern of 80 nm was used in a vacuum pressure UV curing apparatus (VS005-200C-UV) manufactured by Mikado Technos. Fabrication Co., Ltd., 80L RESO), polyethylene terephthalate film (laminate) on which a pattern made of a cured film is formed by irradiating light with a metal halide lamp for 30 seconds under a pressure of 1 MPa and performing light nanoimprinting Got. The used quartz mold was previously subjected to mold release treatment by fluorine-based surface treatment (Daikin Industries, Ltd., OPTOOL HD-1100TH). In order to use a polyethylene terephthalate film (laminated body) on which a pattern made of a cured film was formed as a replica mold for nanoimprinting, it was cut into a size of 20 mm × 20 mm around the pattern. Next, as a pretreatment for performing the mold release treatment, the pattern surface was hydrolyzed under humidified conditions. The hydrolysis treatment was carried out by placing the cut polyethylene terephthalate film (laminated body) in a container containing water and heating the container at 70 ° C. for 2 hours in a heating oven. Thereafter, the patterned surface of the treated laminate was brought into contact with a fluorine-based surface treatment agent (manufactured by Daikin Industries, Ltd., OPTOOL HD-1100TH) to perform a mold release treatment, thereby producing a replica mold.

  A mixture of (C) and (D) produced in Example 1 and a polymerization inhibitor was dropped onto the transfer pattern surface treated with fluorine, and sandwiched between quartz plates. Then, a nanoimprint apparatus (EUN manufactured by Engineering System Co., Ltd.) was used. -4200), light imprinting was performed by applying light at a pressure of 0.3 MPa for 60 seconds from the quartz plate side with an LED 375 nm light source. After peeling off the quartz plate, the obtained pattern surface was observed with an SEM, and it was confirmed that it was transferred to the same pattern as the mold used.

Claims (12)

(A) The following formula (1)

(Where
R ¹ is a hydrogen atom or a methyl group,
R ² is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms,
R ³ 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 ⁴ is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 4 carbon atoms,
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 ^{1, R} 2, ^{R 3} and ^{R 4} respectively, when there are a plurality, the plurality of ^{R 1,} R 2, ^{R 3} and ^{R 4,} respectively, may be the same or different groups) An organosilicon compound having the (meth) acrylic group shown,
(B) a heteropolyacid,
(C) A photocurable nanoimprinting composition containing a polymerizable monomer having a (meth) acrylic group and (D) a photopolymerization initiator. The composition for photocurable nanoimprint according to claim 1, wherein the (B) heteropolyacid is represented by the following formula (4).
_{H x [M m · M '} n O r] · yH 2 O (4)
(In the formula, M represents a hetero element composed of one or two elements selected from silicon, phosphorus, and boron, M ′ represents one or more poly elements selected from tungsten, molybdenum, niobium, and vanadium; An integer of 10 to 100, m is an integer of 1 to 10, n is an integer of 6 to 40, x is an integer of 1 to 10, and y is an integer of 0 to 50.)   2. The photocurable nanoimprint composition according to claim 1, wherein the (B) heteropolyacid is silicotungstic acid.   3 to 300 parts by mass of the organosilicon compound (A) having the (meth) acrylic group, 100 parts by mass of the heteropolyacid (B) 0 with respect to 100 parts by mass of the polymerizable monomer (C) having the (meth) acrylic group. The composition for photocurable nanoimprint according to any one of claims 1 to 3, comprising 0.1 to 50 parts by mass and 0.1 to 10 parts by mass of the photopolymerization initiator (D). . Furthermore, (E) The organosilicon compound shown by following formula (2) is contained, The composition for photocurable nanoimprints of any one of Claims 1-4 characterized by the above-mentioned.

(In the formula, R ⁵ and R ⁶ are the same or different alkyl group having 1 to 4 carbon atoms or hydrogen, R ⁷ is an aryl group, and R ⁸ is an aryl group or an alkoxy group having 1 to 4 carbon atoms. And n is an integer of 1 to 10.)   3 to 300 parts by mass of the organosilicon compound (A) having the (meth) acrylic group, 100 parts by mass of the heteropolyacid (B) 0 with respect to 100 parts by mass of the polymerizable monomer (C) having the (meth) acrylic group. 1 to 50 parts by mass, 10 to 400 parts by mass of the organosilicon compound (E), and 0.1 to 10 parts by mass of the photopolymerization initiator (D). The photocurable nanoimprinting composition according to claim 1. Furthermore, the fluorinated organosilane compound (F) shown by following formula (3) is contained, The composition for photocurable nanoimprints of any one of Claims 1-6 characterized by the above-mentioned.

(Where
R ⁹ and R ¹¹ are each an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms; R ¹⁰ is a fluorine-containing alkyl group having 1 to 100 carbon atoms or a fluorine-containing cyclo group. An alkyl group or a fluorine-containing alkoxy ether group; a is an integer of 1 to 3, b is an integer of 0 to 2, provided that a + b = 1 to 3; R ⁹ , R ¹⁰ and R ^{When a} plurality of ¹¹ are present, the plurality of R ⁹ , R ¹⁰ and R ¹¹ may be the same or different. )   0.001 to 4 parts by mass of the fluorinated organosilane compound (F) and organosilicon having the (meth) acrylic group with respect to 100 parts by mass of the polymerizable monomer (C) having the (meth) acrylic group. 3 to 300 parts by mass of the compound (A), 0.1 to 50 parts by mass of the heteropolyacid (B), 10 to 400 parts by mass of the organosilicon compound (E), and 0.1 to 0.1 of the photopolymerization initiator (D). The composition for photocurable nanoimprint according to claim 7, comprising 10 parts by mass. A photocurable nanoimprinting composition obtained by mixing at least the following components (A) to (D).
(A) The following formula (1)

(Where
R ¹ is a hydrogen atom or a methyl group,
R ² is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms,
R ³ 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 ⁴ is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 4 carbon atoms,
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 ^{1, R} 2, ^{R 3} and ^{R 4} respectively, when there are a plurality, the plurality of ^{R 1,} R 2, ^{R 3} and ^{R 4,} respectively, may be the same or different groups) An organosilicon compound having the (meth) acrylic group shown,
(B) a heteropolyacid,
(C) A polymerizable monomer having a (meth) acryl group, and (D) a photopolymerization initiator. The process of apply | coating the composition for photocurable nanoimprint of any one of Claims 1-9 on a board | substrate, 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.   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 forming method according to claim 10 as a mask Manufacturing method.   A replica mold for nanoimprinting, comprising a cured product of the photocurable nanoimprinting composition according to claim 1.