JP5968041B2 - Photocurable nanoimprint composition and pattern formation method - Google Patents

Description

  The present invention relates to a novel photocurable nanoimprint composition, and further relates to a novel pattern forming method for forming a pattern on a substrate using the photocurable nanoimprint composition.

  In recent years, semiconductor integrated circuits are required to be miniaturized and highly accurate, but such microfabrication is not only applied to advanced semiconductor integrated circuits, but also provides antireflection and light extraction efficiency in LED substrates. In various applications such as optical / illumination applications such as improvement, energy development of secondary batteries, solar cells, fuel cells, biotechnology, etc., fine processing by imprint technology has been actively studied.

  The imprint technology is to transfer a desired pattern onto the substrate surface by pressing and peeling a mold having irregularities in the pattern corresponding to the pattern to be formed on the substrate onto the coating film formed on the substrate surface. It is expected to be 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.

  Regarding this imprint technique, the method is roughly classified into two types according to the characteristics 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 method of optical imprint that transfers a pattern by light irradiation is capable of forming a highly accurate pattern, and thus has been widely used in nanoimprint technology, and is suitably used for the method. Development of photocurable 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, improvement of the adhesion to the substrate has been attempted by treating the surface of the substrate, providing an adhesive layer, or 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.

  For example, in Patent Document 1, in a composition for nanoimprinting using only a hydrolyzed condensate, (1) a phenomenon in which the film breaks (crack) occurs because the elastic modulus of the film is too high, (2) tackiness of the film surface In order to solve the problem that (adhesiveness) does not develop, (3) traces of mold pattern (pattern marks) are not easily left on the film, a hydrolysis monomer, a polymerizable monomer, a photopolymerization initiator A photocurable composition to which is added has been proposed.

  The nanoimprint technique forms a desired pattern on a substrate based on a coating material (hereinafter also referred to as a cured film) having a pattern transferred by a mold. 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 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 for various patterning (hereinafter, this characteristic is also referred to as etching resistance).

  In order to improve this etching resistance, a photocurable composition containing a polymerizable monomer having an aryl substituent has been proposed (for example, see Patent Document 2).

  However, according to the study by the present inventors, it has been found that the photocurable composition described in Patent Document 2 has room for improvement in the following points.

  The photocurable composition described in Patent Document 2 has a high viscosity, and it is difficult to produce a thin film when coating on a substrate. Moreover, although it is thought that it uses only an organic compound, the base material adhesion is poor, and the cured product may be peeled off from the base material during imprinting, and there is room for improvement.

  In general, the use of chlorine-based gas is well studied for dry etching of sapphire substrates. In order to improve etching resistance, it is known to contain a compound containing an aryl group substituent, but a photocurable nanoimprinting composition having etching resistance to chlorine-based gas is not disclosed.

JP 2010-251434 A JP 2009-218550 A

  An object of the present invention is to provide a photocurable nanoimprinting composition which is excellent in etching resistance of a chlorine-based gas and excellent in productivity. In addition, even when the mold is pressed at a relatively low pressure, the pattern can be easily transferred, the adhesion of the pattern to the base material is good, and the mold release property is good. The object is to provide a photocurable nanoimprinting composition having good transferability.

  The present inventor has made various studies on combinations of an organosilicon compound having an aryl substituent and a polymerizable monomer in order to improve the etching resistance and productivity of chlorine gas and improve the pattern transferability. As a result, in addition to the above-mentioned combination, it was found that nanoimprint pattern transferability and etching resistance, particularly etching resistance to chlorine-based gas, can be achieved by adding acrylsilane hydrolyzate, and the present invention has been completed. It was.

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

(Where
R ¹ and R ² are the same or different alkyl groups having 1 to 4 carbon atoms,
R ³ is an aryl group;
R ⁴ is an aryl group or an alkoxy group having 1 to 4 carbon atoms,
n is an integer of 1-10. And a hydrolyzate of an organosilicon compound represented by the following formula (2)

(Where
R ⁵ is a hydrogen atom or a methyl group,
R ⁶ is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms,
R ⁷ 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 ⁸ 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,
When ^{R 5, R 6, R 7} , and ^{where R 8} each, there are a plurality, the plurality of ^{R 5, R 6, R 7} , and ^{R 8} each may be the same or different groups)
A hydrolyzate mixture containing a hydrolyzate of an organosilicon compound having a (meth) acryl group represented by:
(B) a polymerizable monomer having a (meth) acryl group, and (C) a photopolymerization initiator ,
For 100 parts by mass of the polymerizable monomer (B) having the (meth) acryl group,
Hydrolyzing a hydrolysis component mixture containing 10 to 400 parts by mass of the organosilicon compound represented by the formula (1) and 3 to 300 parts by mass of the organosilicon compound having a (meth) acryl group represented by the formula (2) Hydrolyzate mixture (A) obtained by
0.1-10 parts by mass of the photopolymerization initiator (C)
It is a photocurable nanoimprinting composition characterized by including .

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
The substrate is a sapphire substrate, and the surface of the substrate is etched with a chlorine-based gas using the pattern formed by the pattern forming method as a mask.

  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, good adhesion to the substrate of the cured film after curing the composition as a coating film, and excellent pattern transferability and productivity. . Moreover, the conventional photocurable nanoimprint composition has room for improvement in etching resistance, particularly etching resistance to chlorine-based gas, whereas the photocurable nanoimprint composition of the present invention has excellent pattern transferability. Therefore, it is a composition suitable for forming a cured film having etching resistance, particularly chlorine gas etching resistance.

  Moreover, the photocurable nanoimprinting composition containing a hydrolyzate of metal alkoxide further improves the etching resistance to chlorine gas.

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

（式中、
Ｒ^１、Ｒ^２は同種又は異種の炭素数１〜４のアルキル基であり、
Ｒ^３はアリール基であり、
Ｒ^４はアリール基または炭素数１〜４のアルコキシ基であり、
ｎは１〜１０の整数である）
で示される有機珪素化合物の加水分解物、および
下記式（２）

(Where
R ¹ and R ² are the same or different alkyl groups having 1 to 4 carbon atoms,
R ³ is an aryl group;
R ⁴ is an aryl group or an alkoxy group having 1 to 4 carbon atoms,
n is an integer of 1 to 10)
A hydrolyzate of an organosilicon compound represented by formula (2):

（式中、
Ｒ^５は、水素原子、またはメチル基であり、
Ｒ^６は、炭素数１〜２０のアルキレン基または炭素数３〜１０のシクロアルキレン基であり、
Ｒ^７は、炭素数１〜４のアルキル基、炭素数３〜４のシクロアルキル基、または炭素数６〜１２のアリール基であり、
Ｒ^８は、炭素数１〜４のアルキル基または炭素数３〜４のシクロアルキル基であり、
ｌは１〜３の整数であり、ｍは０〜２の整数であり、ｋは１〜３の整数であり、
ｌ＋ｍ＋ｋは４であり、
Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８がそれぞれ、複数存在する場合には、複数のＲ^５、Ｒ^６、Ｒ^７およびＲ^８は、それぞれ、同種又は異種の基であってもよい）
で示される（メタ）アクリル基を有する有機珪素化合物の加水分解物、を含む加水分解物混合物（以下、単に、「加水分解物混合物（Ａ）」ともいう）、（Ｂ）（メタ）アクリル基を有する重合性単量体（以下、単に、「重合性単量体（Ｂ）」ともいう）、並びに（Ｃ）光重合性開始剤を含むものである。

(Where
R ⁵ is a hydrogen atom or a methyl group,
R ⁶ is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms,
R ⁷ 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 ⁸ 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,
When the R ^{5, R} 6, ^{R 7} and ^{R 8} are each, there are a plurality, the plurality of ^{R 5,} R 6, ^{R 7} and ^{R 8} may each be the same or different groups)
A hydrolyzate mixture (hereinafter also referred to simply as “hydrolyzate mixture (A)”), (B) (meth) acrylic group, And a polymerizable monomer (hereinafter, also simply referred to as “polymerizable monomer (B)”), and (C) a photopolymerizable 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 hydrolyzate mixture (A) will be described.

(Hydrolysate mixture (A))
In the present invention, the hydrolyzate mixture (A) is a hydrolyzate of an organosilicon compound represented by the above formula (1) and a hydrolyzate of an organosilicon compound having a (meth) acrylic group represented by the above formula (2). It is a hydrolyzate mixture containing a product. The degree of hydrolysis of the hydrolyzate including the hydrolyzate of the organosilicon compound represented by the formula (1) and the hydrolyzate of the organosilicon compound having a (meth) acrylic group represented by the formula (2) The alkoxy group may be completely hydrolyzed, or a part of the alkoxy group may be hydrolyzed.

(Organic silicon compound)
In the present invention, the following formula (1)

(Where
R ¹ and R ² are the same or different alkyl groups having 1 to 4 carbon atoms,
R ³ is an aryl group;
R ⁴ is an aryl group or an alkoxy group having 1 to 4 carbon atoms,
n is an integer of 1-10. )
A hydrolyzate of an organosilicon compound represented by the following (hereinafter also simply referred to as “organosilicon compound”) is used.

  By using the hydrolyzate of the organosilicon compound, a photocurable nanoimprinting composition capable of forming a cured film excellent in etching resistance, particularly etching resistance to chlorine-based gas is obtained.

In the formula (1), R ¹ and R ² are methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, isobutyl group, and tert-butyl group. Among them, methyl group, Ethyl group, propyl group, isopropyl group and butyl group are preferred. -OR ^1, alkoxy group represented by -OR ² is ^-OR 1 upon hydrolysis, but produces an alcohol from -OR ^2, photocurable composition for imprints of the invention, contain the alcohol Also good. 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 ¹ and R ² 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 ³ , examples of the aryl group include aryl groups such as a phenyl group, a benzyl group, a 1-naphthyl group, and a 2-naphthyl group, and among them, a phenyl group is preferable. The aryl group may have a substituent such as an alkyl group, an ether group, a glycol ether group, a hydroxyl group, or a halogen.

Examples of the alkoxy group of R ⁴ include a methyl alkoxy group, an ethyl alkoxy group, a propyl alkoxy group, an isopropyl alkoxy group, a butyl alkoxy group, a sec-butyl alkoxy group, an isobutyl alkoxy group, a tert-butyl alkoxy group, and the like. Examples of the group include a phenyl group, a benzyl group, a 1-naphthyl group, and a 2-naphthyl group. The alkoxy group and aryl group may have a substituent such as an alkyl group, an ether group, a glycol ether group, a hydroxyl group, or a halogen. Among the alkoxy groups and aryl groups, a methyl alkoxy group, an ethyl alkoxy group, a propyl alkoxy group, an isopropyl alkoxy group, a butyl alkoxy group, and a phenyl group are preferable. The alkoxy group represented by —R ⁴ generates an alcohol derived from R ⁴ upon hydrolysis, but the photocurable nanoimprinting composition of the present invention may contain this alcohol. Therefore, in consideration of becoming an alcohol that can be easily mixed with other components, and an alcohol that can be easily removed after forming a coating film on the substrate, specifically, when R ⁴ is an alkoxy group, 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. .

Among these, R ⁴ is preferably an aryl group having 6 to 12 carbon atoms from the viewpoint of forming a cured film having good etching resistance, in particular, chlorine gas etching resistance.

  The organosilicon compound may be a single compound or a plurality of organosilicons having different values of n as long as n satisfies an integer of 1 to 10 in the formula (1). 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. When a mixture of a plurality of organosilicon compounds is used, the average value of n is preferably 1.1 or more and 10 or less, and further, the pattern transferability at a relatively lower pressure, or 100 nm or less. Taking into account the transfer of a fine pattern such as 1.1 to 7 is more preferable.

  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.

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

(Where
R ⁵ is a hydrogen atom or a methyl group,
R ⁶ is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms,
R ⁷ 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 ⁸ 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 ^{5, R} 6, ^{R 7} and ^{R 8} are each, when there are a plurality, the plurality of ^{R 5,} R 6, ^{R 7} and ^{R 8} each may be the same or different groups. )
A hydrolyzate of an organosilicon compound having a (meth) acryl group represented by the following (hereinafter also simply referred to as “organosilicon compound having a (meth) acryl group”) 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, the inorganic component and the organic component are dispersed in a relatively homogeneous state (the dispersed state is not such that the inorganic component is extremely aggregated). As a result, it is estimated that a uniform transfer pattern and a uniform residual film can be formed.

In the formula (2), R ⁵ 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 ⁶ 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, 2-propylpentylene group, 2,4,4-trimethylpentylene group, 2-methylheptylene group, 3-methylheptylene group, 4-methylheptylene group, 2,2,4-trimethyl Nylene group, 2,2,3-trimethylpentylene group, 2,3,4-trimethylpentylene group, 2,3,3-trimethylpentylene group, 3,3-dimethylhexylene group, 3,4-dimethyl Hexylene group, 2,3-dimethylhexylene group, 2,4-dimethylhexylene group, 2,2-dimethylhexylene group, 2,5-dimethylhexylene group, 2,2,3,3-tetramethyl Butylene group, 3-ethyl-2-methylpentylene group, 3-ethylhexylene group, 3-ethyl-3-methylpentylene group, nonylene group, 2,3,4-trimethylhexylene group, 3,4- Dimethylhexylene, 3,5-dimethylhexylene group, 3,3-dimethylhexylene group, 3,3-diethylpentylene group, 4,4-dimethylhexylene group, 3-ethyl-2,4-dimethylpentyl 2,3,5-trimethylhexylene group, 2,2,4,4-tetramethylpentylene group, 2,2-dimethylheptylene group, 2,6-dimethylheptylene group, 2, 5-dimethylheptylene group, 2,4-dimethylheptylene group, 4-ethylheptylene group, 3-methyloctylene group, 4-methyloctylene group, 2,3 dimethylheptylene group, 4-ethyl 2-methylhexylene group, 3-ethyl-4-methylhexylene group, 2-methyloctylene group, 2,2,5-trimethylhexylene group, 3,3-dimethylheptylene group, 2,2, 3,3-tetramethylpentylene group, 3-ethylheptylene group, 2,2,3-trimethylhexylene group, 2,2,4-trimethylhexylene group, 2,3,3-trimethylhexylene group, 2, 4,4-trimethylhe Silene group, 3,3,4-trimethylhexylene group, 3-ethyl-2,2-dimethylpentylene group, 2,3,3,4-tetramethylpentylene group, 3-ethyl-2-methyl-hexylene Group, dexylene group, 2-methylnonylene group, 2,2,5,5-tetramethylhexylene group, 2,7-dimethyloctylene group, 2,2,6-trimethylheptylene group, 2,6-dimethyl group Octylene group, 2,4,6-trimethylheptylene group, 4-propyl-heptylene group, 2,4,4-trimethylheptylene group, 2,3,6-trimethylheptylene group, 2,4 -Dimethyloctylene group, 3,3-dimethyloctylene group, 3,3,4,4-tetramethylhexylene group, 3-ethyloctylene group, 3-methylnonylene group, 2,3-dimethyloctylene group, 3, 3, 5 Trimethylheptylene, 3-ethyl-2,4-dimethylhexylene, 2,2,3,3-tetramethylhexylene, 3-ethyl-2-methylheptylene, 2,2,4-trimethyl Putylene group, 5-methylnonylene group, 4-ethyloctylene group, 2,2-dimethyloctylene group, 3,5-dimethyloctylene group, 3,6-dimethyloctylene group, 4,4-dimethyloctylene Group, 2,2,4,5-tetramethylhexylene group, 4-methylnonylene group, 3-ethyl-3-methyl-heptylene group, 3,3-dimethylhexylene group, 4-ethyl-4-methylpentylene Group, 3,4-diethylhexylene group, 2,4,5-trimethylheptylene group, 3,4,4-trimethylheptylene group, 3-ethyl-2,2-dimethylhexylene group, 2, 2, 5-trimethylheptylene group, 2,2,4,4-tetramethylhexylene group, 4- (1-methylethyl) -heptylene group, 4-ethyl-2-methylheptylene group, 4-ethyl-3-methylheptylene group Group, 3-ethyl-4-methylheptylene group, 2,2,3-trimethylheptylene group, 2,3,3-trimethylheptylene group, 2,3,4-trimethylheptylene group, 3-ethyl -2,3-dimethylhexylene group, 4-ethyl-2,4-dimethylhexylene group, 3-ethyl-2,5-dimethylhexylene group, 4-ethyl-3,3-dimethylhexylene group, 3 -Ethyl-3,4-dimethylhexylene group, 2,2,3,4-tetramethylhexylene group, 2,2,3,5-tetramethylhexylene group, 2,3,4,4-tetramethyl Hexylene, 2, , 3,5-tetramethylhexylene group, 2,3,4,4-tetramethylhexylene group, 2,3,4,5-tetramethylhexylene group, 3,3-dimethyl-2-methylpentylene Group, dimethyloctylene group, undecylene group, 4-methyldexylene group, 3- (1,1-dimethylethyl) -2,2-dimethylpentylene group, 4-ethylnonylene group, 5,5-dimethylnonylene group 2-methyl-3- (1-methylethyl) -heptylene group, 2-methyldexylene group, 3-methyldexylene, 2,2,3,5,5-pentamethylhexylene group, 3-ethylnonylene group, 5-ethylnonylene Group, 4-propyloctylene group, 2,2-dimethylnonylene group, 3,3-dimethylnonylene group, 3-ethyl-3-methyloctylene group, 3,3-diethyl-heptile Group, 4,4-dimethylnonylene group, 4-ethyl-4-methyloctylene group, 4-methyl-4-propylheptylene group, 4,4-diethylheptylene group, 3,4-dimethylnonyl group Len group, 2,4-dimethylnonylene group, 3,5-dimethylnonylene group, 4,6-dimethylnonylene group, 2,7-dimethylnonylene group, 2,8-dimethylnonylene group, 3, 6-dimethylnonylene group, 2,2,4-trimethyloctylene group, 2,2,6,6-tetramethylheptylene group, 2,3,5,6-tetramethylheptylene group, 2, 3,3,4,5-pentamethyl-hexylene group, 4- (1,1-dimethylethyl) -heptylene group, 2,2,4,4,5-pentamethyl-hexylene group, 2,2,3,3 4,4-hexamethylpentylene group, 3,3-dimethyl-2, 2-dimethylpentylene group, 3-ethyl-2,3-dimethylpentylene group, 4-ethyl-2,3-dimethylpentylene group, 5-ethyl-2,3-dimethylpentylene group, 3-ethyl- 2,4-dimethylpentylene group, 4-ethyl-2,4-dimethylpentylene group, 5-ethyl-2,4-dimethylpentylene group, 3-ethyl-2,5-dimethylpentylene group, 4- Ethyl-2,5-dimethylpentylene group, 5-ethyl-2,5-dimethylpentylene group, 3-ethyl-2,6-dimethylpentylene group, 4-ethyl-2,6-dimethylpentylene group, 4-ethyl-3,3-dimethylpentylene group, 5-ethyl-3,3-dimethylpentylene group, 3-ethyl-3,4-dimethylpentylene group, 4-ethyl-3,4-dimethylpentylene Group, 3-ethyl 4,5-dimethylpentylene group, 3-ethyl-3,5-dimethylpentylene group, 4-ethyl-3,5-dimethylpentylene group, 3-ethyl-4,4-dimethylpentylene group, 2, 2,3,3-tetramethylheptylene group, 2,2,3,4-tetramethylheptylene group, 2,2,3,5-tetramethylheptylene group, 2,2,3,6 -Tetramethylheptylene group, 2,2,4,4-tetramethylheptylene group, 2,2,4,5-tetramethylheptylene group, 2,2,4,6-tetramethylheptyl group Len group, 2,2,5,5-tetramethylheptylene group, 2,2,5,6-tetramethylheptylene group, 2,3,4,4-tetramethylheptylene group, 2, 3,3,5-tetramethylheptylene group, 2,3,3,6-tetramethylheptylene group, 2, , 4,4-tetramethylheptylene group, 2,3,4,5-tetramethylheptylene group, 2,3,4,6-tetramethylheptylene group, 2,3,5,5- Tetramethylheptylene group, 2,4,4,5-tetramethylheptylene group, 2,4,4,6-tetramethylheptylene group, 2,4,5,5-tetramethylheptylene Group, 3,3,4,4-tetramethylheptylene group, 3,3,4,5-tetramethylheptylene group, 3,3,5,5-tetramethylheptylene group, 3,4 , 4,5-tetramethylheptylene group, 2,2-dimethyl-3- (1-methylethyl) hexylene group, 2,3-dimethyl-3- (1-methylethyl) hexylene group, 2,4- Dimethyl-3- (1-methylethyl) hexylene group, 2,5-dimethyl-3- (1-methylethyl) Hexylene group, 3,3-dimethyl-2-methylhexylene group, 3,4-dimethyl-2-methylhexylene group, 4,4-dimethyl-2-methylhexylene group, 3,4-dimethyl-3- Methylhexylene group, 3,3-dimethyl-4-methylhexylene group, 3-ethyl-2,2,3-trimethylhexylene group, 4-ethyl-2,2,3-trimethylhexylene group, 3- Ethyl-2,2,4-trimethylhexylene group, 4-ethyl-2,2,4-trimethylhexylene group, 3-ethyl-2,2,5-trimethylhexylene group, 4-ethyl-2,2 , 5-trimethylhexylene, 4-ethyl-2,3,3-trimethylhexylene, 3-ethyl-2,3,4-trimethylhexylene, 4-ethyl-2,3,4-trimethyl Xylene group, 3-ethyl 2,3,5-trimethylhexylene group, 3-ethyl-2,4,5-trimethylhexylene group, 3-ethyl-2,4,4-trimethylhexylene group, 3-ethyl-3,4,4 -Trimethylhexylene group, 2,2,3,3,4-pentamethylhexylene group, 2,2,3,3,5-pentamethylhexylene group, 2,2,3,4,4-pentamethyl Hexylene group, 2,2,3,4,5-pentamethylhexylene group, 2,3,4-trimethyl-3- (1-methylethyl) pentylene group, 3,3-dimethyl-2,4-dimethyl Pentylene group, 3-ethyl-2,2,3,4-tetramethylpentylene group, 3,5,5-trimethyloctylene group, 4,4,5-trimethyloctylene group, 2-methyl-4- Propylheptylene group, 3-methyl-4-propylhe A tylene group, a 2-methyl-4- (1-methylethyl) heptylene group, a 3-methyl-4- (1-methylethyl) heptylene group, a 4-methyl-4- (1-methylethyl) heptylene group, 3, 4-dimethyl-heptylene group, 3,5-dimethyl-heptylene group, 3-ethyl-2,2-dimethylheptylene group, 4- (1-methylethyl) octylene group, 3-ethyl-2-methyloctylene Group, 4-ethyl-2-methyloctylene group, 4-ethyl-3-methyloctylene group, 5-ethyl-3-methyloctylene group, 3-ethyl-6-methyloctylene group, 3-ethyl- 4-methyloctylene group, 4-ethyl-5-methyloctylene group, 3-ethyl-5-methyloctylene group, 2,2,3-trimethyloctylene group, 2,2,5-trimethyloctylene group 2 , 2,7-trimethyloctylene group, 2,3,3-trimethyloctylene group, 2,3,4-trimethyloctylene group, 2,3,5-trimethyloctylene group, 2,
4,4-trimethyloctylene group, 2,4,5-trimethyloctylene group, 2,4,7-trimethyloctylene group, 2,5,5-trimethyloctylene group, 3,3,4-trimethyloctylene Len group, 3,3,5-trimethyloctylene group, 3,3,6-trimethyloctylene group, 3,4,4-trimethyloctylene group, 2,4,5-trimethyloctylene group, 3,4 , 6-Trimethyloctylene group, 4-ethyl-2,2-dimethylheptylene group, 5-ethyl-2,2-dimethylheptylene group, dodecylene group, 4-ethyl-2,6-dimethyloctylene Group, 3-isopropyl-2,2,3,4-tetramethylpentylene group, 3-isopropyl-2,2,4,4-tetramethylpentylene group, tridexylene, 2-methyldodexylene group, 4-methyldo Xylene group, 2,4,6,8-tetramethylnonylene group, 2,6-dimethylundexylene group, 4,7-dimethylundexylene group, 3-methyldodexylene group, 4-propyldexylene group, 3,3 -Diethylnonylene group, 4-ethyl-4-propyloctylene group, 4,4-dipropylheptylene group, 4,4-diethylnonylene group, 2,2,4,4,6,6-hexa Methylheptylene group, 3- (1,1-dimethylethyl) -2,2,4,4-tetramethylpentylene group, 3,3,7,7-tetramethylnonylene group, 3,5,7 -Trimethyl dexylene group, 4,5,7-trimethyl dexylene group, 5-methyldodexylene group, 6-methyldodexylene group, 2,2,3,5,6,6-hexamethylheptylene group, 4- (1 , 1-Dimethylethyl) -2,6-dimethyl Heptylene group, 2,2,3-trimethyldexylene group, 4,4,6,6-tetramethylnonylene group, 3,5-diethyl-3,5-dimethylheptylene group, 2,3,4, 5,6-pentamethyloctylene group, 3,3,4,5,6-pentamethyloctylene group, 3,3-dimethyl-2,2,4,4-tetramethylpentylene group, 2,2, 3,4,4-pentamethyl-3- (1-methylethyl) -pentylene group, methyldodexylene group, 3-ethyl-3-methyl-4-propylheptylene group, tetradexine group, 2-methyltridexylene group, 3 , 3,4,4-tetraethylhexylene group, 2,3-dimethyldodexylene group, 2,4-dimethyldodexylene group, 5-butyldexylene group, 2,6,10-trimethylundexylene group, 4- Propyl undecylene group 2,11-dimethyldodexylene group, 6-methyltridexylene group, 5-ethyldodexylene group, 6-methyltridexylene group, 5-ethyldodexylene group, 6,7-dimethyldodexylene group, 6-ethyl-5 -Methylundexylene group, 4-methyl-5-propylnonylene group, 4,5-dipropyloctylene group, 2,2,3,5,5-pentamethyl-3- (1-methylethyl) hexylene group 2,5,6,9-tetramethyldexylene group, 3,6-diethyl-4,5-dimethyloctylene group, 2,2,4,5,7,7-hexamethyloctylene group, 3- (1,1-dimethylethyl) -2,2,5,5-tetramethylhexylene group, 2,2-dimethyldodexylene group, 4-ethyl-2,2,4,6,6-pentamethylhexene Peptylene group, 5-ethyl-4-propyl Nylene group, 5-methyl-4-propyldexylene group, 5-ethyl-6-methylundexylene group, 3-methyltridexylene group, 4-methyltridexylene group, 5-methyltridexylene group, 5, 5, 6,6-tetramethyldexylene group, 3-ethyldodexylene group, 4,6,8-trimethylundexylene group, 2,2,6,6-tetramethyl-4- (1-methylethyl) heptylene group, 2, 6-dimethyldodexylene group, 2,2,3,3,4,4,5,5-octamethylhexylene group, 2,4,7,9-tetramethyldexylene group, 2,6,9- Trimethylundexylene group, 2,4,4,5,5,7-hexamethyloctylene group, 5,5-dimethyldodexylene group, 3,7-dimethyldodexylene group, 3,3,8,8 -Tetramethyldexylene group, 3,4,7,8- Tramethyldexylene group, 5,8-dodexene group, 6-ethyldodexylene group, 4-ethyldodexylene group, 5-propylundexylene group, 2,5-dimethyl-3,4-bis (1-methylethyl) hexylene group, Pentadexylene group, 2-methyltetradexylene group, 2,6,10-tetramethyldodexylene group, 2,2,3-tetramethyldodexylene group, 7-methyltetradexylene group, 2,3-dimethyl Tridexylene group, 4-methyltetradexylene group, 5-methyltetradexylene group, 6-methyltetradexylene group, 6,8-dimethyltridexylene group, 2,6,11-tetramethyldodexylene group, 3-methyltetradexylene group, 4- (1,1-dimethylethyl) -2,2,6,6-tetramethylheptylene group, 3- (1,1-dimethylethyl) -2,2,3 5,5-pentamethylheptylene group, 2,2-dimethyltridexylene group, 4-ethyl-3-methyldodexylene group, 6-ethyltridexylene group, 2,3,5,7,8-hexamethylnonylene Group, 2,4,8,10-tetramethylundexylene group, 5-ethyltridexylene group, 5,5,7,7-tetramethylundexylene group, 4,6-diethyl-4,6-dimethylnonylene Group, 2,2,5,5,8,8-hexamethylnonylene group, 3,5,7-triethylnonylene group, 5,9-dimethyltridexylene group, hexadexylene group, 2-methylpentadexylene group 7,8-dimethyltetradexylene group, 3-methylpentadexylene group, 2,6,10-tetramethyltridexylene group, 2,2,4,4,6,8,8-heptamethylnonylene group , 2, 2, 4, 4 5,5,7,7-octamethyloctylene group, 5-butyldodexylene group, 7-methylpentadexylene group, 2,3-dimethyltetradexylene group, 8-methylpentadexylene group, 2,4,6 , 8,10-pentamethylundecylene group, 2,5,8,11-tetramethyldodexylene group, 4-methylpentadexylene group, 5-methylpentadexylene group, 6-methylpentadexylene group, 3,7,11-trimethyltridexene group, 2,5,5,6,6,9-hexamethyldexylene group, 2,2-dimethyltetradexylene group, 4,6,7,9-tetramethyldexylene Len group, 6-ethyltetradexylene group, 2,2,3,8,9,9-hexamethyldexylene group, 3-ethyltetradexylene group, 2,2,4,7,9,9-hexa Methyl dexylene group, 3,3,6,6-te Traethyldexylene group, 2,6,9,10-tetramethyldodexylene group, 6-ethyl-2,10-dimethyldodexylene group, 5,7-diethyldodexylene group, 2,5,9 -Trimethyltridexene group, 7-ethyltetradexylene group, 5-ethyltetradexylene group, 6-butyldodexylene group, 4-methyl-9-propyldodexylene group, heptadexylene group, 3,3-bis (1, 1-dimethylethyl) -2,2,4,4-tetramethylpentylene group, 5,5-dibutylnonylene group, 3-methylhexadexylene group, 4-methylhexadexylene group, 5-methylhexadexene Len group, 6-methylhexadexylene group, 7-methylhexadexene group, 8-methylhexadexylene group, 2,2,4,4,6,6,8,8-octamethylnonylene group, 3 , 7,11-teto Methyltetradexylene group, 2,6-dimethylpentadexylene group, 6-ethylpentadexylene group, 3,8-dimethylpentadexylene group, 2,3,10-tetramethylpentadexylene group, 6,10 -Dimethylpentadexylene group, 7-ethyl-3,11-dimethyl-tridexene group, 6,7-diethyltridexylene group, 2,5,9-trimethyltetradexylene group, 2,5,9,12-tetra Methyltridexylene group, octadexylene group, 2-methylheptadexylene group, 3-methylheptadexylene group, 4-methylheptadexylene group, 5-methylheptadexylene group, 6-methylheptadexylene group, 7- Methylheptadexylene group, 8-methylheptadexylene group, 2,15-dimethylhexadexylene group, 2,6,10-trimethylpentadexylene group, 9-mes Ruheptadexylene group, 2,2-dimethylhexadexene group, 3,7,11-trimethylpentadexylene group, 5,6-diethyl-2,5,6,9-tetramethyldexylene group, 3,4-bis (1,1-dimethylethyl) -2,2,5,5-tetramethylhexylene group, 6-ethylhexadexylene group, 3,5,7,8-tetramethyltetradexylene group, 2,6, 9,13-tetramethyltetradexylene group, 2,5-dimethylhexadexene group, 4,6-dipropyldodexylene group, 5,7-dimethoxyhexadexylene group, trimethylpentadexylene group, 7, 10-dimethoxyhexadexene group, 2,2,5,5,10,10-hexamethyldodexylene group, nonadexylene group, 2-methyloctadexylene group, 3-methyloctadexylene group, 4-methyloctane Tadexylene group, 5-methyloctadexylene group, 6-methyloctadexylene group, 7-methyloctadexylene group, 8-methyloctadexylene group, 9-methyloctadexylene group, 2,16-dimethylheptadex Len group, 2,6,10,10-tetramethylpentadexylene group, 2,6,10,14-tetramethylpentadexylene group, 2,4,6,10-tetramethylpentadexylene group, 3- Ethylheptadexylene group, 3,7,11-triethylhexadexylene group, 2,2-dimethylheptadexylene group, 2,6-dimethylheptadexylene group, 2,10,14-trimethylhexadexylene group, 2,6,14-trimethylhexadexylene group, 6-ethylheptadexylene group, 2,4,6,8,10,11-hexamethyltridexylene group, 2,4,6,8,9, 2-hexamethyltridexylene group, 5-ethylheptadexylene group, 2,4,6,8,10,12-hexamethyltridexylene group, 9-ethylheptadexylene group, 2,3,10-trimethylhexa Dexylene group, 6,10-dimethylheptadexylene group, eicosylene group, 2,6,11,15-tetramethylhexadexylene group, 2,6,10,14-tetramethylhexadexylene group, 2-methyl Nonadexylene group, 3-methylnonadexylene group, 4-methylnonadexylene group, 5-methylnonadexylene group, 6-methylnonadexylene group, 7-methylnonadexylene group, 8-methylnonadexylene Len group, 9-methylnonadexylene group, 10-methylnonadexylene group, 3-ethyloctadexylene group, 2,6,11,15-tetramethylhexadexylene group, 2,6,10 14-tetramethylhexadexene group, 6,6,11,11-tetramethylhexadexene group, 2,6,7,8,8,12-hexamethyltetradexylene group, 2,17-dimethyloctadexylene Len group, 5,5,11,11-tetramethyloctadexylene group, 2,2,15,15-tetramethyloctadexylene group, 9,10-dimethyloctadexylene group, 8,11-dimethyloctadexylene Len group, 2,4-dimethyloctadexylene group, 7,11-dimethyloctadexylene group, 2,4,6,9,11,13-hexamethyltetradexylene group, 2,4,6,8, 11,12-hexamethyltetradexylene group, 2,6-dimethyloctadexylene group, 5,6-dibutyl-5,6-dimethyldexylene group, 2,6,10-trimethyl-7- (3-methylbutyl ) Alkylene groups such as dodecylene group, 6-pentyl-7-propyldodecylene group, 4,6,8-tripropylundecylene group, 7,10-dimethyloctadexylene group, 6,10-dimethyloctadexylene group A cycloalkylene group such as a cyclopropylene group, a cyclobutylene group, a cyclopropylmethylene group, a cyclopentylylene group, a cyclohexylene group, and 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 ⁷ 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 ⁸ 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.

Alkoxy group represented by the -OR ^8, which produces an alcohol derived from R ⁸ upon hydrolysis, photocurable composition for imprints of the invention may contain the alcohol. Therefore, considering that it becomes an alcohol that can be easily mixed with other components, and that it becomes an alcohol that can be easily removed after forming a coating film on a substrate, specifically, R ⁸ is 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 n, that is, l + m + n is 4.

  Specific examples of such an organosilicon compound having a (meth) acryl group include trimethoxysilylmethylene (meth) acrylate, trimethoxysilyldimethylene (meth) acrylate, trimethoxysilyltrimethylene (meth) acrylate, Triethoxysilylmethylene (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 Rate, 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, di Toxiethylsilylmethylene (meth) acrylate, diethoxyethylsilyldimethylene (meth) acrylate, diethoxyethylsilyltrimethylene (meth) acrylate, methoxydimethylsilylmethylene (meth) acrylate, methoxydimethylsilyldimethylene (meth) acrylate, Methoxydimethylsilyltrimethylene (meth) acrylate, ethoxydimethylsilylmethylene (meth) acrylate, ethoxydimethylsilyldimethylene (meth) acrylate, ethoxydimethylsilyltrimethylene (meth) acrylate, methoxydiethylsilylmethylene (meth) acrylate, methoxydiethyl Silyldimethylene (meth) acrylate, methoxydiethylsilyltrimethylene (meth) acrylate, ethoxydiethylsilyl Examples include methylene (meth) acrylate, ethoxydiethylsilyldimethylene (meth) acrylate, and ethoxydiethylsilyltrimethylene (meth) acrylate. Of these, trimethoxysilyltrimethylene (meth) acrylate and triethoxysilyltrimethylene (meth) acrylate are preferable.

(Other hydrolyzate components (metal alkoxide))
In the present invention, the hydrolyzate mixture (A) is further represented by the following formula (3):

(Where
M is tungsten, tin, indium, hafnium, antimony,
R ⁹ is an alkyl group having 1 to 10 carbon atoms, and may be the same or different group,
When M is tungsten, p is 5,
When M is tin or hafnium, p is 4,
When M is indium or antimony, p is 3. )
A hydrolyzate of a metal alkoxide represented by (hereinafter also simply referred to as “metal alkoxide”).

  The photocurable nanoimprint composition of the present invention can form a cured film having excellent etching resistance, particularly etching resistance to chlorine-based gas. By using this metal alkoxide, etching resistance to chlorine-based gas can be formed. Can be further improved. And the etching rate of chlorine gas can also be adjusted with the usage-amount of the hydrolyzate of a metal alkoxide.

  In the above formula (3), M is preferably tungsten in order to further improve the etching resistance against chlorine gas.

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

R ⁹ is more preferably an alkyl group having 2 to 4 carbon atoms from the viewpoint of an appropriate hydrolysis rate. The alkoxy group represented by -OR ⁹ also produces an alcohol derived from R ⁹ upon hydrolysis as in the case of the organosilicon compound and the like. However, the photocurable nanoimprint composition of the present invention contains this alcohol. May be. Therefore, considering that —OR ⁹ 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 ⁹ is: An alkyl group having 2 to 4 carbon atoms such as an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable.

  Examples of suitable metal alkoxides include pentamethyl tungsten alkoxide, pentaethyl tungsten alkoxide, pentaisopropyl tungsten alkoxide, pentapropyl tungsten alkoxide, pentaisobutyl tungsten alkoxide, pentabutyl tungsten alkoxide, pentapentyl tungsten alkoxide, pentahexyl tungsten alkoxide, penta Heptyl tungsten alkoxide, pentaoctyl tungsten alkoxide, pentanonyl tungsten alkoxide, pentadecyl tungsten alkoxide; tetramethyltin alkoxide, tetraethyltin alkoxide, tetraisopropyltin alkoxide, tetrapropyltin alkoxide, tetraisobutyltin alkoxide Sid, tetrabutyltin alkoxide, tetrapentyltin alkoxide, tetraheptyltin alkoxide, tetrahexyltin alkoxide, tetraheptyltin alkoxide, tetraoctyltin alkoxide, tetranonyltin alkoxide, tetradecyltin alkoxide; tetramethylhafnium alkoxide, tetraethylhafnium alkoxide , Tetraisopropyl hafnium alkoxide, tetrapropyl hafnium alkoxide, tetraisobutyl hafnium alkoxide, tetrabutyl hafnium alkoxide, tetrapentyl hafnium alkoxide, tetraheptyl hafnium alkoxide, tetrahexyl hafnium alkoxide, tetraheptyl hafnium alkoxide, tetraoctyl hafnium alkoxide , Tetranonyl hafnium alkoxide, tetradecyl hafnium alkoxide; trimethyl indium alkoxide, triethyl indium alkoxide, triisopropyl indium alkoxide, tripropyl indium alkoxide, triisobutyl indium alkoxide, tributyl indium alkoxide, tripentyl indium alkoxide, trihexyl indium alkoxide, tri Heptylindium alkoxide, trioctylindium alkoxide, trinonylindium alkoxide, tridecylindium alkoxide; trimethylantimony alkoxide, triethylantimony alkoxide, triisopropylantimony alkoxide, tripropylantimony alkoxide, triisobutylan Timon alkoxide, tributyl antimony alkoxide, tripentyl antimony alkoxide, trihexyl antimony alkoxide, triheptyl antimony alkoxide, trioctyl antimony alkoxide, trinonyl antimony alkoxide, tridecyl antimony alkoxide. Among these, pentaethyl tungsten alkoxide, pentaisopropyl tungsten alkoxide, pentapropyl tungsten alkoxide, pentaisobutyl tungsten alkoxide, and pentabutyl tungsten alkoxide are preferable.

(Production method of hydrolyzate mixture (A))
In the present invention, the organosilicon compound constituting the hydrolyzate mixture (A) and the organosilicon compound having a (meth) acryl group are preferably used in the following amounts. That is, the hydrolyzate mixture (A) is an organic compound having 10 to 400 parts by mass of an organosilicon compound and (meth) acrylic group with respect to 100 parts by mass of the polymerizable monomer (B) described in detail below. It is preferable to hydrolyze a hydrolysis component mixture containing 3 to 300 parts by mass of a silicon compound. All the alkoxy groups may be hydrolyzed by hydrolysis, or a part of the alkoxy group may be partially hydrolyzed. The amount of water used for the hydrolysis is not particularly limited, but considering the wettability of the coating film and better nanoimprint pattern transferability, it is 0.1 times the number of moles of all alkoxy groups in the mixture. It can be preferably selected from a mole of 2.0 or more and 2.0 moles or less.

  When the blending amount of the organosilicon compound and the organosilicon compound having a (meth) acrylic group satisfies the above range, the hydrolyzate mixture has a highly dispersible photocurable nanoimprint composition and is easily purified by filtration. Can improve productivity. Moreover, since nanoimprinting at a relatively low pressure is possible, the life of the mold to be used can be extended. Considering the dispersibility of the hydrolyzate mixture and nanoimprinting at a relatively low pressure, the amount of the organosilicon compound used may be 30 to 300 parts by mass with respect to 100 parts by mass of the polymerizable monomer (B). More preferably, the amount of the organosilicon compound having a (meth) acryl group is more preferably 5 to 250 parts by mass. Furthermore, the amount of the organic silicon compound used is preferably 30 to 200 parts by mass, and the amount of the organic silicon compound having a (meth) acryl group is preferably 10 to 200 parts by mass. The amount of the compound used is particularly preferably 35 to 140 parts by mass, and the amount of the organosilicon compound having a (meth) acryl group is particularly preferably 15 to 180 parts by mass.

  In the present invention, the hydrolyzate mixture (A) can further contain a hydrolyzate of a metal alkoxide. By including the hydrolyzate of a metal alkoxide, the etching resistance with respect to the chlorine-type gas of a cured film can further be improved. The metal alkoxide is preferably used in the following amount. That is, with respect to 100 parts by mass of the polymerizable monomer (B) described below in detail, the hydrolysis component mixture is further made into a hydrolysis component mixture containing 0.1 to 150 parts by mass of a metal alkoxide, It is preferable to hydrolyze the hydrolysis component mixture.

  When the blending amount of the organosilicon compound having a (meth) acrylic group and the metal alkoxide satisfies the above range, it becomes a photocurable nanoimprinting composition having good dispersibility of the hydrolysis mixture, and more favorable pattern transferability and filtration. Purification is easy and productivity can be improved. Moreover, since nanoimprinting at a relatively low pressure is possible, the life of the mold to be used can be extended. Further, by adding a hydrolyzate of metal alkoxide, etching resistance, particularly etching resistance of chlorine-based gas is improved. Considering the dispersibility of the hydrolysis mixture and nanoimprinting at a relatively low pressure, the amount of metal alkoxide used is 0.5 to 100 parts by mass with respect to 100 parts by mass of the polymerizable monomer (B). Is more preferable. Furthermore, it is more preferable that the usage-amount of a metal alkoxide is 1-80 mass parts, and it is especially preferable that it is 3-50 mass parts.

  Moreover, it is preferable that a metal alkoxide is 0.2-50 mass parts with respect to a total of 100 mass parts of an organosilicon compound and the organosilicon compound which has a (meth) acryl group. By setting the amount of metal alkoxide used within the above range, the etching resistance due to the chlorine-based gas is particularly improved. Therefore, the usage-amount of a metal alkoxide becomes like this. More preferably, it is 1-40 mass parts, More preferably, it is 2-30 mass parts.

(Production method of hydrolyzate mixture (A): water used for hydrolysis and its amount)
In the present invention, the amount of water used to obtain the hydrolysis mixture (A) is not particularly limited, but is an amount of 0.1 to 2.0 times the mole of the total number of alkoxide groups. From the viewpoint of wettability of the coating film and better nanoimprint nanoimprint pattern transferability.

  The number of moles of all alkoxy groups is the product of the number of moles of the organosilicon compound having a (meth) acryl group and the number of alkoxy groups present in one molecule of the organosilicon compound having the (meth) acryl group. And the number of moles of metal alkoxide used and the number of alkoxy groups present in one molecule of the metal alkoxide, and when an organosilicon compound is used, the mole number of organosilicon compound used and the organosilicon compound 1 It is the product of the number of alkoxy groups present in the molecule.

  When the amount of water is less than 0.1 times mol, the condensation becomes insufficient, and the wettability is poor when forming a coating film, and repelling is likely to occur. On the other hand, when the amount is 2.0 times or more, the nanoimprint nanoimprint pattern transferability at a relatively low pressure is lowered, which may cause damage to the mold. In consideration of the degree of condensation and pattern formation at a relatively low pressure, the amount of water is preferably 0.2 to 1.5 times the mole of the total number of alkoxide groups in the mixture, It is preferable that they are 0.5 times mole or more and 1.2 times mole or less.

  In the present invention, the water may contain an acid. 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 hydrolyzate mixture (A) is a component to be hydrolyzed (an organosilicon compound having an aryl group and an organosilicon compound having a (meth) acryl group (including a metal alkoxide when a metal alkoxide is used)). ) With the above amount of water. The method of mixing with water is not particularly limited, but in order to produce a uniform photocurable nanoimprint composition, the components to be hydrolyzed are first mixed to form a hydrolyzed component mixture, It is preferable to carry out hydrolysis by adding water to the hydrolysis component mixture.

  What is necessary is just to implement mixing with 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. It is preferable that the usage-amount of a dilution solvent is 50-400 mass parts with respect to 100 mass parts of the said hydrolysis component mixture.

(Production method of hydrolysis mixture (A): 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 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.

(Method of using hydrolyzate mixture (A), physical properties)
A hydrolyzate mixture (A) can be prepared according to the above method. In addition to the hydrolyzate mixture (A), the photocurable nanoimprinting composition 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.

  The hydrolyzate mixture (A) obtained has a viscosity at 25 ° C. of 0.1 to 100 mPa · sec, considering the ease of mixing with other components and the productivity of the photocurable nanoimprint composition. Preferably there is. 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.

  Moreover, it is preferable to mix a hydrolyzate mixture (A) with another component immediately after manufacture to make a composition for photocurable nanoimprint. However, if this is not possible, it is preferably stored at a temperature of −30 ° C. to 15 ° C. or lower in order not to change with time after production. Also in this case, it is preferable that the viscosity of the hydrolyzate mixture (A) satisfies the above range.

  Next, the polymerizable monomer (B) having a (meth) acryl group used in combination with the hydrolyzate mixture (A) obtained by the above method will be described.

(Polymerizable monomer having (meth) acrylic group (B))
In the present invention, the polymerizable monomer (B) having a (meth) acryl group (hereinafter, also simply referred to as “polymerizable monomer (B)”) is not particularly limited, and is used for photopolymerization. Any known polymerizable monomer can be used. This polymerizable monomer (B) does not contain an organosilicon compound having a (meth) acryl group represented by the formula (2). A preferable compound includes a polymerizable monomer having a (meth) acryl group and containing no silicon atom in the molecule. These polymerizable monomers (B) 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 (B) 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, phenoxy polyalkylene glycol acrylate, alkylphenol ethylene glycol modified (meth) acrylate, alkylphenol propylene glycol modified (meth) acrylate, ethoxylated o-phenyl Phenol (meth) acrylate, following formula (4)

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

  As a polyfunctional polymerizable monomer having two (meth) acryl groups in one molecule (bifunctional polymerizable monomer), for example, a monomer having an alkylene oxide bond in the molecule is preferable. Include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, the following formula (5)

(Where
R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or a methyl group;
a and b are each an integer of 0 or more, provided that the average value of a + b is 2 to 25)
And polyolefin glycol di (meth) acrylate represented by

  The polyolefin glycol di (meth) acrylate represented by the above formula (5) is usually obtained from a mixture of molecules having different molecular weights. Therefore, the value of a + b is an average value. In order for the effect of the present invention to be more exerted, the average value of a + b is preferably 2 to 15, and particularly preferably 2 to 10.

  Other bifunctional polymerizable monomers include 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-hydroxy-1,3-dimethacryloxypropane, dioxane glycol di (meth) acrylate, tricyclode Candimethanol 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, Butylethylpropanediol di (meth) acrylate, 3 -Aliphatic di (meth) acrylates such as methyl-1,5-pentanediol di (meth) acrylate; ethoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, engineered bisphenol F di (meth) acrylate, following formula (7)

(Where
R ¹⁶ and R ¹⁷ are each independently a hydrogen atom or a methyl group,
R ¹⁸ and R ¹⁹ are an alkylene group having 1 to 10 carbon atoms, a hydroxyalkylene group having 1 to 10 carbon atoms, a (poly) ethylene glycol group having 2 to 10 carbon atoms, or (poly) propylene having 3 to 12 carbon atoms. It is a glycol group, and each may be the same or different group. )
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 (B), a monomer having a ο-phenylphenol group in the molecule and a monomer having a fluorene structure in the molecule from the point that the etching resistance of chlorine gas can be improved. A mer is preferable, specifically, an ethoxylated o-phenylphenol (meth) acrylate, a monomer having an o-phenylphenol group in the molecule represented by the formula (4), and the formula (7). Di (meth) acrylate having a fluorene structure is preferred.

  In the present invention, these polymerizable monomers (B) can be used alone or in combination of a plurality of types depending on the intended use and the shape of the pattern to be formed.

  A monomer having an o-phenylphenol group in the molecule represented by the formula (4) will be described.

  Following formula (4)

(Where
R ¹⁰ is a hydrogen atom or a methyl group,
R ¹¹ is an alkylene group having 1 to 10 carbon atoms or a hydroxyalkylene group having 1 to 10 carbon atoms. )
In the formula, R ¹⁰ is a hydrogen atom or a methyl group.

R ¹¹ is an alkylene group having 1 to 10 carbon atoms or a hydroxyalkylene group having 1 to 10 carbon atoms. 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, 2-propylpentylene group, 2,4,4-trimethylpentylene group, 2-methylheptylene group, 3-methylheptylene group, 4-methylheptylene group, 2,2,4-trimethyl Nylene group, 2,2,3-trimethylpentylene group, 2,3,4-trimethylpentylene group, 2,3,3-trimethylpentylene group, 3,3-dimethylhexylene group, 3,4-dimethyl Hexylene group, 2,3-dimethylhexylene group, 2,4-dimethylhexylene group, 2,2-dimethylhexylene group, 2,5-dimethylhexylene group, 2,2,3,3-tetramethyl Butylene group, 3-ethyl-2-methylpentylene group, 3-ethylhexylene group, 3-ethyl-3-methylpentylene group, nonylene group, 2,3,4-trimethylhexylene group, 3,4- Dimethylhexylene, 3,5-dimethylhexylene group, 3,3-dimethylhexylene group, 3,3-diethylpentylene group, 4,4-dimethylhexylene group, 3-ethyl-2,4-dimethylpentyl 2,3,5-trimethylhexylene group, 2,2,4,4-tetramethylpentylene group, 2,2-dimethylheptylene group, 2,6-dimethylheptylene group, 2, 5-dimethylheptylene group, 2,4-dimethylheptylene group, 4-ethylheptylene group, 3-methyloctylene group, 4-methyloctylene group, 2,3 dimethylheptylene group, 4-ethyl 2-methylhexylene group, 3-ethyl-4-methylhexylene group, 2-methyloctylene group, 2,2,5-trimethylhexylene group, 3,3-dimethylheptylene group, 2,2, 3,3-tetramethylpentylene group, 3-ethylheptylene group, 2,2,3-trimethylhexylene group, 2,2,4-trimethylhexylene group, 2,3,3-trimethylhexylene group, 2, 4,4-trimethylhe Silene group, 3,3,4-trimethylhexylene group, 3-ethyl-2,2-dimethylpentylene group, 2,3,3,4-tetramethylpentylene group, 3-ethyl-2-methyl-hexylene Group, dexylene group, 2-methylnonylene group, 2,2,5,5-tetramethylhexylene group, 2,7-dimethyloctylene group, 2,2,6-trimethylheptylene group, 2,6-dimethyl group Octylene group, 2,4,6-trimethylheptylene group, 4-propyl-heptylene group, 2,4,4-trimethylheptylene group, 2,3,6-trimethylheptylene group, 2,4 -Dimethyloctylene group, 3,3-dimethyloctylene group, 3,3,4,4-tetramethylhexylene group, 3-ethyloctylene group, 3-methylnonylene group, 2,3-dimethyloctylene group, 3, 3, 5 Trimethylheptylene, 3-ethyl-2,4-dimethylhexylene, 2,2,3,3-tetramethylhexylene, 3-ethyl-2-methylheptylene, 2,2,4-trimethyl Putylene group, 5-methylnonylene group, 4-ethyloctylene group, 2,2-dimethyloctylene group, 3,5-dimethyloctylene group, 3,6-dimethyloctylene group, 4,4-dimethyloctylene Group, 2,2,4,5-tetramethylhexylene group, 4-methylnonylene group, 3-ethyl-3-methyl-heptylene group, 3,3-dimethylhexylene group, 4-ethyl-4-methylpentylene Group, 3,4-diethylhexylene group, 2,4,5-trimethylheptylene group, 3,4,4-trimethylheptylene group, 3-ethyl-2,2-dimethylhexylene group, 2, 2, 5-trimethylheptylene group, 2,2,4,4-tetramethylhexylene group, 4- (1-methylethyl) -heptylene group, 4-ethyl-2-methylheptylene group, 4-ethyl-3-methylheptylene group Group, 3-ethyl-4-methylheptylene group, 2,2,3-trimethylheptylene group, 2,3,3-trimethylheptylene group, 2,3,4-trimethylheptylene group, 3-ethyl -2,3-dimethylhexylene group, 4-ethyl-2,4-dimethylhexylene group, 3-ethyl-2,5-dimethylhexylene group, 4-ethyl-3,3-dimethylhexylene group, 3 -Ethyl-3,4-dimethylhexylene group, 2,2,3,4-tetramethylhexylene group, 2,2,3,5-tetramethylhexylene group, 2,3,4,4-tetramethyl Hexylene, 2, , 3,5-tetramethylhexylene group, 2,3,4,4-tetramethylhexylene group, 2,3,4,5-tetramethylhexylene group, 3,3-dimethyl-2-methylpentylene Group, alkylene group such as dimethyloctylene group; polymethylene group such as trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene 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 Droxy-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- Droxy-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-ethyl Tylene 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-methylpen Tylene 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 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 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 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-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-hydroxyhept Len 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-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, 6-hydroxy-3-heptylene, 7-hydroxy-3-heptylene, 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-2-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 Group, 6-hydroxy-2-ethylhexylene group, 1-hydroxy-6-methyl-2-heptylene group, 2-hydroxy-6-methyl-2-heptyl group 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-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-hydroxyoctyl Len, 2-hydroxyoctylene, 3-hydroxyoctylene, 4-hydroxyoctylene, 5-hydroxyoctylene, 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-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-hydro Xyl-2-propylpentylene group, 3-hydroxy-2-propylpentylene group, 4-hydroxy-2-propylpentylene group, 5-hydroxy-2-propylpentylene group, 1-hydroxy-2,4, 4-trimethylpentylene group, 2-hydroxy-2,4,4-trimethylpentylene group, 3-hydroxy-2,4,4-trimethylpentylene group, 5-hydroxy-2,4,4-trimethylpentylene And hydroxyalkylene groups such as groups.

  Among these, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, a trimethylene group, a tetramethylene group, etc., a C1-C4 alkylene group or a C3-C4 polymethylene group; or a hydroxymethylene group 1-hydroxymethylene group, 2-hydroxymethylene group, 1-hydroxypropylene group, 2-hydroxypropylene group, 3-hydroxypropylene group, 1-hydroxyisopropylene group, 2-hydroxyisopropylene group, 3-hydroxyisopropylene It is preferably a hydroxyalkylene group having 1 to 4 carbon atoms such as a group, 1-hydroxybutylene group, 2-hydroxybutylene group, 3-hydroxybutylene group, 4-hydroxybutylene group.

  Among the monomers having an o-phenylphenol group in the molecule represented by the formula (4), preferred compounds include 3-O-phenylphenol ethyl acrylate, 3-O-phenylphenol propyl acrylate, 3-O -Phenylphenol butyl acrylate, 2-hydroxy-3-O-phenylphenol propyl acrylate, 2-hydroxy-3-O-phenylphenol butyl acrylate, 3-hydroxy-3-O-phenylphenol propyl acrylate and the like.

  A monomer having an o-phenylphenol group in the molecule represented by the formula (7) will be described.

  Following formula (7)

(Where
R ¹⁶ and R ¹⁷ are a hydrogen atom or a methyl group,
R ¹⁸ and R ¹⁹ are an alkylene group having 1 to 10 carbon atoms, a hydroxyalkylene group having 1 to 10 carbon atoms, (poly) ethylene glycol having 1 to 10 carbon atoms, and (poly) propylene glycol having 1 to 12 carbon atoms. is there. )
In the formula, R ¹⁶ and R ¹⁷ are a hydrogen atom or a methyl group.

R ¹⁸ and R ¹⁹ are each an alkylene group having 1 to 10 carbon atoms, a hydroxyalkylene group having 1 to 10 carbon atoms, (poly) ethylene glycol having 1 to 10 carbon atoms, or (poly) propylene glycol having 1 to 12 carbon atoms. It is. 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, ethylene glycol group, diethylene glycol group, triethylene glycol group, tetraethylene glycol group, polyethylene glycol group such as pentaethylene glycol group, propylene glycol group, di Examples include polypropylene glycol groups such as propylene 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, C1-C4 hydroxyalkylene group such as 4-hydroxybutylene group and 1-hydroxyisobutylene group, C2-C4 polyethylene glycol group such as ethylene glycol group and diethylene glycol group, or propylene glycol carbon number 3 Polypropylene Glycol groups are preferred.

  Among monomers having an o-phenylphenol group in the molecule represented by the formula (7), 9,9-bis [4- (2- (meth) acryloyloxymethoxy) phenyl] fluorene is preferable as a suitable compound. 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) acryloyl) Oxyhydroxypropyloxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxyhydroxyisopropyloxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxyhydroxy) Butyloxy) 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 (C) will be described.

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

  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 (B), and 0.1-5 mass parts It is more preferable from the viewpoint of etching resistance.

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

  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 can also be mix | blended for the objective which stabilizes the composition for photocurable nanoimprint of this invention, or the other 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, propylene glycol, propylene glycol methyl ether, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethylene glycol monoethyl ether acetate, ethyl lactate, ethyl-3-ethoxypropionate, butyl acetate, Examples include 2-heptanone, methyl isobutyl ketone, acetylacetone, diacetone alcohol, polyethylene glycol, water, and alcohol. It is possible. In addition, water and alcohol can also be newly blended, and may be water used when the hydrolyzate mixture (A) is produced, and alcohol by-produced. Moreover, the solvent used as a dilution solvent when manufacturing a hydrolyzate mixture (A) may be contained in the said solvent.

  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.

  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, per 100 parts by weight of the polymerizable monomer (B). 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 (B). 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 and is appropriately selected within a range not affecting the formation of the pattern from the mold, and is usually 1 to 100 parts by mass of the polymerizable monomer (B). It is suitably selected from the range of 50 parts by mass. Among these, it is preferable that it is 5-30 mass parts, when low viscosity of the composition for photocurable nanoimprint, the mechanical strength of a pattern, etc. are considered.

  In addition, spherical fine particles such as a piper branch polymer can be added as another additive component. 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 (B).

  The photocurable nanoimprint composition of the present invention is a mixture of a hydrolyzate mixture (A), a polymerizable monomer (B), a photopolymerization initiator (C), and other additive components blended as necessary. To be prepared. 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.

  By applying the photocurable nanoimprint composition of the present invention on these substrates 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. What is necessary is just to form a coating film. 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.

  The drying temperature is not particularly limited as long as the coating film is dried. Usually, the drying temperature can be selected from a range of 40 ° C to 150 ° C.

  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 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, it is expected that the light extraction efficiency of the LED is improved and the homogeneous GaN growth with little crystal transition is expected.

  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 filterability When 10 ml of the composition for photocurable nanoimprint obtained in the following Examples and Comparative Examples was filtered by hand with a 0.2 μmφ pore diameter, a 25 mm diameter syringe filter and a 10 ml syringe, Those that could be filtered within 20 sec were marked with ◯, those that could be filtered within 1 minute were marked with Δ, and those that were clogged in the middle and could not be filtered were marked with x.

(2) Evaluation of substrate adhesion of cured film The obtained composition for photocurable nanoimprint was diluted with 1-methoxy-2-propanol, and a sapphire substrate (single mirror surface, thickness 430 μm, surface roughness Ra ≦ 0.1 nm, surface orientation C surface), spin-coated at 3000 rpm for 30 seconds, dried at 110 ° C. for 2 minutes, and then irradiated with UV to form a photocured film by a photocurable nanoimprint composition having a thickness of about 1 μm , Using Nichiban Co., Ltd. 15mm width cellophane tape 405 (length 5cm), peeled after 3 reciprocal contact with finger pressure,
The cured film was not removed at all: 5
The peeled area is less than 10%: 4
Exfoliation area of 10% or more and less than 50%: 3
Exfoliation area 50% or more and less than 100%: 2
With peeling area of 100% (full peeling): 1
As evaluated.

(3) Evaluation of transferability (application of photocurable nanoimprint composition)
The obtained composition for photocurable nanoimprint was diluted with 1-methoxy-2-propanol to 60 wt%. The diluted photocurable nanoimprint composition is spin-coated on a silicon wafer (P-type, single mirror surface, no oxide film) at 3000 rpm for 30 seconds and dried at 110 ° C. for 2 minutes to be used for photocurable nanoimprint A silicon wafer having a coating film of the composition coated to a thickness of about 1 μm 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 0.5 MPa and irradiating light from an LED 365 nm light source for 10 seconds. The quartz mold used was previously subjected to mold release treatment by fluorine-based surface treatment (manufactured by Daikin Industries, Ltd., OPTOOL HD-1100DH).

  The shape transferability of the pattern formed on the sapphire substrate (base material) using the photocurable nanoimprint composition was evaluated by observation with a scanning electron microscope (SEM). In the evaluation of transferability, “◯” indicates that all the patterns formed with a total of 100 lines having a width of 200 nm at intervals of 200 nm can be transferred, and “△” indicates that the pattern shape is partially defective. The case where all the patterns were not transferred was evaluated as “x”.

(4) Evaluation of etching resistance (Etching to 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 mass of the sapphire substrate) was measured.
<Dry etching conditions with chlorine gas>
Chlorine gas flow rate: 20sccm
Bias power: 80W
Substrate cooling temperature: 5 ° C
(Etching cured film)
The obtained photocurable nanoimprinting composition was diluted with 1-methoxy-2-propanol and spin-coated on a silicon wafer (P-type, one mirror surface, no oxide film) at 3000 rpm for 30 seconds, 110 After drying for 2 minutes at ° C., UV irradiation was performed to obtain a silicon wafer coated with a cured film of a photocurable nanoimprint composition having a thickness of about 1 μm. The silicon wafer coated with the obtained cured film was dry-etched under the same conditions as dry etching with a chlorine gas on a sapphire substrate, and the reduced mass of the cured film over a certain time was measured.

(Calculation of sapphire selectivity)
Calculate the ratio of the reduced mass of the sapphire substrate to the reduced mass of the cured film of the photocurable nanoimprint composition (the reduced mass of the sapphire substrate / the reduced mass of the cured film of the photocurable nanoimprint composition). This was used as the sapphire selectivity of the cured film of the photocurable nanoimprint composition. 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. .

Example 1
(Production of hydrolyzate mixture (A))
13.6 g of ethanol, 3.0 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as a (meth) acrylic group-containing silicon compound, and phenyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd.) as an organosilicon compound )) 9.2 g was mixed, and while stirring and mixing this mixture, ethanol 4.3 g / water 1.3 g / 2 N-HCl 0.2 g 2N-HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. . Further, an ethanol aqueous solution of 1.0 g of ethanol / 0.6 g of water was gradually added dropwise and stirred at room temperature for 1 hour to mix a hydrolyzate of an organosilicon compound and a hydrolyzate of a (meth) acryl group-containing silicon compound. A hydrolyzate mixture (A) containing was obtained.

(Production of photocurable nanoimprint composition)
As a polymerizable monomer (B) 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 (C), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (BASF Japan Ltd.) 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 (B), photopolymerization initiator (C), and polymerization inhibitor were uniformly mixed, and 1.0 g of the mixture was collected. 4.1 g of the obtained hydrolyzate mixture (A) was added to 1.0 g of the mixture, and the mixture was stirred at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition. Tables 1 and 2 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 2
(Production of hydrolyzate mixture (A))
13.6 g of ethanol, 3.0 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as a (meth) acrylic group-containing silicon compound, and diphenyldimethoxysilane (Shin-Etsu Chemical Co., Ltd.) as an organosilicon compound LS-5300 manufactured by LS-5300) was mixed, and while stirring and mixing the mixture, ethanol 4.3 g / water 0.9 g / 2 N-HCl 0.2 g 2N-HCl / ethanol mixed aqueous solution was gradually added at room temperature. It was dripped. Further, an ethanol aqueous solution of 1.0 g of ethanol / 0.5 g of water was gradually added dropwise and stirred at room temperature for 1 hour, so A decomposition product mixture (A) was obtained.

(Production of photocurable nanoimprint composition)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 4.2 g of the hydrolyzate mixture (A), the mixture was stirred and mixed at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition. Tables 1 and 2 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 3
(Production of hydrolyzate mixture (A))
The same operation as in Example 2 was performed to obtain a hydrolyzate mixture (A).

(Production of photocurable nanoimprint composition)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 1.1 g of the hydrolyzate mixture (A), the mixture was stirred and mixed at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition. Tables 1 and 2 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 4
(Production of hydrolyzate mixture (A))
A hydrolyzate mixture (A) was obtained in the same manner as in Example 2.

(Production of photocurable nanoimprint composition)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 10.0 g of the hydrolyzate mixture (A) to the mixture, the mixture was stirred and mixed at room temperature for 15 minutes to obtain a photocurable nanoimprint composition. Tables 1 and 2 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 5
(Production of hydrolyzate mixture (A))
13.6 g of ethanol, 3.0 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as a (meth) acrylic group-containing silicon compound, and diphenyldimethoxysilane (Shin-Etsu Chemical Co., Ltd.) as an organosilicon compound LS-5300 (manufactured by LS-5300) was mixed, and while stirring this mixture, 4.3 g of ethanol / 1.4 g of water / 2 N-HCl 0.2 g of a 2N-HCl / ethanol mixed aqueous solution was gradually added at room temperature. It was dripped. Further, an ethanol aqueous solution of 1.0 g of ethanol / 0.7 g of water was gradually added dropwise and stirred at room temperature for 1 hour to obtain a hydrolyzate containing a hydrolyzate of an organosilicon compound and a hydrolyzate of a (meth) acryl group-containing silicon compound. A decomposition product mixture (A) was obtained.

(Production of photocurable nanoimprint composition)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), 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 hydrolyzate mixture (A), the mixture was stirred and mixed at room temperature for 15 minutes (?) To obtain a photocurable nanoimprinting composition. Tables 1 and 2 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 6
(Production of hydrolyzate mixture (A))
A hydrolyzate mixture (A) was obtained in the same manner as in Example 5.

(Production of photocurable nanoimprint composition)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 4.4 g of the hydrolyzate mixture (A), the mixture was stirred and mixed at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition. Tables 1 and 2 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 7
(Production of hydrolyzate mixture (A))
13.6 g of ethanol, 3.0 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as a (meth) acrylic group-containing silicon compound, and diphenyldimethoxysilane (Shin-Etsu Chemical Co., Ltd.) as an organosilicon compound LS-5300 (manufactured by LS-5300) was mixed, and while stirring this mixture, 4.3 g of ethanol / 0.7 g of water / 2 N-HCl 0.1 g of a 2N-HCl / ethanol mixed aqueous solution was gradually added at room temperature. It was dripped. Further, an ethanol aqueous solution of 1.0 g of ethanol / 0.4 g of water was gradually added dropwise and stirred at room temperature for 1 hour to prepare a hydrolyzate containing a hydrolyzate of an organosilicon compound and a hydrolyzate of a (meth) acryl group-containing silicon compound. A decomposition product mixture (A) was obtained.

(Production of photocurable nanoimprint composition)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 4.2 g of the hydrolyzate mixture (A), the mixture was stirred and mixed at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition. Tables 1 and 2 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 8
(Production of hydrolyzate mixture (A))
11.8 g of ethanol, 3.0 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as a (meth) acrylic group-containing silicon compound, diphenyldimethoxysilane (Shin-Etsu Chemical Co., Ltd.) as an organosilicon compound LS-5300 (manufactured by LS-5300) was mixed and the mixture was stirred and mixed. It was dripped. Further, an ethanol aqueous solution of 0.9 g of ethanol / 1.5 g of water was gradually added dropwise and stirred at room temperature for 1 hour, so A decomposition product mixture (A) was obtained.

(Production of photocurable nanoimprint composition)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 4.3 g of the hydrolyzate mixture (A), the mixture was stirred and mixed at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition. Tables 1 and 2 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 9
(Production of hydrolyzate mixture (A))
The same operation as in Example 2 was performed to obtain a hydrolyzate mixture (A).

(Production of photocurable nanoimprint composition)
In Example 1, as a polymerizable monomer having a (meth) acryl group, ethoxylated bisphenol A diacrylate (Shin Nakamura Chemical Co., Ltd.) was used instead of 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene. A photocurable nanoimprinting composition was obtained in the same manner as in Example 1 except that 5.0 g of ABE-300 manufactured by Co., Ltd. was used and 4.3 g of the hydrolyzate mixture (A) was added. Tables 1 and 2 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 10
(Production of hydrolyzate mixture (A))
13.6 g of ethanol, 3.0 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as a (meth) acrylic group-containing silicon compound, and diphenyldimethoxysilane (Shin-Etsu Chemical Co., Ltd.) as an organosilicon compound LS-5300 manufactured by LS-5300) and 5.4 g phenyltriethoxysilane (LS-4800 manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed, and while stirring and mixing the mixture, 4.2 g ethanol / 0.9 g water / 2N-HCl 0.2 g of a 2N-HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. Further, an ethanol aqueous solution of 1.0 g of ethanol / 0.5 g of water was gradually added dropwise and stirred at room temperature for 1 hour, so A decomposition product mixture (A) was obtained.

(Production of photocurable nanoimprint composition)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 4.2 g of the hydrolyzate mixture (A), the mixture was stirred and mixed at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition. Tables 1 and 2 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 11
(Production of hydrolyzate mixture (A))
13.6 g of ethanol, 3.0 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as a (meth) acrylic group-containing silicon compound, and diphenyldimethoxysilane (Shin-Etsu Chemical Co., Ltd.) as an organosilicon compound LS-5300 (manufactured by LS-5300) and 3.6 g of phenyltriethoxysilane (LS-4800 manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed. While stirring and mixing the mixture, 4.3 g of ethanol / 0.9 g / water 2N-HCl 0.2 g of a 2N-HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. Further, an ethanol aqueous solution of 1.0 g of ethanol / 0.5 g of water was gradually added dropwise and stirred at room temperature for 1 hour, so A decomposition product mixture (A) was obtained.

(Production of photocurable nanoimprint composition)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 4.2 g of the hydrolyzate mixture (A), the mixture was stirred and mixed at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition. Tables 1 and 2 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 12
(Production of hydrolyzate mixture (A))
8.4 g of ethanol, 1.5 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as a (meth) acrylic group-containing silicon compound, and diphenyldimethoxysilane (Shin-Etsu Chemical Co., Ltd.) as an organosilicon compound LS-5300 (manufactured by LS-5300) and 1.6 g of tungsten (V) ethoxide (manufactured by Alfa Aesar) were mixed. While stirring and mixing the mixture, ethanol 2.6 g / water 0.6 g / 2N-HCl 1 g of a 2N-HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. Further, an ethanol aqueous solution of ethanol 0.6 g / water 0.3 g was gradually added dropwise and stirred at room temperature for 1 hour to hydrolyze an organosilicon compound, a hydrolyzate of a (meth) acryl group-containing silicon compound, and a metal alkoxide. A hydrolyzate mixture (A) containing the hydrolyzate was obtained.

(Production of photocurable nanoimprint composition)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 4.2 g of the hydrolyzate mixture (A), the mixture was stirred and mixed at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition. Tables 1 and 2 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 13
(Production of hydrolyzate mixture (A))
8.4 g of ethanol, 1.5 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as a (meth) acrylic group-containing silicon compound, and diphenyldimethoxysilane (Shin-Etsu Chemical Co., Ltd.) as an organosilicon compound LS-5300 (manufactured by LS-5300) and 0.8 g of tungsten (V) ethoxy (manufactured by Alfa Aesar) were mixed. While stirring and mixing the mixture, ethanol 2.6 g / water 0.5 g / 2N-HCl 0 0.1 2N-HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. Further, an ethanol aqueous solution of ethanol 0.6 g / water 0.3 g was gradually added dropwise and stirred at room temperature for 1 hour to hydrolyze an organosilicon compound, a hydrolyzate of a (meth) acryl group-containing silicon compound, and a metal alkoxide. A hydrolyzate mixture (A) containing the hydrolyzate was obtained.

(Production of photocurable nanoimprint composition)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 4.9 g of the hydrolyzate mixture (A), the mixture was stirred and mixed at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition. Tables 1 and 2 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 14
(Production of hydrolyzate mixture (A))
14.8 g of ethanol, 3.0 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as a (meth) acrylic group-containing silicon compound, diphenyldimethoxysilane (Shin-Etsu Chemical Co., Ltd.) as an organosilicon compound LS-5300 manufactured by LS-5300) and 1.0 g of ethyl silicate 40 (average pentamer of tetraethoxysilane manufactured by Corcor Co., Ltd.) were mixed and 4.6 g of ethanol / water was stirred and mixed. 1.1 g / 2N-HCl 0.1 2N-HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. Furthermore, an ethanol aqueous solution of 1.1 g of ethanol / 0.5 g of water was gradually added dropwise and stirred at room temperature for 1 hour, so that a hydrolyzate containing a hydrolyzate of an organosilicon compound and a hydrolyzate of a (meth) acrylic group-containing silicon compound was obtained. A decomposition product mixture (A) was obtained.

(Production of photocurable nanoimprint composition)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 4.1 g of the hydrolyzate mixture (A), the mixture was stirred and mixed at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition. Tables 3 and 4 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 15
(Production of hydrolyzate mixture (A))
13.4 g of ethanol, 3.0 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as a (meth) acrylic group-containing silicon compound, and diphenyldimethoxysilane (Shin-Etsu Chemical Co., Ltd.) as an organosilicon compound LS-5300 manufactured by LS-5300) and 2.9 g of ethyl silicate 40 (average pentamer of tetraethoxysilane manufactured by Corcor Co., Ltd.), and while stirring and mixing the mixture, 4.2 g of ethanol / water 1.1 g / 2N-HCl 0.2 2N-HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. Further, an ethanol aqueous solution of 1.00 g of ethanol / 0.6 g of water was gradually added dropwise and stirred at room temperature for 1 hour. A decomposition product mixture (A) was obtained.

(Production of photocurable nanoimprint composition)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 3.8 g of the hydrolyzate mixture (A), the mixture was stirred and mixed at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition. Tables 3 and 4 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 16
(Production of hydrolyzate mixture (A))
The same operation as in Example 2 was performed to obtain a hydrolyzate mixture (A).

(Production of photocurable nanoimprint composition)
In Example 1, as the polymerizable monomer (B) having a (meth) acrylic group, the amount of hydroxyethylated o-phenylphenol acrylate was adjusted to 2.0 g, and tricyclodecane dimethanol diacrylate (Shin Nakamura Chemical Co., Ltd.). Stirring was performed at room temperature for 15 minutes in the same manner as in Example 1 except that 3.0 g of NK ester A-DCP (produced by Kogyo Co., Ltd.) was added and 4.2 g of the hydrolyzate mixture (A) was added. By mixing, a photocurable nanoimprinting composition was obtained. Tables 3 and 4 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 17
(Production of hydrolyzate mixture (A))
24.1 g of ethanol, 3.0 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as the (meth) acrylic group-containing silicon compound, diphenyldimethoxysilane (Shin-Etsu Chemical Co., Ltd.) as the organosilicon compound LS-5300 (manufactured by LS-5300) was mixed, and while stirring this mixture, 7.5 g of ethanol / 1.8 g of water / 2 N-HCl 0.2 g of a 2N-HCl / ethanol mixed aqueous solution was gradually added at room temperature. It was dripped in. Further, an ethanol aqueous solution of 1.8 g of ethanol / 0.9 g of water was gradually added dropwise and stirred at room temperature for 1 hour to prepare a hydrolyzate containing a hydrolyzate of an organosilicon compound and a hydrolyzate of a (meth) acryl group-containing silicon compound. A decomposition product mixture (A) was obtained.

(Production of photocurable nanoimprint composition)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 4.3 g of the hydrolyzate mixture (A), the mixture was stirred and mixed at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition. Tables 3 and 4 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 18
(Production of hydrolyzate mixture (A))
3.0 g of ethanol, 3.0 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as a (meth) acrylic group-containing silicon compound, and diphenyldimethoxysilane (Shin-Etsu Chemical Co., Ltd.) as an organosilicon compound LS-5300 (manufactured by LS-5300) was mixed, and while stirring this mixture, 1.0 g of ethanol / 0.4 g of water / 2 g of 2N HCl 0.2 g of 2N HCl / ethanol mixed aqueous solution was gradually added at room temperature. It was dripped in. Further, an ethanol aqueous solution of 1.0 g of ethanol / 0.2 g of water was gradually added dropwise and stirred at room temperature for 1 hour. A decomposition product mixture (A) was obtained.

(Production of photocurable nanoimprint composition)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 4.2 g of the hydrolyzate mixture (A), the mixture was stirred and mixed at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition. Tables 3 and 4 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 19
(Production of hydrolyzate mixture (A))
A hydrolyzate mixture (A) was obtained in the same manner as in Example 2.

(Production of photocurable nanoimprint composition)
In Example 1, 10.0 g of an acrylate fluorene derivative (Ogsol EA-F5503, manufactured by Osaka Gas Chemical Co., Ltd.) was used as the polymerizable monomer (B) having a (meth) acryl group, and a hydrolyzate mixture ( A) A photocurable nanoimprinting composition was obtained by stirring and mixing at room temperature for 15 minutes in the same manner as in Example 1 except that 4.2 g was added. Tables 3 and 4 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 20
(Production of hydrolyzate mixture (A))
A hydrolyzate mixture (A) was obtained in the same manner as in Example 2.

(Production of photocurable nanoimprint composition)
In Example 1, 10.0 g of an acrylate fluorene derivative (Ogsol EA-F5003, manufactured by Osaka Gas Chemical Co., Ltd.) was used as the polymerizable monomer (B) having a (meth) acryl group, and a hydrolyzate mixture ( A) A photocurable nanoimprinting composition was obtained by stirring and mixing at room temperature for 15 minutes in the same manner as in Example 1 except that 4.2 g was added. Tables 3 and 4 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 21
(Production of hydrolyzate mixture (A))
A hydrolyzate mixture (A) was obtained in the same manner as in Example 2.

(Production of photocurable nanoimprint composition)
In Example 1, as a polymerizable monomer (B) having a (meth) acryl group, an acrylate fluorene derivative (Osaka Gas) was used instead of 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene. Photocuring was performed by stirring and mixing at room temperature for 15 minutes in the same manner as in Example 1 except that 5.0 g of Ogsol EA-F5503 manufactured by Chemical Co., Ltd. and 4.2 g of the hydrolyzate mixture (A) were added. A nano-imprinting composition was obtained. Tables 3 and 4 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 22
(Production of hydrolyzate mixture (A))
A hydrolyzate mixture (A) was obtained in the same manner as in Example 2.

(Production of photocurable nanoimprint composition)
As the photopolymerization initiator (C), 0.05 g of 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one was used, A photocurable nanoimprinting composition was obtained in the same manner as in Example 1 except that 4.2 g of the hydrolyzate mixture (A) was added. Tables 3 and 4 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 23
(Production of hydrolyzate mixture (A))
A hydrolyzate mixture (A) was obtained in the same manner as in Example 2.

(Production of photocurable nanoimprint composition)
In Example 1, as a polymerizable monomer (B) having a (meth) acryl group, polyethylene glycol # 200 diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-200) 5.0 g, tricyclo Example 1 was used except that 5.0 g of decanedimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-DCP) was added and 4.2 g of the hydrolyzate mixture (A) was added. The mixture was stirred and mixed at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition. Tables 3 and 4 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Comparative Example 1
(Production of photocurable nanoimprint composition)
A photocurable nanoimprinting composition was obtained in the same manner as in Example 1 except that the hydrolyzate mixture (A) was not added. Tables 3 and 4 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Comparative Example 2
(Production of hydrolyzate mixture (A))
4.3 g of ethanol and 4.5 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as a (meth) acrylic group-containing silicon compound are mixed, and the mixture is stirred and mixed with ethanol 1 0.4 g / water 0.4 g / 2N-HCl 0.07 g of a 2N-HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. Further, an ethanol aqueous solution of ethanol 0.4 g / water 0.3 g was gradually added dropwise and stirred at room temperature for 1 hour to obtain a hydrolyzate mixture (A) containing a hydrolyzate of a (meth) acryl group-containing silicon compound. It was.

(Production of photocurable nanoimprint composition)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 4.3 g of the hydrolyzate mixture (A), the mixture was stirred and mixed at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition. Tables 3 and 4 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6. The cure shrinkage of the coating film was large, and uneven projections were seen on the surface, so the sapphire selectivity could not be calculated.

Comparative Example 3
(Production of hydrolyzate mixture (A))
3.1 g of ethanol and 3.0 g of diphenyldimethoxysilane (LS-5300 manufactured by Shin-Etsu Chemical Co., Ltd.) as an organic silicon compound were mixed, and 1.0 g of ethanol / 0.2 g / water of water was stirred and mixed. 2N-HCl 0.03 g of a 2N-HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. Furthermore, ethanol aqueous solution of ethanol 0.2g / water 0.1g was gradually dripped, and it stirred at room temperature for 1 hour, and obtained the hydrolyzate mixture (A) containing the hydrolyzate of an organosilicon compound.

(Production of photocurable nanoimprint composition)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 4.4 g of the hydrolyzate mixture (A), the mixture was stirred and mixed at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition. Tables 3 and 4 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6. The photocurable nanoimprint composition was insufficient in photocurability and could not form a pattern. In addition, the sapphire selectivity could not be calculated due to insufficient photocurability.

Comparative Example 4
(Production of hydrolyzate mixture (A))
13.6 g of ethanol, 3.0 g of trimethoxysilyl trimethylene acrylate (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) as the (meth) acrylic group-containing silicon compound, and tetraethoxysilane (Tokyo Chemical Industry Co., Ltd.) as the organosilicon compound 9.4 g) was mixed, and while stirring and mixing this mixture, ethanol 4.3 g / water 1.2 g / 2 N-HCl 0.2 g 2N-HCl / ethanol mixed aqueous solution was gradually added dropwise at room temperature. Further, an ethanol aqueous solution of ethanol 1.0 g / water 0.6 g was gradually added dropwise and stirred at room temperature for 1 hour to hydrolyze an organosilicon compound, a hydrolyzate of a (meth) acrylic group-containing silicon compound, and a metal alkoxide. A hydrolyzate mixture (A) containing the hydrolyzate was obtained.

(Production of photocurable nanoimprint composition)
After mixing the same type, the same amount of the polymerizable monomer (B), the photopolymerization initiator (C), and the polymerization inhibitor as used in Example 1, the same amount of the mixture (1.0 g) After adding 4.1 g of the hydrolyzate mixture (A), the mixture was stirred and mixed at room temperature for 15 minutes to obtain a photocurable nanoimprinting composition. Tables 3 and 4 show the blending ratio of the photocurable nanoimprint composition.

  Using the obtained composition for photo-curable nanoimprint, filterability, substrate adhesion of a cured film, transferability, and sapphire selectivity were evaluated. The results are shown in Tables 5 and 6.

Example 24
(Manufacture of surface processed sapphire substrates)
The photocurable nanoimprinting composition obtained in Example 2 was diluted with 1-methoxy-2-propanol to 10 wt%. 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 110 ° 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.

Claims (6)

(A) The following formula (1)

(Where
R ¹ and R ² are the same or different alkyl groups having 1 to 4 carbon atoms,
R ³ is an aryl group;
R ⁴ is an aryl group or an alkoxy group having 1 to 4 carbon atoms,
n is an integer of 1 to 10) and a hydrolyzate of an organosilicon compound represented by the following formula (2)

(Where
R ⁵ is a hydrogen atom or a methyl group,
R ⁶ is an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms,
R ⁷ 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 ⁸ 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,
When ^{R 5, R 6, R 7} , and ^{where R 8} each, there are a plurality, the plurality of ^{R 5, R 6, R 7} , and ^{R 8} each may be the same or different groups)
A hydrolyzate mixture containing a hydrolyzate of an organosilicon compound having a (meth) acryl group represented by:
(B) a polymerizable monomer having a (meth) acryl group, and (C) a photopolymerization initiator ,
For 100 parts by mass of the polymerizable monomer (B) having the (meth) acryl group,
Hydrolyzing a hydrolysis component mixture containing 10 to 400 parts by mass of the organosilicon compound represented by the formula (1) and 3 to 300 parts by mass of the organosilicon compound having a (meth) acryl group represented by the formula (2) Hydrolyzate mixture (A) obtained by
0.1-10 parts by mass of the photopolymerization initiator (C)
The composition for photocurable nanoimprint characterized by including this. The hydrolyzate mixture (A) is further represented by the following formula (3)

(Where
M is tungsten, tin, indium, antimony or hafnium;
R ⁹ is an alkyl group having 1 to 10 carbon atoms, and may be the same or different group,
p is 5 when M is tungsten, 4 when M is tin or hafnium, and 3 when M is indium or antimony)
In photocurable composition for imprints of claim 1, characterized in that it comprises a hydrolyzate of a metal alkoxide represented. For 100 parts by mass of the polymerizable monomer (B) having the (meth) acryl group,
10 to 400 parts by weight of an organic silicon compound represented by the formula (1), represented by the formula (2) (meth) organosilicon compound having an acrylic group 3 to 300 parts by weight, and the formula (3) Hydrolyzate mixture (A) obtained by hydrolyzing a hydrolysis component mixture containing 0.1 to 150 parts by mass of metal alkoxide, and
It contains 0.1-10 mass parts of said photoinitiators (C), The composition for photocurable nanoimprints of Claim 2 characterized by the above-mentioned. The hydrolyzate mixture (A), an organic silicon compound represented by the formula (1), and the total 100 parts by weight of the formula organosilicon compound having a (meth) acrylic group represented by (2) photocuring of claim 3, characterized in that the above formula (3) hydrolyzate mixture obtained by hydrolysis component mixture is hydrolyzed comprising 0.2 to 50 parts by mass of the metal alkoxide represented by Nanoimprint composition. The process of apply | coating the composition for photocurable nanoimprint in any one of Claims 1-4 on a board | substrate, and forming the coating film which consists of this composition,
A step of bringing the mold pattern forming surface on which the pattern is formed into contact 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. 6. A surface-processed sapphire substrate, characterized in that the substrate surface 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 5 as a mask. Manufacturing method.