JP2011057565A - Compound and curable composition comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound that achieves both low viscosity and low volatility. <P>SOLUTION: The compound is represented by general formula (1), (2), (3), (4) or (5) and has a molecular weight of at least 310. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel compound and a curable composition using the same. In particular, it relates to a curable composition suitable for imprinting. Furthermore, the present invention relates to a cured product using these curable compositions and a method for producing the cured product.

  Two types of nanoimprint methods have been proposed: a case where a thermoplastic resin is used as a material to be processed (Non-Patent Document 1) and a case where a curable composition for optical nanoimprint lithography is used (Non-Patent Document 2). In the case of thermal nanoimprinting using a thermoplastic resin, the mold is pressed onto a polymer resin heated to a glass transition temperature or higher, and the mold is released after cooling to transfer the microstructure to the resin on the substrate. Since it can be applied to various resin materials and glass materials, it is expected to be applied in various fields. For example, Patent Document 1 and Patent Document 2 disclose a nanoimprint method for forming a nanopattern at low cost using a thermoplastic resin.

  On the other hand, in the optical nanoimprint method in which light is irradiated through a transparent mold and the curable composition for nanoimprint is photocured, imprinting at room temperature becomes possible. Recently, new developments such as a nanocasting method combining the advantages of both and a reversal imprint method for producing a three-dimensional laminated structure have been reported.

  In such a nanoimprint method, the following applied technologies have been proposed. The first technique is to apply high-precision alignment and high integration to the fabrication of high-density semiconductor integrated circuits and fabrication of liquid crystal display transistors in place of conventional lithography. . The second technique is the case where the molded shape (pattern) itself has a function and can be applied as various nanotechnology element parts or structural members. Examples include various micro / nano optical elements, Examples include high-density recording media, optical films, and structural members in flat panel displays. In addition, as another technique, there is a technique in which a laminated structure is constructed by simultaneous integral molding of a micro structure and a nano structure, or simple interlayer alignment, and is applied to manufacture of μ-TAS and a biochip. In recent years, efforts to put nanoimprinting methods into practical use for these applications, including the aforementioned technologies, have become active.

  First, an application example of the first technique for creating a high-density semiconductor integrated circuit will be described. 2. Description of the Related Art In recent years, semiconductor integrated circuits have been miniaturized and integrated, and photolithography apparatuses have been improved in accuracy as a pattern transfer technique for realizing the fine processing. On the other hand, the use of a nanoimprint lithography technique (optical nanoimprint method) proposed as a technique for performing fine pattern formation at low cost has been studied. For example, a nanoimprint technique is known in which a silicon wafer is used as a stamper and a fine structure of 25 nm or less is formed by transfer.

  On the other hand, an application example of nanoimprint lithography to a flat display such as a liquid crystal display (LCD) or a plasma display (PDP) in the second technique will be described. With the trend toward larger and higher definition LCD substrates and PDP substrates, optical nanoimprint lithography has attracted attention in recent years as an inexpensive lithography that can replace conventional photolithography methods used in the manufacture of thin film transistors (TFTs) and electrode plates. Therefore, it has become necessary to develop a photo-curable resist that replaces the etching photoresist used in the conventional photolithography method. In addition, application of optical nanoimprint lithography is also being studied for transparent protective film materials used as structural members for LCDs, spacers for defining cell gaps in liquid crystal displays, and the like. Unlike the etching resist, such a resist for a structural member is finally left in the display, and is sometimes referred to as “permanent resist” or “permanent film”.

As a permanent film to which a conventional photolithography technique is applied, for example, a protective film provided on a TFT substrate of a liquid crystal panel, or an ITO film that reduces a step between red (R), green (G), and blue (B) layers. For example, a protective film provided on the color filter for imparting resistance to high-temperature treatment during sputtering film formation.
In the field of spacers used in liquid crystal displays, photocurable compositions comprising a resin, a photopolymerizable monomer, and a photopolymerization initiator have generally been widely used in conventional photolithography methods. The spacer generally forms a pattern having a size of about 10 μm to 20 μm by photolithography using a photocurable composition on the color filter substrate after forming the color filter or after forming the color filter protective film. Further, it is formed by heat curing by post-baking.

  Here, the low viscosity and low volatility are calculated | required by the compound used for the curable composition for imprints. This is because if the composition viscosity is low, the pattern accuracy is excellent, while if the volatility is low, contamination of the imprint apparatus can be reduced.

US Pat. No. 5,772,905 US Pat. No. 5,956,216 S.Chou et al.:Appl.Phys.Lett.Vol.67,3114 (1995) M.Colbun et al,: Proc.SPIE, Vol. 3676,379 (1999)

  As described above, the compounds used in the curable composition for imprints are required to have both low viscosity and low volatility. In general, low viscosity compounds are easily volatile and less volatile compounds are viscous. Tend to be high. That is, it can be said that low viscosity and low volatility are contradictory properties. The object of the present invention is to solve such problems and to provide a compound capable of achieving both low viscosity and low volatility. Furthermore, it aims at providing the curable composition for imprints which uses this compound.

（一般式（１）、（２）、（３）、（４）および（５）中、Ｒ¹およびＲ²は、それぞれ、水素原子またはメチル基を表す。一般式（１）中、Ｒ³は炭素数４〜１０の炭化水素基を表す。一般式（２）中、Ｒ⁴は炭素数８〜１４のアルキル基を表す。一般式（３）中、Ｒ⁵は炭素数４〜１５の、アルキル基または不飽和炭化水素基を表す。一般式（４）中、Ｒ⁶は炭素数２〜１０の直鎖状アルキル基を表し、Ｒ⁷は炭素数２〜１２の不飽和炭化水素基、あるいは（メタ）アクリロイルオキシエチル基を表す。一般式（５）中、Ｒ⁸は炭素数６〜１５の炭化水素基を表す。）
（２）（１）において、一般式（１）で表される化合物であって、Ｒ³が炭素数４〜１０の脂肪族炭化水素基である化合物、一般式（２）で表される化合物であって、Ｒ⁴が炭素数８〜１４のアルキル基である化合物、一般式（３−１）で表される化合物、一般式（３−２）で表される化合物、一般式（４−１）で表される化合物、一般式（４−２）で表される化合物、一般式（５）で表される化合物であって、Ｒ⁸が炭素数６〜１５の脂肪族炭化水素基である化合物、または下記の化合物。
一般式（３−１）

（一般式（３−１）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子またはメチル基を表す。Ｒ⁵¹は、炭素数４〜８のアルキル基を表す。）
一般式（３−２）

（一般式（３−２）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子またはメチル基を表す。Ｒ⁵²は、炭素数５〜９のアルキル基を表す。）
一般式（３−３）

（一般式（３−３）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子またはメチル基を表す。Ｒ⁵³は、総炭素数５〜１２の炭化水素基であって、−ＣＨ＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ₃）−、−Ｃ（ＣＨ₃）＝Ｃ（ＣＨ₃）−、−ＣＨ＝ＣＨ₂、−ＣＨ＝ＣＨ（ＣＨ₃）、−Ｃ（ＣＨ₃）＝ＣＨ₂および−Ｃ（ＣＨ₃）＝ＣＨ（ＣＨ₃）から選択される基の少なくとも１つと、アルキル基およびアルキレン基の少なくとも１つとの組み合わせからなる基である。）
一般式（４−１）

（一般式（４−１）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子またはメチル基を表す。Ｒ⁶¹は、炭素数２〜８の直鎖のアルキル基を表す。）
一般式（４−２）

（一般式（４−２）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子またはメチル基を表す。Ｒ⁷¹は、炭素数２〜１２の不飽和炭化水素基または（メタ）アクリロイルオキシエチル基を表し、Ｒ⁷²はメチル基またはエチル基を表す。）

（３）（１）において、一般式（１）で表される化合物であって、Ｒ³が炭素数４〜８の直鎖のアルキル基である化合物、一般式（２）で表される化合物であって、Ｒ⁴が炭素数１０〜１２のアルキル基である化合物、一般式（３−１）で表される化合物、一般式（３−２）で表される化合物、一般式（３−３）で表される化合物、一般式（４−１）で表される化合物、一般式（５）で表される化合物であって、Ｒ⁸は炭素数６〜１３の直鎖アルキル基である化合物、または下記のいずれかの化合物。
一般式（３−１）

（一般式（３−１）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子またはメチル基を表す。Ｒ⁵¹は、炭素数４〜８のアルキル基を表す。）
一般式（３−２）

（一般式（３−２）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子またはメチル基を表す。Ｒ⁵²は、炭素数５〜９のアルキル基を表す。）
一般式（３−３）

（一般式（３−３）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子またはメチル基を表す。Ｒ⁵³は、総炭素数５〜１２の炭化水素基であって、−ＣＨ＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ₃）−、−Ｃ（ＣＨ₃）＝Ｃ（ＣＨ₃）−、−ＣＨ＝ＣＨ₂、−ＣＨ＝ＣＨ（ＣＨ₃）、−Ｃ（ＣＨ₃）＝ＣＨ₂および−Ｃ（ＣＨ₃）＝ＣＨ（ＣＨ₃）から選択される基の少なくとも１つと、アルキル基およびアルキレン基の少なくとも１つとの組み合わせからなる基である。）
一般式（４−１）

（一般式（４−１）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子またはメチル基を表す。Ｒ⁶¹は、炭素数２〜８の直鎖のアルキル基を表す。）

（４）下記のいずれかの化合物。

（５）（１）〜（４）のいずれか１項に記載の化合物と、光重合開始剤を含む、硬化性組成物。
（６）光照射により硬化することを特徴とする（５）に記載の硬化性組成物。
（７）加熱により硬化することを特徴とする（５）に記載の硬化性組成物。
（８）ナノインプリント用である、（５）〜（７）のいずれか１項に記載の硬化性組成物。
（９）（５）〜（８）のいずれか１項に記載の組成物を硬化させた硬化物。
（１０）（１）〜（４）のいずれか１項に記載の化合物と、光重合開始剤を含むナノインプリント用硬化性組成物を基板上に適用して層状とする工程と、該層状に形成した層にモールドに押圧する工程と、前記層状に形成した層に光照射する工程を含むことを特徴とする硬化物の製造方法。
（１１）さらに、前記形成された層に、光を照射後、加熱する工程を含むことを特徴とする（１０）に記載の硬化物の製造方法。
（１２）（９）に記載の硬化物を含む液晶表示装置用部材。 Under such circumstances, the inventor of the present application has intensively studied to study a compound having a low viscosity and a low volatility, and has completed the present invention. Specifically, the object of the present invention has been achieved by the following means.
(1) A compound having a molecular weight of 310 or more, represented by the following general formula (1), the following general formula (2), the following general formula (3), the following general formula (4) or the following general formula (5).

(In the general formulas (1), (2), (3), (4) and (5), R ¹ and R ² each represent a hydrogen atom or a methyl group. In the general formula (1), R ³ Represents a hydrocarbon group having 4 to 10 carbon atoms, in formula (2), R ⁴ represents an alkyl group having 8 to 14 carbon atoms, and in formula (3), R ⁵ represents a group having 4 to 15 carbon atoms. In general formula (4), R ⁶ represents a linear alkyl group having 2 to 10 carbon atoms, and R ⁷ represents an unsaturated hydrocarbon group having 2 to 12 carbon atoms. Or a (meth) acryloyloxyethyl group, wherein R ⁸ represents a hydrocarbon group having 6 to 15 carbon atoms in the general formula (5).
(2) In (1), a compound represented by the general formula (1), wherein R ³ is an aliphatic hydrocarbon group having 4 to 10 carbon atoms, a compound represented by the general formula (2) Wherein R ⁴ is an alkyl group having 8 to 14 carbon atoms, a compound represented by the general formula (3-1), a compound represented by the general formula (3-2), a general formula (4- 1), a compound represented by the general formula (4-2), a compound represented by the general formula (5), wherein R ⁸ is an aliphatic hydrocarbon group having 6 to 15 carbon atoms. A certain compound or the following compound.
General formula (3-1)

(In General Formula (3-1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ⁵¹ represents an alkyl group having 4 to 8 carbon atoms.)
Formula (3-2)

(In general formula (3-2), R ¹ and R ² each independently represents a hydrogen atom or a methyl group. R ⁵² represents an alkyl group having 5 to 9 carbon atoms.)
General formula (3-3)

(In General Formula (3-3), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ⁵³ is a hydrocarbon group having 5 to 12 carbon atoms in total, and —CH═ CH -, - CH = C ( CH 3) -, - C (CH 3) = C (CH 3) -, - CH = CH 2, -CH = CH (CH 3), - C (CH 3) = CH ₂ and a group consisting of a combination of at least one group selected from —C (CH ₃ ) ═CH (CH ₃ ) and at least one of an alkyl group and an alkylene group.
Formula (4-1)

(In General Formula (4-1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ⁶¹ represents a linear alkyl group having 2 to 8 carbon atoms.)
General formula (4-2)

(In General Formula (4-2), R ¹ and R ² each independently represents a hydrogen atom or a methyl group. R ⁷¹ represents an unsaturated hydrocarbon group having 2 to 12 carbon atoms or (meth) acryloyloxy. Represents an ethyl group, and R ⁷² represents a methyl group or an ethyl group.)

(3) In (1), a compound represented by the general formula (1), wherein R ³ is a linear alkyl group having 4 to 8 carbon atoms, a compound represented by the general formula (2) Wherein R ⁴ is an alkyl group having 10 to 12 carbon atoms, a compound represented by the general formula (3-1), a compound represented by the general formula (3-2), a general formula (3- 3), a compound represented by the general formula (4-1), a compound represented by the general formula (5), wherein R ⁸ is a linear alkyl group having 6 to 13 carbon atoms. A compound or one of the following compounds:
General formula (3-1)

(In General Formula (3-1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ⁵¹ represents an alkyl group having 4 to 8 carbon atoms.)
Formula (3-2)

(In general formula (3-2), R ¹ and R ² each independently represents a hydrogen atom or a methyl group. R ⁵² represents an alkyl group having 5 to 9 carbon atoms.)
General formula (3-3)

(In General Formula (3-3), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ⁵³ is a hydrocarbon group having 5 to 12 carbon atoms in total, and —CH═ CH -, - CH = C ( CH 3) -, - C (CH 3) = C (CH 3) -, - CH = CH 2, -CH = CH (CH 3), - C (CH 3) = CH ₂ and a group consisting of a combination of at least one group selected from —C (CH ₃ ) ═CH (CH ₃ ) and at least one of an alkyl group and an alkylene group.
Formula (4-1)

(In General Formula (4-1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ⁶¹ represents a linear alkyl group having 2 to 8 carbon atoms.)

(4) Any of the following compounds.

(5) A curable composition comprising the compound according to any one of (1) to (4) and a photopolymerization initiator.
(6) The curable composition as described in (5), which is cured by light irradiation.
(7) The curable composition as described in (5), which is cured by heating.
(8) The curable composition according to any one of (5) to (7), which is for nanoimprinting.
(9) A cured product obtained by curing the composition according to any one of (5) to (8).
(10) A step of applying a curable composition for nanoimprinting comprising the compound according to any one of (1) to (4) and a photopolymerization initiator on a substrate to form a layer, and forming the layer A method for producing a cured product, comprising: a step of pressing a molded layer against a mold; and a step of irradiating the layer formed in the layer shape with light.
(11) The method for producing a cured product according to (10), further comprising a step of heating the formed layer after irradiation with light.
(12) A liquid crystal display member comprising the cured product according to (9).

 According to the present invention, it has become possible to provide a compound having low viscosity and low volatility. Moreover, the composition using the compound of the present invention is excellent in curability and can suppress contamination in the apparatus during curing. Furthermore, by using the compound of the present invention for a curable composition for nanoimprint, it has become possible to provide a pattern having high transfer pattern accuracy after curing. In particular, since it has low volatility and excellent vacuum resistance, a highly accurate pattern can be formed without contaminating the inside of the imprint apparatus.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

The present invention is described in detail below. In the present specification, (meth) acrylate represents acrylate and methacrylate, (meth) acryl represents acryl and methacryl, and (meth) acryloyl represents acryloyl and methacryloyl. Moreover, in this specification, a monomer and a monomer are the same. The monomer in the present invention is a compound having a mass average molecular weight of 1,000 or less, distinguished from oligomers and polymers. In the present specification, the functional group refers to a group involved in polymerization.
The “imprint” referred to in the present invention preferably refers to pattern transfer having a size of 1 nm to 10 mm, and more preferably refers to pattern transfer having a size (nanoimprint) of approximately 10 nm to 100 μm.

（一般式（１）、（２）、（３）、（４）、（５）中のＲ¹およびＲ²は、それぞれ、水素原子またはメチル基を表す。一般式（１）中、Ｒ³は炭素数４〜１０の炭化水素基を表す。一般式（２）中、Ｒ⁴は炭素数８〜１４のアルキル基を表す。一般式（３）中、Ｒ⁵は炭素数４〜１５の直鎖状炭化水素基を表す。一般式（４）中、Ｒ⁶は炭素数２〜１０の直鎖状アルキル基を表し、Ｒ⁷は炭素数２〜１２の不飽和炭化水素基、あるいは（メタ）アクリロイルオキシエチル基を表す。一般式（５）中、Ｒ⁸は炭素数６〜１５の炭化水素基を表す。） The compound disclosed by the present invention is a compound represented by the following general formula (1), general formula (2), general formula (3), general formula (4), or general formula (5), and has a molecular weight of 310. These compounds. Such a compound has both low viscosity and low volatility, and can be preferably employed in a curable composition, particularly a curable composition for imprints.

(R ¹ and R ² in the general formulas (1), (2), (3), (4), (5) each represent a hydrogen atom or a methyl group. In the general formula (1), R ³ Represents a hydrocarbon group having 4 to 10 carbon atoms, in formula (2), R ⁴ represents an alkyl group having 8 to 14 carbon atoms, and in formula (3), R ⁵ represents a group having 4 to 15 carbon atoms. In the general formula (4), R ⁶ represents a linear alkyl group having 2 to 10 carbon atoms, R ⁷ represents an unsaturated hydrocarbon group having 2 to 12 carbon atoms, or ( Represents a (meth) acryloyloxyethyl group, and R ⁸ represents a hydrocarbon group having 6 to 15 carbon atoms in the general formula (5).

The molecular weight of the compound of the present invention is preferably 310 or more, more preferably 320 or more, and particularly preferably 330 or more from the viewpoint of low volatility. The upper limit is not particularly defined, but is preferably 600 or less.
In general formulas (1) to (5), R ¹ and R ² are each preferably a hydrogen atom.
In general formulas (1) to (5), R ^{1 to} R ⁸ may each have a substituent, and in this case, the substituent is preferably a hydrocarbon group, more preferably an alkyl group, An alkyl group having 3 or less carbon atoms is more preferable. R ^{1 to} R ⁸ preferably have no substituent.

(Compound represented by the general formula (1))
In general formula (1), R ³ represents a hydrocarbon group having 4 to 10 carbon atoms, preferably a hydrocarbon group having 4 to 9 carbon atoms, and more preferably a hydrocarbon group having 4 to 8 carbon atoms. The hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. More preferably, the alkyl group is a linear alkyl group.
Moreover, the following compound is also preferable as a compound represented by General formula (1).

(Compound represented by the general formula (2))
In general formula (2), R ⁴ represents an alkyl group having 8 to 14 carbon atoms, preferably an alkyl group having 9 to 14 carbon atoms, and more preferably an alkyl group having 10 to 12 carbon atoms. More preferably, the alkyl group is a linear alkyl group.

（一般式（３−１）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子またはメチル基を表す。Ｒ⁵¹は、炭素数４〜８のアルキル基を表す。）
Ｒ⁵¹は、直鎖のアルキル基であることがさらに好ましい。
一般式（３−２）

（一般式（３−２）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子またはメチル基を表す。Ｒ⁵²は、炭素数５〜９のアルキル基を表す。）
Ｒ⁵²は、直鎖のアルキル基であることがさらに好ましい。
一般式（３−３）

（一般式（３−３）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子またはメチル基を表す。Ｒ⁵³は、総炭素数５〜１２の炭化水素基であって、−ＣＨ＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ₃）−、−Ｃ（ＣＨ₃）＝Ｃ（ＣＨ₃）−、−ＣＨ＝ＣＨ₂、−ＣＨ＝ＣＨ（ＣＨ₃）、−Ｃ（ＣＨ₃）＝ＣＨ₂および−Ｃ（ＣＨ₃）＝ＣＨ（ＣＨ₃）から選択される基の少なくとも１つと、アルキル基およびアルキレン基の少なくとも１つとの組み合わせからなる基である。）
−ＣＨ＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ₃）−、−Ｃ（ＣＨ₃）＝Ｃ（ＣＨ₃）−、−ＣＨ＝ＣＨ₂、−ＣＨ＝ＣＨ（ＣＨ₃）、−Ｃ（ＣＨ₃）＝ＣＨ₂および−Ｃ（ＣＨ₃）＝ＣＨ（ＣＨ₃）から選択される基は１つでも２つ以上であってもよいが、好ましくは１つである。これらの基の中で、−ＣＨ＝ＣＨ−または−ＣＨ＝ＣＨ₂であることが好ましく、少なくとも、−ＣＨ＝ＣＨ₂を含むことがより好ましい。
アルキル基およびアルキレン基の少なくとも１つは、少なくともアルキレン基を含むことが好ましい。
Ｒ⁵³の総炭素数は、６〜１１が好ましく、７〜１０がより好ましい。
Ｒ⁵³は、−アルキル基−ＣＨ＝ＣＨ₂であることが好ましく、この場合のアルキル基は、炭素数５〜８の直鎖のアルキル基であることがより好ましい。 (Compound represented by the general formula (3))
In general formula (3), R ⁵ represents a linear hydrocarbon group having 4 to 15 carbon atoms, preferably a linear hydrocarbon group having 4 to 14 carbon atoms, and a linear hydrocarbon group having 4 to 13 carbon atoms. A hydrogen group is more preferable. The general formula (3) is preferably represented by the general formula (3-1), the general formula (3-2), or the general formula (3-3).
General formula (3-1)

(In General Formula (3-1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ⁵¹ represents an alkyl group having 4 to 8 carbon atoms.)
R ⁵¹ is more preferably a linear alkyl group.
Formula (3-2)

(In general formula (3-2), R ¹ and R ² each independently represents a hydrogen atom or a methyl group. R ⁵² represents an alkyl group having 5 to 9 carbon atoms.)
R ⁵² is more preferably a linear alkyl group.
General formula (3-3)

(In General Formula (3-3), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ⁵³ is a hydrocarbon group having 5 to 12 carbon atoms in total, and —CH═ CH -, - CH = C ( CH 3) -, - C (CH 3) = C (CH 3) -, - CH = CH 2, -CH = CH (CH 3), - C (CH 3) = CH ₂ and a group consisting of a combination of at least one group selected from —C (CH ₃ ) ═CH (CH ₃ ) and at least one of an alkyl group and an alkylene group.
-CH = CH -, - CH = C (CH 3) -, - C (CH 3) = C (CH 3) -, - CH = CH 2, -CH = CH (CH 3), - C (CH 3 ) = CH ₂ and —C (CH ₃ ) ═CH (CH ₃ ) may be one or more groups, but preferably one. Among these groups, —CH═CH— or —CH═CH ₂ is preferable, and at least —CH═CH ₂ is more preferably included.
It is preferable that at least one of the alkyl group and the alkylene group includes at least an alkylene group.
6-11 are preferable and, as for the total carbon number of ^R53 , 7-10 are more preferable.
R ⁵³ is preferably an -alkyl group —CH═CH ₂ , and the alkyl group in this case is more preferably a linear alkyl group having 5 to 8 carbon atoms.

（一般式（４−１）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子またはメチル基を表す。Ｒ⁶¹は、炭素数２〜８の直鎖のアルキル基を表す。）
一般式（４−２）

（一般式（４−２）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子またはメチル基を表す。Ｒ⁷¹は、炭素数２〜１２の不飽和炭化水素基または（メタ）アクリロイルオキシエチル基を表し、Ｒ⁷²はメチル基またはエチル基を表す。）
炭素数２〜１２の不飽和炭化水素基としては、炭素炭素二重結合を１つまたは２つ以上含む基が好ましい。一般式（４−２）で表される化合物としては、下記の化合物が例示される。

(Compound represented by the general formula (4))
In the general formula (4), R ⁶ represents a linear alkyl group having 2 to 10 carbon atoms, preferably a linear alkyl group having 2 to 9 carbon atoms, and a linear alkyl group having 2 to 8 carbon atoms. More preferred. By setting it as such a range, a compound becomes low volatility and preferable. On the other hand, R ⁷ represents an unsaturated hydrocarbon group having 2 to 12 carbon atoms or a (meth) acryloyloxyethyl group, preferably a hydrocarbon group having 2 to 12 carbon atoms, and a hydrocarbon group having 2 to 11 carbon atoms. Further preferred. The general formula (4) is preferably a compound represented by the following general formula (4-1) or (4-2).
Formula (4-1)

(In General Formula (4-1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ⁶¹ represents a linear alkyl group having 2 to 8 carbon atoms.)
General formula (4-2)

(In General Formula (4-2), R ¹ and R ² each independently represents a hydrogen atom or a methyl group. R ⁷¹ represents an unsaturated hydrocarbon group having 2 to 12 carbon atoms or (meth) acryloyloxy. Represents an ethyl group, and R ⁷² represents a methyl group or an ethyl group.)
The unsaturated hydrocarbon group having 2 to 12 carbon atoms is preferably a group containing one or more carbon-carbon double bonds. Examples of the compound represented by the general formula (4-2) include the following compounds.

(Compound represented by the general formula (5))
In general formula (5), R ⁸ represents a hydrocarbon group having 6 to 15 carbon atoms, preferably a hydrocarbon group having 6 to 14 carbon atoms, and more preferably a hydrocarbon group having 6 to 13 carbon atoms. The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably an alkyl group, and even more preferably a linear alkyl group.
Moreover, as a compound represented by General formula (5), the following compound is also preferable.

  The compound of the present invention can be synthesized according to a known method. For example, it can be synthesized by considering the method described in JP-A-2009-114091.

Preferred examples of the compound of the present invention are shown below.

  The viscosity of the compound of the present invention is preferably 50 mPa · s or less, more preferably 30 mPa · s or less. The lower limit is not particularly defined, but is preferably 3 mPa · s or more.

 The curable composition of the present invention using the above compound (hereinafter sometimes simply referred to as “the composition of the present invention”) has a low viscosity before curing, and has excellent ability to form a fine uneven pattern. be able to. Moreover, after hardening, it is excellent in surface hardness and scratch resistance, and furthermore, it can be made to have excellent coating film properties in other respects. Therefore, the composition of the present invention can be preferably used for optical nanoimprint lithography as well as a curable composition.

That is, the composition of the present invention can have the following characteristics when used in optical nanoimprint lithography.
(1) Since the solution fluidity at room temperature is excellent, the composition easily flows into the cavity of the mold recess, and the atmosphere is difficult to be taken in. Residues hardly remain after curing.
(2) The cured film after curing has excellent pattern accuracy, excellent mechanical properties such as surface hardness and scratch resistance, excellent adhesion between the coating film and the substrate, and excellent peelability between the coating film and the mold. A good pattern can be formed because pattern breakage or stringing does not occur on the surface of the coating film and cause surface roughness when peeling off.
(3) Since it is excellent in coating uniformity, it is suitable for the field of coating / microfabrication on large substrates.

 For example, the composition of the present invention can be applied to semiconductor integrated circuits and liquid crystal display members that have been difficult to develop (particularly, thin film transistors for liquid crystal displays, protective films for liquid crystal color filters, spacers, and other liquid crystal display device members). For other applications such as plasma display panel partition materials, flat screens, micro electromechanical systems (MEMS), sensor elements, optical disks, high-density memory disks, etc., Optical components such as diffraction grating relief holograms, nanodevices, optical devices, optical films and polarizing elements, organic transistors, color filters, overcoat layers, pillar materials, rib materials for liquid crystal alignment, microlens arrays, immunoassay chips, DNA Separation chip, microreactor, nanobio device It can be widely applied to the production of optical waveguides, optical waveguides, optical filters, photonic liquid crystals, and the like.

(Polymerizable monomer)
The composition of the present invention contains the above compound as a polymerizable monomer for the purpose of increasing hardness after curing and improving scratch resistance. The content of the compound of the present invention in the composition of the present invention is, for example, preferably from 30 to 95% by weight, more preferably from 40 to 90% by weight when used in a curable composition for imprints.
Furthermore, the composition of the present invention may contain other polymerizable monomers other than the above compounds. Examples of the other polymerizable monomer include a polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group (monofunctional polymerizable unsaturated monomer). By including such a compound, the viscosity of the composition can be further reduced. As the polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group (monofunctional polymerizable unsaturated monomer), those described in paragraph No. 0046 of JP-A-2009-73078 are preferred. Can be adopted.

  Furthermore, it is also preferable to use a polyfunctional polymerizable unsaturated monomer having two or more ethylenically unsaturated bond-containing groups as another polymerizable monomer. As the bifunctional polymerizable unsaturated monomer having two ethylenically unsaturated bond-containing groups that can be preferably used in the present invention, those described in paragraph No. 0047 of JP-A-2009-73078 are preferably employed. be able to.

  Among these, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene Glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and the like are preferably used in the present invention.

  In the composition of the present invention, for the purpose of further increasing the crosslinking density, a polyfunctional oligomer or polymer having a molecular weight higher than that of the other polyfunctional polymerizable monomer is blended within a range to achieve the object of the present invention. Can do. Examples of the polyfunctional oligomer or polyfunctional polymer having photoradical polymerizability include polyester acrylate, ester acrylate oligomer, polyurethane acrylate, urethane acrylate oligomer, polyether acrylate, ether acrylate oligomer, polyepoxy acrylate, and epoxy acrylate oligomer.

 As another polymerizable monomer used in the present invention, a compound having an oxirane ring can also be employed. Examples of the compound having an oxirane ring include polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, polyglycidyl ethers of aromatic polyols, and aromatics. Mention may be made, for example, of hydrogenated compounds of polyglycidyl ethers of polyols, urethane polyepoxy compounds and epoxidized polybutadienes. These compounds can be used alone or in combination of two or more thereof.

 As an example of the epoxy compound used in the present invention, those described in paragraph Nos. 0053 to 0055 of JP-A-2009-73078 are preferably used, and the more preferable range is also the same.

  The production method of these compounds having an oxirane ring is not limited. For example, Maruzen KK Publishing, 4th edition Experimental Chemistry Course 20 Organic Synthesis II, 213, 1992, Ed. By Alfred Hasfner, The chemistry of cyclic compounds-Small Ring Heterocycles part3 Oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, Adhesion, Vol. 29, No. 12, 32, 1985, Yoshimura, Adhesion, Vol. 30, No. 5, 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, Japanese Patent Application Laid-Open No. 11-1000037, Japanese Patent No. 2906245, Japanese Patent No. 2926262 and the like can be synthesized.

As other polymerizable monomer used in the present invention, a vinyl ether compound may be used in combination.
A well-known thing can be selected suitably for a vinyl ether compound, For example, the thing of paragraph number 0057 of Unexamined-Japanese-Patent No. 2009-73078 can be employ | adopted preferably.

  These vinyl ether compounds can be obtained, for example, by the method described in Stephen C. Lapin, Polymers Paint Color Journal. 179 (4237), 321 (1988), that is, reaction of a polyhydric alcohol or polyhydric phenol with acetylene, or They can be synthesized by the reaction of a polyhydric alcohol or polyhydric phenol and a halogenated alkyl vinyl ether, and these can be used singly or in combination of two or more.

 Other examples of styrene derivatives that can be used in combination with the monofunctional polymer of the present invention include styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, Examples thereof include p-methoxy-β-methylstyrene, p-hydroxystyrene, etc. Examples of vinylnaphthalene derivatives include 1-vinylnaphthalene, α-methyl-1-vinylnaphthalene, β-methyl-1-vinyl. Naphthalene, 4-methyl-1-vinylnaphthalene, 4-methoxy-1-vinylnaphthalene and the like can be mentioned.

 On the other hand, it is preferable not to use a styrene derivative as a polymerizable monomer in the composition of the present invention. This is because when a styrene derivative is incorporated in the composition of the present invention, the photocurability is extremely deteriorated and the resist pattern is likely to have a tackiness.

 In addition, trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, perfluorobutyl-hydroxypropyl ( Use compounds containing fluorine atoms such as (meth) acrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, etc. Can do.

 As another polymerizable monomer used in the present invention, propenyl ether and butenyl ether can be blended. For example, 1-dodecyl-1-propenyl ether, 1-dodecyl-1-butenyl ether, 1-butenoxymethyl-2-norbornene, 1-4-di (1-butenoxy) butane, 1,10-di (1-butenoxy) Decane, 1,4-di (1-butenoxymethyl) cyclohexane, diethylene glycol di (1-butenyl) ether, 1,2,3-tri (1-butenoxy) propane, propenyl ether propylene carbonate, and the like can be suitably applied.

  In the composition of the present invention, the content of the compound other than the compound of the present invention is usually 10 to 80% by mass, preferably 30 to 75% by mass in the composition.

(Polymerization initiator)
The composition of the present invention usually contains a photopolymerization initiator. The photoinitiator used for this invention contains 0.1-15 mass% in all the compositions, for example, Preferably it is 0.2-12 mass%, More preferably, it is 0.3-10 mass %. When using 2 or more types of photoinitiators, the total amount becomes the said range.
It is preferable that the ratio of the photopolymerization initiator is 0.1% by mass or more because sensitivity (fast curability), resolution, line edge roughness, and coating film strength tend to be improved. On the other hand, when the ratio of the photopolymerization initiator is 15% by mass or less, the light transmittance, the colorability, the handleability and the like tend to be improved, which is preferable.

  As the photopolymerization initiator used in the present invention, one that has activity with respect to the wavelength of the light source to be used is blended, and one that generates appropriate active species is used. Moreover, only one type of photopolymerization initiator may be used, or two or more types may be used.

 As the radical photopolymerization initiator used in the present invention, for example, a commercially available initiator can be used. As these examples, for example, those described in paragraph No. 0091 of JP-A No. 2008-105414 can be preferably used.

  The light for initiating polymerization of the present invention includes not only light having a wavelength in the region of ultraviolet light, near ultraviolet light, far ultraviolet light, visible light, infrared light, or electromagnetic waves, but also radiation. For example, microwave, electron beam, EUV, and X-ray are included. Laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used. The light may be monochromatic light (single wavelength light) that has passed through an optical filter, or may be light with a plurality of different wavelengths (composite light). The exposure can be multiple exposure, and after the pattern is formed for the purpose of increasing the film strength and etching resistance, the entire surface can be further exposed.

  The photopolymerization initiator used in the present invention needs to be selected in a timely manner with respect to the wavelength of the light source to be used, but is preferably one that does not generate gas during mold pressurization and exposure. When the gas is generated, the mold is contaminated, so the mold must be frequently cleaned, or the curable composition for nanoimprinting of the present invention is deformed in the mold and deteriorates the transfer pattern accuracy. Cause problems. For those that do not generate gas, the mold is less likely to be contaminated, the frequency of cleaning the mold is reduced, and the curable composition for nanoimprinting of the present invention is less likely to be deformed in the mold, so the transfer pattern accuracy is less likely to deteriorate. It is preferable from the viewpoint.

(Antioxidant)
The composition of the present invention can contain a known antioxidant. The antioxidant used for this invention contains 0.01-10 mass% in all the compositions, for example, Preferably it is 0.2-5 mass%. When using 2 or more types of antioxidant, the total amount becomes the said range.
The antioxidant suppresses fading caused by heat or light irradiation and fading caused by various oxidizing gases such as ozone, active oxygen, NO _x , SO _x (X is an integer). In particular, in the present invention, the addition of an antioxidant has an advantage that the cured film can be prevented from being colored, or the film thickness reduction due to decomposition can be reduced. Such antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates, Examples include thiourea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like. Among these, hindered phenol antioxidants and thioether antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness.

  As commercially available products of antioxidants, Irganox 1010, 1035, 1076, 1222 (above, manufactured by Ciba Geigy Co., Ltd.), Antigene P, 3C, FR, Smither S, Smither GA80 (manufactured by Sumitomo Chemical Co., Ltd.), ADK STAB AO70, AO80, AO503 (made by ADEKA Co., Ltd.) etc. are mentioned, These may be used independently and may be used in mixture.

(Surfactant)
A surfactant may be included in the composition of the present invention. The surfactant used in the present invention contains, for example, 0.001 to 5% by mass, preferably 0.002 to 4% by mass, and more preferably 0.005 to 3% by mass in the entire composition. It is. When using 2 or more types of surfactant, the total amount becomes the said range. If the surfactant is less than 0.001 in the composition, the effect of coating uniformity is insufficient. On the other hand, if it exceeds 5% by mass, the mold transfer characteristics are deteriorated, which is not preferable.
The surfactant preferably contains at least one of a fluorine-based surfactant, a silicone-based surfactant, and a fluorine / silicone-based surfactant. Both the fluorine-based surfactant and the silicone-based surfactant or fluorine -More preferably, a silicone-based surfactant is included, and most preferably, a fluorine-silicone-based surfactant is included.
Here, the fluorine / silicone surfactant refers to one having both requirements of a fluorine surfactant and a silicone surfactant.
By using such a surfactant, the composition of the present invention can be applied to a silicon wafer for manufacturing semiconductor devices, a glass square substrate for manufacturing liquid crystal devices, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, and tantalum. Striations and scale-like patterns (such as alloy films, silicon nitride films, amorphous silicone films, tin oxide-doped indium oxide (ITO) films, tin oxide films, etc.) The purpose is to solve the problem of poor coating such as uneven drying of the resist film), and the fluidity of the composition into the cavity of the mold recess is improved, the peelability between the mold and the resist is improved, and between the resist and the substrate It becomes possible to improve the adhesion and to lower the viscosity of the composition.

As examples of the nonionic fluorosurfactant used in the present invention, those described in paragraph No. 0072 of JP-A-2009-73078 are preferably used.
Examples of fluorine / silicone surfactants used in the present invention include trade names X-70-090, X-70-091, X-70-092, X-70-093 (all Shin-Etsu Chemical Co., Ltd.). Manufactured), and trade names Megafuk R-08 and XRB-4 (all manufactured by Dainippon Ink & Chemicals, Inc.).

  The surfactant used in the composition of the present invention is preferably a nonionic (nonionic) surfactant from the viewpoint of voltage holding ratio.

Other components In addition to the above components, the composition of the present invention may include a release agent, a silane coupling agent, an ultraviolet absorber, a light stabilizer, an anti-aging agent, a plasticizer, an adhesion promoter, and thermal polymerization. An agent, a colorant, an elastomer particle, a photoacid growth agent, a photobase generator, a basic compound, a flow regulator, an antifoaming agent, a dispersant, and the like may be added.

  For the purpose of further improving the peelability, a release agent can be arbitrarily blended in the composition of the present invention. Specifically, it is added for the purpose of enabling the mold pressed against the layer of the composition of the present invention to be peeled cleanly without causing the resin layer to become rough or take off the plate. Examples of the release agent include conventionally known release agents such as silicone-based release agents, polyethylene wax, amide wax, solid wax such as Teflon powder (Teflon is a registered trademark), fluorine-based compounds, phosphate ester-based compounds, etc. Can also be used. Moreover, these mold release agents can be adhered to the mold.

  Silicone release agents have particularly good releasability from the mold when combined with the above-mentioned photocurable resin used in the present invention, and the phenomenon of taking a plate is difficult to occur. The silicone release agent is a release agent having an organopolysiloxane structure as a basic structure, for example, unmodified or modified silicone oil, polysiloxane containing trimethylsiloxysilicate, silicone acrylic resin, and the like. It is also possible to apply a silicone leveling agent generally used in hard coat compositions.

The modified silicone oil is obtained by modifying the side chain and / or terminal of polysiloxane, and is classified into a reactive silicone oil and a non-reactive silicone oil. Examples of the reactive silicone oil include amino modification, epoxy modification, carboxyl modification, carbinol modification, methacryl modification, mercapto modification, phenol modification, one-end reactivity, and different functional group modification. Examples of the non-reactive silicone oil include polyether modification, methylstyryl modification, alkyl modification, higher fatty ester modification, hydrophilic special modification, higher alkoxy modification, higher fatty acid modification, and fluorine modification.
Two or more of the above-described modification methods can be performed on one polysiloxane molecule.

  The modified silicone oil is preferably compatible with the composition components. In particular, when using a reactive silicone oil that is reactive with other coating film forming components blended as necessary in the composition, it is chemically bonded in the cured film obtained by curing the composition of the present invention. Therefore, since it is fixed, problems such as adhesion inhibition, contamination, and deterioration of the cured film are unlikely to occur. In particular, it is effective for improving the adhesion with the vapor deposition layer in the vapor deposition step. In addition, in the case of silicone modified with a photocurable functional group such as (meth) acryloyl-modified silicone or vinyl-modified silicone, it is excellent in characteristics after curing because it is crosslinked with the composition of the present invention.

Polysiloxane containing trimethylsiloxysilicic acid is easy to bleed out to the surface and has excellent peelability, excellent adhesion even when bleeded out to the surface, and excellent adhesion to metal deposition and overcoat layer This is preferable.
The said mold release agent can be added only in 1 type or in combination of 2 or more types.

When a release agent is added to the composition of the present invention, it is preferably added in a proportion of 0.001 to 10% by mass in the total amount of the composition, more preferably 0.01 to 5% by mass. preferable. If the ratio of a mold release agent is less than the said range, the peelable improvement effect of a mold and the curable composition layer for optical nanoimprint lithography will become inadequate. On the other hand, if the ratio of the release agent exceeds the above range, the surface of the coating film may be rough due to repelling during coating of the composition, or the substrate itself and the adjacent layer in the product, for example, the adhesion of the vapor deposition layer It is not preferable from the viewpoint of inhibiting the properties and causing film breakage or the like during transfer (film strength becomes too weak).
When the ratio of the release agent is 0.01% by mass or more, the effect of improving the peelability between the mold and the curable composition layer for photo nanoimprint lithography is sufficient. On the other hand, if the ratio of the release agent is within the above range of 10% by mass, the problem of surface roughness of the coating film due to repelling during coating of the composition is unlikely to occur, and the substrate itself and adjacent layers in the product, for example, It is preferable in that it hardly inhibits the adhesion of the deposited layer and hardly causes film breakage or the like (film strength becomes too weak) during transfer.

  In the composition of the present invention, an organic metal coupling agent may be blended in order to improve the heat resistance, strength, or adhesion to the metal vapor deposition layer of the surface structure having a fine concavo-convex pattern. In addition, the organometallic coupling agent is effective because it has an effect of promoting the thermosetting reaction. As the organometallic coupling agent, for example, various coupling agents such as a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and a tin coupling agent can be used.

As the silane coupling agent in the present invention, for example, a silane coupling agent described in paragraph No. 0083 of JP-A-2009-73078 can be preferably used.
As a titanium coupling agent in this invention, the titanium coupling agent as described in the paragraph number 0084 of Unexamined-Japanese-Patent No. 2009-73078 can be used preferably, for example.
As a zirconium coupling agent in this invention, the zirconium coupling agent of the paragraph number 0085 of Unexamined-Japanese-Patent No. 2009-73078 can be used preferably, for example.
As the aluminum coupling agent in the present invention, for example, the aluminum coupling agent described in paragraph No. 0086 of JP-A-2009-73078 can be preferably used.

  The said organometallic coupling agent can be arbitrarily mix | blended in the ratio of 0.001-10 mass% in solid content whole quantity of the curable composition for optical nanoimprint lithography. By setting the ratio of the organometallic coupling agent to 0.001% by mass or more, there is a tendency to be more effective in improving heat resistance, strength, and adhesion with the vapor deposition layer. On the other hand, it is preferable that the ratio of the organometallic coupling agent is 10% by mass or less because the stability of the composition and the deficiency in film formability can be suppressed.

  As a commercial item of an ultraviolet absorber, Tinuvin P, 234, 320, 326, 327, 328, 213 (above, manufactured by Ciba Geigy Co., Ltd.), Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350 400 (above, manufactured by Sumitomo Chemical Co., Ltd.). It is preferable to mix | blend an ultraviolet absorber arbitrarily in the ratio of 0.01-10 mass% with respect to the whole quantity of the curable composition for optical nanoimprint lithography.

  Commercially available light stabilizers include Tinuvin 292, 144, 622LD (above, manufactured by Ciba Geigy Co., Ltd.), Sanol LS-770, 765, 292, 2626, 1114, 744 (above, manufactured by Sankyo Kasei Kogyo Co., Ltd.) Etc. The light stabilizer is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the composition.

  Examples of commercially available anti-aging agents include Antigene W, S, P, 3C, 6C, RD-G, FR, and AW (manufactured by Sumitomo Chemical Co., Ltd.). The anti-aging agent is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the composition.

  A plasticizer can be added to the composition of the present invention in order to adjust adhesion to the substrate, flexibility of the film, hardness, and the like. Specific examples of preferred plasticizers include, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, dimethyl adipate, diethyl adipate , Di (n-butyl) adipate, dimethyl suberate, diethyl suberate, di (n-butyl) suberate and the like, and a plasticizer can be optionally added at 30% by mass or less in the composition. Preferably it is 20 mass% or less, More preferably, it is 10 mass% or less. In order to obtain the effect of adding a plasticizer, 0.1% by mass or more is preferable.

  An adhesion promoter may be added to the composition of the present invention in order to adjust adhesion to the substrate. Adhesion promoters include benzimidazoles and polybenzimidazoles, lower hydroxyalkyl-substituted pyridine derivatives, nitrogen-containing heterocyclic compounds, urea or thiourea, organophosphorus compounds, 8-oxyquinoline, 4-hydroxypteridine, 1,10-phenanthroline 2,2'-bipyridine derivatives, benzotriazoles, organophosphorus compounds and phenylenediamine compounds, 2-amino-1-phenylethanol, N-phenylethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-ethylethanol Amines and derivatives, benzothiazole derivatives, and the like can be used. The adhesion promoter in the composition is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. The addition of the adhesion promoter is preferably 0.1% by mass or more in order to obtain the effect.

  When hardening the composition of this invention, a thermal-polymerization initiator can also be added as needed. Preferred examples of the thermal polymerization initiator include peroxides and azo compounds. Specific examples include benzoyl peroxide, tert-butyl-peroxybenzoate, azobisisobutyronitrile, and the like.

  The composition of the present invention may contain a photobase generator as necessary for the purpose of adjusting the pattern shape, sensitivity, and the like. For example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) Oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitro Benzyloxycarbonyl) pyrrolidine, hexaamminecobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,6-dimethyl-3,5- Diacetyl-4 Preferred examples include (2′-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4- (2 ′, 4′-dinitrophenyl) -1,4-dihydropyridine, and the like. It is done.

A colorant may be optionally added to the composition of the present invention for the purpose of improving the visibility of the coating film. As the colorant, pigments and dyes used in UV inkjet compositions, color filter compositions, CCD image sensor compositions, and the like can be used as long as the object of the present invention is not impaired. As the pigment that can be used in the present invention, for example, those described in paragraph No. 0121 of JP-A No. 2008-105414 can be preferably used.
The colorant is preferably blended at a ratio of 0.001 to 2% by mass with respect to the total amount of the composition.

In the composition of the present invention, elastomer particles may be added as optional components for the purpose of improving mechanical strength, flexibility and the like.
The elastomer particles that can be added as an optional component to the composition of the present invention preferably have an average particle size of 10 nm to 700 nm, more preferably 30 to 300 nm. For example, polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer, styrene / butadiene copolymer, styrene / isoprene copolymer, ethylene / propylene copolymer, ethylene / α-olefin copolymer, ethylene / α-olefin / Particles of elastomer such as polyene copolymer, acrylic rubber, butadiene / (meth) acrylic ester copolymer, styrene / butadiene block copolymer, styrene / isoprene block copolymer. Further, core / shell type particles in which these elastomer particles are coated with a methyl methacrylate polymer, a methyl methacrylate / glycidyl methacrylate copolymer or the like can be used. The elastomer particles may have a crosslinked structure.

  Examples of commercially available elastomer particles include Resin Bond RKB (manufactured by Resinas Kasei Co., Ltd.), Techno MBS-61, MBS-69 (manufactured by Techno Polymer Co., Ltd.), and the like.

  These elastomer particles can be used alone or in combination of two or more. The content of the elastomer component in the composition of the present invention is preferably 1 to 35% by mass, more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass.

  A basic compound may be optionally added to the composition of the present invention for the purpose of suppressing curing shrinkage and improving thermal stability. Examples of the basic compound include amines, nitrogen-containing heterocyclic compounds such as quinoline and quinolidine, basic alkali metal compounds, basic alkaline earth metal compounds, and the like. Among these, amine is preferable from the viewpoint of compatibility with the photopolymerization monomer, for example, octylamine, naphthylamine, xylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, dimethylaniline, quinuclidine, tributylamine, Examples include octylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine, hexamethylenetetramine, and triethanolamine.

 A chain transfer agent may be added to the composition of the present invention in order to improve photocurability. Specifically, 4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 1,3,5-triazine-2,4,6 (1H, 3H , 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate).

(Organic solvent)
In the composition of the present invention, the content of the organic solvent is preferably 3% by mass or less in the entire composition. That is, since the composition of the present invention preferably contains a specific monofunctional or bifunctional monomer as a reactive diluent, the organic solvent for dissolving the components of the composition of the present invention is not necessarily contained. There is no need. In addition, if an organic solvent is not included, a baking process for the purpose of volatilization of the solvent is not necessary, so that there is a great merit that it is effective for simplifying the process. Therefore, in the composition of the present invention, the content of the organic solvent is preferably 3% by mass or less, more preferably 2% by mass or less, and it is particularly preferable not to contain it. As described above, the composition of the present invention does not necessarily contain an organic solvent. However, in the case of dissolving a compound that does not dissolve in the reactive diluent as the composition of the present invention, or when finely adjusting the viscosity. Any of these may be added. The organic solvent that can be preferably used in the composition of the present invention is a solvent generally used in curable compositions for nanoimprints and photoresists, which dissolves and uniformly disperses the compound used in the present invention. It is not particularly limited as long as it is sufficient and does not react with these components.

Examples of the solvent that can be used in the present invention include those described in paragraph No. 0066 of JP-A-2009-73078.
Further, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. A high boiling point solvent can also be added. These may be used alone or in combination of two or more.
Among these, methoxypropylene glycol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, methyl isobutyl ketone, 2-heptanone and the like are particularly preferable.

(viscosity)
The viscosity of the composition of the present invention will be described. The viscosity in the present invention means a viscosity at 25 ° C. unless otherwise specified. In the composition of the present invention, the viscosity of the composition excluding the solvent at 25 ° C. is usually 18 mPa · s or less, preferably 12 mPa · s or less. The lower limit is not particularly defined, but is preferably 3 mPa · or more. By setting the viscosity of the composition of the present invention to 3 mPa · s or more, there is a tendency that problems of substrate coating suitability and a decrease in mechanical strength of the film hardly occur. Specifically, by setting the viscosity to 3 mPa · s or more, it is preferable that unevenness on the surface is generated during the application of the composition or the composition can be prevented from flowing out of the substrate during the application. On the other hand, by setting the viscosity of the composition of the present invention to 18 mPa · s or less, even when a mold having a fine concavo-convex pattern is adhered to the composition, the composition flows into the cavity of the concave portion of the mold, and the atmosphere Is less likely to be taken in, so that it is difficult to cause bubble defects, and it is difficult for residues to remain after photocuring in the mold convex portion.

(surface tension)
The composition of the present invention preferably has a surface tension in the range of 18 to 30 mN / m, and more preferably in the range of 20 to 28 mN / m. By setting it as such a range, the effect of improving surface smoothness is acquired.

(amount of water)
In addition, the water content at the time of preparation of the composition of the present invention is preferably 2.0% by mass or less, more preferably 1.5% by mass, and still more preferably 1.0% by mass or less. By making the water content at the time of preparation 2.0% by mass or less, the storage stability of the composition of the present invention can be made more stable.

(Preparation)
The composition of the present invention can be prepared as a solution by mixing each of the above components and then filtering with a filter having a pore size of 0.05 μm to 5.0 μm, for example. The mixing / dissolution of the curable composition for nanoimprint is usually performed in the range of 0 ° C to 100 ° C. Filtration may be performed in multiple stages or repeated many times. Moreover, the filtered liquid can be refiltered. Materials used for filtration can be polyethylene resin, polypropylene resin, fluorine resin, nylon resin, etc., but are not particularly limited.

[Curing film]
Next, the cured film of the present invention (in particular, a fine uneven pattern) using the composition of the present invention will be described. In the present invention, the composition of the present invention can be applied and cured to form the cured film of the present invention.

  In addition, by applying the composition of the present invention on a substrate or a support and exposing the layer made of the composition, curing, and drying (baking) as necessary, permanent layers such as overcoat layers and insulating films can be obtained. A film can also be produced.

  In permanent films (resist for structural members) used for liquid crystal displays (LCDs), it is preferable to avoid contamination of metal or organic ionic impurities in the resist as much as possible so as not to hinder the operation of the display. The concentration is preferably 1000 ppm or less, more preferably 100 ppm or less.

  Permanent films (resist for structural members) used for liquid crystal displays (LCDs) are bottled in containers such as gallon bottles and coated bottles after manufacture, and are transported and stored. In this case, the purpose is to prevent deterioration. The inside of the container may be replaced with inert nitrogen, argon, or the like. Further, at the time of transportation and storage, the room temperature may be used, but the temperature may be controlled in the range of −20 ° C. to 0 ° C. in order to prevent the permanent film from being deteriorated. Of course, it is necessary to shield from light at a level where the reaction does not proceed.

[Components for liquid crystal display devices]
Further, the cured product of the present invention can be preferably applied as a semiconductor integrated circuit, a recording material, or a liquid crystal display member, more preferably a liquid crystal display member, and an etching resist such as a flat panel display. It is particularly preferable to apply as

[Method for producing cured film]
Below, the manufacturing method of the cured film using the composition of this invention is described.
The composition of the present invention is preferably cured by light or light and heat. Specifically, at least the composition of the present invention is applied onto a substrate, the solvent is dried to form a layer comprising the composition of the present invention, and a pattern receptor is produced. A mold is pressed against the surface of the substrate, a process of transferring the mold pattern is performed, and the fine concavo-convex pattern is cured by light irradiation and heating. Usually, light irradiation and heating are performed a plurality of times. Nanoimprint lithography according to the method for producing a cured film of the present invention can be laminated and multiple patterned, and can be used in combination with ordinary thermal imprint.

  The composition of the present invention is generally known methods such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spin coating, and slit scanning. For example, it can be applied on the substrate. The film thickness of the layer comprising the composition of the present invention is 0.05 μm to 30 μm, although it varies depending on the application used. Further, the composition of the present invention may be applied multiple times.

  Substrates for applying the composition of the present invention are quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflection film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG, polyester film Polymer substrates such as polycarbonate films and polyimide films, TFT array substrates, PDP electrode plates, glass and transparent plastic substrates, conductive substrates such as ITO and metals, insulating substrates, silicone, silicone nitride, polysilicone, oxidation There are no particular restrictions on semiconductor fabrication substrates such as silicone and amorphous silicone. The shape of the substrate may be a plate shape or a roll shape.

  The light for curing the composition of the present invention is not particularly limited, and examples thereof include high energy ionizing radiation, light or radiation having a wavelength in the region of near ultraviolet, far ultraviolet, visible, infrared or the like. As the high-energy ionizing radiation source, for example, an electron beam accelerated by an accelerator such as a cockcroft accelerator, a handagraaf accelerator, a linear accelerator, a betatron, or a cyclotron is industrially most conveniently and economically used. However, radiation such as γ rays, X rays, α rays, neutron rays, proton rays emitted from radioisotopes or nuclear reactors can also be used. Examples of the ultraviolet ray source include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a solar lamp. Examples of radiation include microwaves and EUV. Also, laser light used in semiconductor microfabrication such as LED, semiconductor laser light, or 248 nm KrF excimer laser light or 193 nm ArF excimer laser can be suitably used in the present invention. These lights may be monochromatic light, or may be light having a plurality of different wavelengths (mixed light).

During exposure is preferably in the range of exposure intensity of ^{1mW / cm 2 ~50mW / cm 2} . By making the exposure time 1 mW / cm ² or more, the exposure time can be shortened so that productivity is improved, and by making the exposure time 50 mW / cm ² or less, deterioration of the properties of the permanent film due to side reactions can be suppressed. It tends to be preferable. The exposure dose is desirably in the range of 5 mJ / cm ^{2 to} 1000 mJ / cm ² . By setting it to 5 mJ / cm ² or more, the exposure margin becomes narrow, photocuring becomes insufficient, and problems such as adhesion of unreacted substances to the mold are less likely to occur. On the other hand, it is preferable to set it to 1000 mJ / cm ² or less because deterioration of the permanent film due to decomposition of the composition tends to decrease.
Further, during exposure, in order to prevent radical polymerization from being inhibited by oxygen, an inert gas such as nitrogen or argon may be flowed to control the oxygen concentration to less than 100 mg / L.

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

Next, the molding material that can be used in the present invention will be described. In optical nanoimprint lithography using the composition of the present invention, it is necessary to select a light transmissive material for at least one of the molding material and / or the substrate. In photoimprint lithography applied to the present invention, a curable composition for nanoimprint is applied on a substrate, a light-transmissive mold is pressed, light is irradiated from the back of the mold, and the curable composition for nanoimprint is applied. Harden. Alternatively, the nanoimprint curable composition can be applied on a light-transmitting substrate, pressed against the mold, and irradiated with light from the back surface of the mold to cure the nanoimprint curable composition.
The light irradiation may be performed in a state where the mold is attached, or may be performed after the mold is peeled off, but in the present invention, it is preferably performed in a state where the mold is adhered.

As the mold that can be used in the present invention, a mold having a pattern to be transferred is used. The mold can form a pattern according to the desired processing accuracy by, for example, photolithography, electron beam drawing, or the like, but the mold pattern forming method is not particularly limited in the present invention.
The light-transmitting mold material used in the present invention is not particularly limited as long as it has predetermined strength and durability. Specifically, a light transparent resin such as glass, quartz, PMMA, and polycarbonate resin, a transparent metal vapor-deposited film, a flexible film such as polydimethylsiloxane, a photocured film, and a metal film are exemplified.

  The non-light transmissive mold material used in the case of using the transparent substrate of the present invention is not particularly limited as long as it has a predetermined strength. Specific examples include ceramic materials, deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicone, silicone nitride, polysilicon, silicone oxide, and amorphous silicone. There are no particular restrictions. The shape may be either a plate mold or a roll mold. The roll mold is applied particularly when continuous transfer productivity is required.

  The mold used in the present invention may be a mold that has been subjected to a release treatment in order to improve the releasability between the composition of the present invention and the mold. Those having been treated with a silane coupling agent such as a silicone type or a fluorine type, for example, a commercially available release agent such as Daikin Industries, Optool DSX, Sumitomo 3M, Novec EGC-1720, etc. can be suitably used.

  When performing photoimprint lithography using the method for producing a cured film of the present invention, it is usually preferred that the mold pressure be 10 atm or less. Setting the mold pressure to 10 atm or less is preferable because the mold and the substrate are less likely to be deformed and the pattern accuracy tends to be improved, and since the pressure is low, the apparatus can be reduced. The mold pressure is preferably selected in a region where the mold transfer uniformity can be ensured within a range where the residual film of the composition of the present invention on the mold convex portion is reduced.

In the present invention, the light irradiation in the photoimprint lithography may be sufficiently larger than the irradiation amount necessary for curing. The amount of irradiation necessary for curing is determined by examining the consumption of unsaturated bonds of the curable composition for nanoimprints and the tackiness of the cured film.
In the photoimprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually room temperature, but the light irradiation may be performed while heating in order to increase the reactivity. As a pre-stage of light irradiation, if it is kept in a vacuum state, it is effective in preventing bubbles from being mixed, suppressing the decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the curable composition for nanoimprinting. You may do it. In the present invention, the preferable degree of vacuum is 10 ⁻¹ Pa to normal pressure.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

1. Preparation of photocurable composition The following polymerizable monomer M-1, the following photopolymerization initiator P-1 (2% by mass with respect to M-1), the following surfactant W-1 (with respect to M-1) 1% by mass) was added to prepare a photocurable composition of Example 1.

[Examples 2 to 22]
In Example 1, the composition of Examples 2-22 was prepared like Example 1 except having changed the said compound M-1 into the compound of the following Table 1-Table 5, respectively.

＜比較例＞

＜その他の化合物＞
Ｍ−２５：テトラエチレングリコールジアクリレート（東亞合成製：アロニックスＭ−２４０）
Ｍ−２６：トリプロピレングリコールジアクリレート（東亞合成製：アロニックスＭ−２２０）
Ｍ−２７：特許第３６４８６３６号公報に記載の下記（メタ）アクリレート

Ｍ−２８：ジペンタエリスリトールヘキサアクリレート（日本化薬社製：カヤラッドＤＰＨＡ）
Ｍ−２９：シクロヘキシルアクリレート（大阪有機製：ビスコート＃１５５） Below, the material of a photocurable composition is shown.
<Polymerizable monomer of the present invention>

<Comparative example>

<Other compounds>
M-25: Tetraethylene glycol diacrylate (manufactured by Toagosei: Aronix M-240)
M-26: Tripropylene glycol diacrylate (manufactured by Toagosei: Aronix M-220)
M-27: The following (meth) acrylate described in Japanese Patent No. 3648636

M-28: Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd .: Kayarad DPHA)
M-29: cyclohexyl acrylate (Osaka Organic: Biscoat # 155)

<Synthesis example of polymerizable monomer>
(Synthesis of M-1)
20.0 g of 3- (acryloyloxy) -2-hydroxy-propyl methacrylate (manufactured by Aldrich) was dissolved in 100 ml of acetone, cooled in an ice bath, and 14.1 g of triethylamine (manufactured by Wako Pure Chemical Industries) was added. A solution of 17.6 g of n-hexanoic acid chloride (manufactured by Wako Pure Chemical Industries, Ltd.) in acetone (20 mL) was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour, and then an aqueous sodium hydrogen carbonate solution (sodium hydrogen carbonate 5 g + water 250 ml) was added. After 250 ml of ethyl acetate was added for liquid separation, the aqueous layer was further extracted with 150 mL of ethyl acetate. The obtained organic layer was washed with 200 ml of 0.2N hydrochloric acid aqueous solution and dried with 15 g of magnesium sulfate, and then the filtrate was concentrated to obtain a crude product of M-1.
The obtained crude product was purified by silica gel column chromatography to obtain 17.3 g of M-1 (yield 59%).

The ¹ H NMR data of the obtained M-1 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ 6.4 (d, 1 H), δ 6.2 (dd, 1 H), δ 6.2 (d, 1 H), δ 5.9 (d, 1 H), δ 5.6 (d , 1H), δ5.5-5.3 (m, 1H), δ4.5-4.2 (m, 4H), δ2.3 (t, 2H), δ1.9 (s, 3H), δ1. 6 (td, 2H), δ1.4-1.2 (m, 4H), δ0.8 (t, 3H)

(Synthesis of M-2)
In the same manner as in M-1, 15.0 g of 3- (acryloyloxy) -2-hydroxy-propyl methacrylate (manufactured by Aldrich) and 20.5 g of n-octanoic acid chloride (manufactured by Wako Pure Chemical Industries) were reacted and obtained. The crude product was purified by silica gel column chromatography to obtain 15.5 g of M-2. (Yield 65%)

The ¹ H NMR data of the obtained M-2 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ 6.4 (d, 1 H), δ 6.2 (dd, 1 H), δ 6.2 (d, 1 H), δ 5.9 (d, 1 H), δ 5.6 (d , 1H), δ5.5-5.3 (m, 1H), δ4.5-4.2 (m, 4H), δ2.3 (t, 2H), δ1.9 (s, 3H), δ1. 6 (td, 2H), δ1.4-1.2 (m, 8H), δ0.8 (t, 3H)

(Synthesis of M-3)
In the same manner as in M-1, 20.0 g of 3- (acryloyloxy) -2-hydroxy-propyl methacrylate (Aldrich) and 17.1 g of benzyl chloride (Tokyo Kasei) were reacted, and the resulting crude product was Purification by silica gel column chromatography gave 20.3 g of M-3. (Yield 68%)

The ¹ H NMR data of the obtained M-3 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ 8.0 (d, 2H), δ 7.6 (dd, 2H), δ 7.4 (dd, 2H), δ 6.4 (d, 1H), δ 6.2-6 .1 (m, 2H), δ5.8 (d, 1H), δ5.7-5.6 (m, 2H), δ4.6-4.3 (m, 4H), δ1.9 (s, 3H) )

(Synthesis of M-4)
In the same manner as M-1, 15.0 g of 1,2-dodecanediol (manufactured by Tokyo Chemical Industry) and 17.4 g of acrylic acid chloride (manufactured by Tokyo Chemical Industry) were reacted, and the resulting crude product was subjected to silica gel column chromatography. Purification gave 15.6 g of M-4. (Yield 68%)

The ¹ H NMR data of the obtained M-4 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ 6.9 (d, 1 H), δ 6.8 (d, 1 H), δ 6.3 (dd, 1 H), δ 6.2 (dd, 1 H), δ 5.7 (d , 1H), δ5.7 (d, 1H), δ5.3 (tdd, 1H), δ4.6 (dd, 1H), δ4.3 (dd, 1H), δ1.6 (td, 2H), δ1 4-1.2 (m, 16H), δ 0.7 (t, 3H)

(Synthesis of M-5)
Dissolve 23.8 g of heptanoic acid (manufactured by Tokyo Chemical Industry) in 150 mL of dimethylacetamide, add 25.3 g of potassium carbonate (manufactured by Wako Pure Chemical Industries), and 20.3 g of epichlorohydrin (manufactured by Tokyo Chemical Industry) to 100 ° C. Heat and stir for 2 hours. After allowing to cool, 200 mL of water and 200 mL of ethyl acetate were added to the reaction mixture and the phases were separated, and the organic layer was extracted twice with 100 mL of 0.2N hydrochloric acid. The organic layer was dried over 15 g of magnesium sulfate, and the crude product obtained by concentrating the filtrate was purified by Ricagel column chromatography to obtain 15.0 g of M-5 intermediate (M-5A).
Subsequently, M-5A was dissolved in 25 mL of toluene, and 6.4 g of acrylic acid (manufactured by Tokyo Chemical Industry), 1.3 g of tetrabutylammonium bromide (manufactured by Wako Pure Chemical Industries), and a small amount of 4-methoxyphenol (manufactured by Tokyo Chemical Industry) were added. The mixture was heated to 90 ° C. and stirred for 7 hours.
After allowing to cool, the reaction mixture was dissolved in 100 mL of acetone, cooled in an ice bath, 13.0 g of triethylamine (manufactured by Wako Pure Chemical Industries) was added, and then 10.9 g of acetone (10 mL) of acrylic acid chloride (manufactured by Tokyo Chemical Industry). ) The solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and then an aqueous sodium hydrogen carbonate solution (5 g of sodium hydrogen carbonate + 150 ml of water) was added. After 200 ml of ethyl acetate was added for liquid separation, the aqueous layer was further extracted with 100 mL of ethyl acetate. The obtained organic layer was washed with 100 ml of 0.1N hydrochloric acid aqueous solution and dried with 20 g of magnesium sulfate, and then the filtrate was concentrated to obtain a crude product of M-5.
The resulting crude product was purified by silica gel column chromatography to obtain 18.5 g of M-5 (3 step yield: 32%).

The ¹ H NMR data of the obtained M-5 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ 6.4 (d, 1 H), δ 6.4 (d, 1 H), δ 6.2-6.1 (m, 2 H), δ 5.8 (d, 1 H), δ 5 .8 (d, 1H) δ 5.4 (dddd, 1H), δ 4.5-4.2 (m, 4H), δ 2.3 (t, 2H), δ 1.6 (t, 2H), δ 1.4 -1.2 (m, 8H), δ0.8 (t, 3H)

(Synthesis of M-6)
In the same manner as M-5, the crude product of M-6 obtained in 3 steps from 16.1 g of nonanoic acid (manufactured by Tokyo Chemical Industry) was purified by silica gel column chromatography to obtain 8.5 g of M-6. (3 process yield 25%).

The ¹ H NMR data of the obtained M-6 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ 6.4 (d, 1 H), δ 6.4 (d, 1 H), δ 6.2-6.1 (m, 2 H), δ 5.8 (d, 1 H), δ 5 .8 (d, 1H) δ 5.4 (dddd, 1H), δ 4.5-4.2 (m, 4H), δ 2.3 (t, 2H), δ 1.6 (t, 2H), δ 1.4 -1.2 (m, 12H), δ0.8 (t, 3H)

(Synthesis of M-7)
trans-2-octenoic acid (Tokyo Kasei) 12.1 g and glycidol (Tokyo Kasei) 6.0 g are dissolved in toluene 20 mL, tetrabutylammonium bromide (Wako Pure Chemicals) 1.3 g, 4-methoxyphenol ( (Manufactured by Tokyo Chemical Industry) A small amount was added and heated to 90 ° C. and stirred for 7 hours.
After allowing to cool, the reaction mixture was dissolved in 170 mL of acetone and cooled in an ice bath, 24.6 g of triethylamine (manufactured by Wako Pure Chemical Industries) was added, and then 20.5 g of acetone (20 mL) of acrylic acid chloride (manufactured by Tokyo Chemical Industry). ) The solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and then an aqueous sodium hydrogen carbonate solution (5 g of sodium hydrogen carbonate + 250 ml of water) was added. After adding 300 ml of ethyl acetate for liquid separation, the organic layer was washed with 150 ml of 0.1N aqueous hydrochloric acid solution and dried over 20 g of magnesium sulfate, and then the filtrate was concentrated to obtain a crude product of M-7. .
The obtained crude product was purified by silica gel column chromatography to obtain 19.3 g of M-7 (2 step yield: 70%).

The ¹ H NMR data of the obtained M-7 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ 7.0 (td, 1H), δ 6.5 (d, 1 H), δ 6.4 (d, 1 H), 6.2 (dd, 1 H), δ 6.1 (dd , 1H), δ5.9 (d, 1H), δ5.9 (d, 1H), δ5.8 (d, 1H) δ5.5-5.3 (m, 1H), δ4.5-4.2 (M, 4H), δ 2.2 (td, 2H), δ 1.5-1.4 (m, 2H), δ 1.3-1.1 (m, 4H), δ 0.8 (t, 3H)

(Synthesis of M-8)
In the same manner as M-7, a crude product of M-8 obtained in 2 steps from 13.3 g of trans-2-nonenoic acid (manufactured by Tokyo Chemical Industry) was purified by silica gel column chromatography. 0.5 g was obtained (2 step yield 68%).

The ¹ H NMR data of the obtained M-8 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ 7.0 (td, 1 H), δ 6.5 (d, 1 H), δ 6.4 (d, 1 H), 6.2 (dd, 1 H), δ 6.1 (dd , 1H), δ5.9 (d, 1H), δ5.9 (d, 1H), δ5.8 (d, 1H) δ5.5-5.3 (m, 1H), δ4.5-4.2 (M, 4H), δ 2.2 (td, 2H), δ 1.5-1.4 (m, 2H), δ 1.3-1.1 (m, 6H), δ 0.8 (t, 3H)

(Synthesis of M-9)
In the same manner as for M-7, the crude product of M-9 obtained in 2 steps from 14.5 g of trans-2-decenoic acid (manufactured by Tokyo Chemical Industry) was purified by silica gel column chromatography. 0.6 g was obtained (2 step yield 69%).

The ¹ H NMR data of the obtained M-9 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ 7.0 (td, 1H), δ 6.4 (d, 1 H), δ 6.4 (d, 1 H), 6.2 (dd, 1 H), δ 6.1 (dd , 1H), δ5.9 (d, 1H), δ5.9 (d, 1H), δ5.8 (d, 1H) δ5.5-5.3 (m, 1H), δ4.5-4.2 (M, 4H), δ 2.2 (td, 2H), δ 1.5-1.4 (m, 2H), δ 1.4-1.2 (m, 8H), δ 0.8 (t, 3H)

(Synthesis of M-10)
In the same manner as M-7, a crude product of M-10 obtained in two steps from 6.4 g of 10-undecenoic acid (manufactured by Tokyo Chemical Industry) was purified by silica gel column chromatography, and 9.2 g of M-10 was purified. Obtained (2 step yield 75%).

The ¹ H NMR data of the obtained M-10 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ 6.5 (d, 1 H), δ 6.4 (d, 1 H), δ 6.2 (d, 1 H), 6.1 (d, 1 H), δ 5.9 (d , 1H), δ5.9 (d, 1H), δ5.8-5.7 (m, 1H), δ5.5-5.4 (m, 1H) δ5.0 (d, 1H), δ4.9 (D, 1H), δ4.5-4.2 (m, 4H), δ2.4 (t, 2H), δ2.0 (t, 2H), δ1.6 (t, 2H), δ1.4- 1.2 (m, 10H)

(Synthesis of M-11)
15.0 g of 1-hexanal (manufactured by Wako Pure Chemical Industries, Ltd.) is added to 249.9 g of an aqueous solution of formaldehyde (36%) (manufactured by Wako Pure Chemical Industries, Ltd.), triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) 1.5 is added, and the mixture is heated at 40 ° C. for 8 hours. Stir. After standing to cool, the solution was separated twice with 155 g of hexane, extracted by adding 200 mL of ethyl acetate to the water tank obtained by removing the hexane layer, and then the organic layer was dried with 15 g of magnesium sulfate and filtered, and the filtrate was concentrated. did. The concentrated solution was separated again with distilled water (100 mL) and ethyl acetate (100 mL). The organic layer was dried over magnesium sulfate (15 g) and then filtered, and the filtrate was concentrated.
To the obtained intermediate crude product (M-11A), 22.6 g of 30% aqueous hydrogen peroxide was added dropwise, heated to 60 ° C. and stirred for 5 hours. After allowing to cool, 50 mL of distilled water and 3 g of sodium thiosulfate were removed from the reaction mixture, and then 1N hydrochloric acid (30 mL) and ethyl acetate (100 mL) were added to separate the solution. Extracted once. The organic layer was dried over 30 g of magnesium sulfate and filtered, and the filtrate was concentrated.
The obtained intermediate crude product (M-11B) was added to 100 mL of N-methylpyrrolidone, and 10.1 g of sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries) and 14.5 g of allyl bromide (manufactured by Tokyo Chemical Industry) were added. The mixture was heated to 80 ° C. and stirred for 2 hours. After allowing to cool, 30,5 g of 3-chloropropionyl chloride (manufactured by Tokyo Chemical Industry) was added dropwise to the reaction mixture, followed by stirring at 50 ° C. for 30 minutes. After allowing to cool, 300 mL of a saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture in an ice bath, and 300 mL of ethyl acetate was added for liquid separation. The organic layer was washed with 150 mL of 0.1N hydrochloric acid, dried over 20 g of magnesium sulfate and filtered, and the filtrate was concentrated.
The obtained intermediate crude product (M-11C) was dissolved in 100 mL of acetone and cooled in an ice bath, and 25.3 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. After stirring at 40 ° C. for 2 hours, 200 mL of distilled water and 250 mL of ethyl acetate were added and separated, and the organic layer was washed with 100 mL of 0.1N aqueous hydrochloric acid. The organic layer was dried over 20 g of magnesium sulfate, and then the filtrate was concentrated to obtain a crude product of M-11.
The obtained crude product was purified by silica gel column chromatography to obtain 2.7 g of M-11 (5 step yield: 6%).

¹ H NMR data of the obtained M-11 are shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ6.4 (d, 2H), δ6.1 (dd, 1H), δ5.9 (tdd, 1H), 5.8 (d, 2H), δ5.3 (d , 1H), δ5.2 (d, 1H), δ4.6 (d, 2H), δ4.4 (s, 4H) δ1.6 (q, 2H), δ1.9-1.6 (m, 4H) ), Δ 0.9 (t, 3H)

(Synthesis of M-12)
In the same manner as M-11, the crude product of M-12 obtained in 5 steps from 15.0 g of 1-heptanal (manufactured by Wako Pure Chemical Industries, Ltd.) was purified by silica gel column chromatography, and 11.7 g of M-12 was purified. Obtained (5 step yield 26%).

The ¹ H NMR data of the obtained M-12 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ6.4 (d, 2H), δ6.1 (dd, 1H), δ5.9 (tdd, 1H), 5.8 (d, 2H), δ5.3 (d , 1H), δ5.2 (d, 1H), δ4.6 (d, 2H), δ4.4 (s, 4H) δ1.6 (q, 2H), δ1.9-1.6 (m, 6H) ), Δ 0.9 (t, 3H)

(Synthesis of M-13)
In the same manner as M-11, the crude product of M-13 obtained in 1 step from 15.6 g of 1-octanal (manufactured by Wako Pure Chemical Industries) was purified by silica gel column chromatography, and 5.7 g of M-13 was purified. Obtained (5 step yield 13%).

¹ H NMR data of the obtained M-13 are shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ6.4 (d, 2H), δ6.1 (dd, 1H), δ5.9 (tdd, 1H), 5.8 (d, 2H), δ5.3 (d , 1H), δ5.2 (d, 1H), δ4.6 (d, 2H), δ4.4 (s, 4H) δ1.6 (q, 2H), δ1.9-1.6 (m, 8H) ), Δ 0.9 (t, 3H)

(Synthesis of M-14)
In the same manner as in M-11, the crude product of M-14 obtained in 5 steps from 20.0 g of 1-nonanal (manufactured by Wako Pure Chemical Industries) was purified by silica gel column chromatography, and 4.4 g of M-14 was purified. Obtained (5 step yield 9%).

The ¹ H NMR data of the obtained M-14 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ6.4 (d, 2H), δ6.1 (dd, 1H), δ5.9 (tdd, 1H), 5.8 (d, 2H), δ5.3 (d , 1H), δ5.2 (d, 1H), δ4.6 (d, 2H), δ4.4 (s, 4H) δ1.6 (q, 2H), δ1.9-1.6 (m, 10H) ), Δ 0.9 (t, 3H)

(Synthesis of M-15)
After adding 12.6 g of 2,7-octadienol (manufactured by Tokyo Chemical Industry) to 50 mL of acetone and 20 g of pyridine (manufactured by Wako Pure Chemical Industries, Ltd.), 15 g of methanesulfonic acid chloride (manufactured by Tokyo Chemical Industry) is added while cooling with ice. And stirred for 5 hours under reflux. After allowing to cool, 200 mL of 0.2N hydrochloric acid and 300 mL of ethyl acetate were added to the reaction mixture, and the mixture was separated. The organic layer was dried over 20 g of magnesium sulfate, and the filtrate was concentrated to obtain Reactant A. .
11.8 g of 2,2-bis (hydroxymethyl) butyric acid (manufactured by Tokyo Chemical Industry) is dissolved in 80 mL of acetone, 16.6 g of potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.), the total amount of the reagent A prepared previously, potassium iodide ( Tokyo Chemical Co., Ltd.) 0.5 g was added and stirred for 8 hours under reflux. After standing to cool, 150 mL of distilled water and 200 mL of ethyl acetate were added and separated, and the organic layer was dried over 15 g of magnesium sulfate, and the filtered filtrate was concentrated to obtain a crude product of the reaction intermediate (M-15A). Obtained. The obtained crude product was purified by silica gel column chromatography to obtain 3.5 g of M-15A.
The obtained M-15A was dissolved in 30 mL of acetone and cooled in an ice bath. After adding 3.5 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.), 2.7 g of acrylic acid chloride (manufactured by Tokyo Chemical Industry) was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and then an aqueous sodium bicarbonate solution (3 g of sodium bicarbonate + 100 ml of water) was added. After 120 ml of ethyl acetate was added for liquid separation, the organic layer was washed with 50 ml of 0.1N aqueous hydrochloric acid solution and dried over 5 g of magnesium sulfate, and then the filtrate was concentrated to obtain a crude product of M-15. .
The obtained crude product was purified by silica gel column chromatography to obtain 3.8 g of M-15 (2 step yield: 13%).

The ¹ H NMR data of the obtained M-15 is shown. (E, Z-isomer mixture)
¹ H NMR (300 MHz, CDCl ₃ ) δ6.4 (d, 2H), δ6.1 (dd, 2H), δ5.8 (d, 2H), δ5.8-5.7 (m, 2H), δ5 .6-5.4 (m, 1 H), δ 5.0 (d, 1 H), δ 4.9 (d, 1 H), δ 4, 7 (d, 2 H), δ 4.6 (d, 2 H), δ 4.. 4 (s, 4H), δ2.2-2.0 (m, 4H), δ1.7 (q, 2H), δ1.5 (tt, 2H), δ0.9 (t, 3H)

(Synthesis of M-16)
12.2 g of 2,2-bis (hydroxymethyl) butyric acid (manufactured by Tokyo Chemical Industry) is dissolved in 80 mL of acetone, 13.7 g of potassium carbonate (manufactured by Wako Pure Chemical Industries), 0.5 g of copper bromide (manufactured by Tokyo Chemical Industry), 3 -After adding 13.3 g of bromocyclohexene (manufactured by Tokyo Chemical Industry), the mixture was stirred for 6 hours under reflux. After standing to cool, 150 mL of distilled water and 200 mL of ethyl acetate were added and separated. The organic layer was dried over 15 g of magnesium sulfate, and the filtrate was concentrated to obtain a crude product of the reaction intermediate (M-16A). Obtained.
The obtained M-16A was dissolved in 100 mL of acetone, cooled in an ice bath, 20.2 g of triethylamine (manufactured by Wako Pure Chemical Industries) was added, and then 16.5 g of acetone (15 mL) of acrylic acid chloride (manufactured by Tokyo Chemical Industry). The solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and then an aqueous sodium hydrogen carbonate solution (5 g of sodium hydrogen carbonate + 200 ml of water) was added. After 250 ml of ethyl acetate was added for liquid separation, the organic layer was washed with 150 ml of 0.1N aqueous hydrochloric acid solution and dried with 15 g of magnesium sulfate, and then the filtrate was concentrated to obtain a crude product of M-16. .
The obtained crude product was purified by silica gel column chromatography to obtain 11.6 g of M-16 (2 step yield: 42%).

The ¹ H NMR data of the obtained M-16 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ 6.4 (d, 2H), δ 6.1 (dd, 2H), δ 5.9 (dd, 1H), δ 5.8 (d, 2H), δ 5.7 (td , 1H), δ5.3 (td, 1H), δ4.4 (s, 4H), δ2.1-1.9 (m, 2H), δ1.8-1.5 (m, 6H), δ0. 9 (t, 3H)

(Synthesis of M-17)
20.8 g of 2,2-bis (hydroxymethyl) propionic acid (manufactured by Tokyo Chemical Industry) is added to 200 mL of N-methylpyrrolidone, 14.3 g of sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries), 2-bromoethanol (manufactured by Tokyo Chemical Industry) 21.3 g of each was added, heated to 80 ° C., and stirred for 8 hours. After allowing to cool, 82.7 g of 3-chloropropionyl chloride (manufactured by Tokyo Chemical Industry) was added dropwise to the reaction mixture, followed by stirring at 50 ° C. for 4 hours. After allowing to cool, 400 mL of a saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture in an ice bath, and 400 mL of ethyl acetate was added for liquid separation. The organic layer was washed with 200 mL of 0.1N hydrochloric acid, dried over 20 g of magnesium sulfate and filtered, and the filtrate was concentrated.
The obtained intermediate crude product (M-17A) was dissolved in 150 mL of acetone and cooled in an ice bath, and 65.9 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. After stirring at 40 ° C. for 2 hours, 200 mL of distilled water and 300 mL of ethyl acetate were added and separated, and the organic layer was washed with 150 mL of 0.1 N hydrochloric acid aqueous solution. The organic layer was dried over 20 g of magnesium sulfate, and then the filtrate was concentrated to obtain a crude product of M-17.
The resulting crude product was purified by silica gel column chromatography to obtain 33.3 g of M-17 (3 step yield: 63%).

The ¹ H NMR data of the obtained M-17 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ6.5 (d, 2H), δ6.4 (d, 1H), δ6.2 (dd, 1H), 6.1 (dd, 2H), δ5.8 (d , 1H), δ5.8 (d, 2H), δ4.4-4.3 (m, 8H), δ1.3 (s, 3H)

(Synthesis of M-18)
n-octanol (Tokyo Kasei) 10.1 g and epichlorohydrin (Tokyo Kasei) 14.4 g are mixed, tetrabutylammonium bromide (Wako Pure Chemical) 1.6 g, sodium hydroxide (Wako Pure Chemical) ) 4 and 7 g were added and stirred at 40 ° C. for 6 hours. After allowing to cool, 100 mL of distilled water and 150 mL of ethyl acetate were added to the reaction mixture, and the mixture was separated. The organic layer was dried over 15 g of magnesium sulfate, filtered, and the filtrate was concentrated to obtain a reaction intermediate (M-18A). A crude product was obtained.
The obtained M-18A was dissolved in 20 mL of toluene, 6.5 g of acrylic acid (manufactured by Tokyo Chemical Industry), 1.2 g of tetrabutylammonium bromide (manufactured by Wako Pure Chemical Industries), and a small amount of 4-methoxyphenol (manufactured by Tokyo Chemical Industry), respectively. The mixture was added, heated to 90 ° C. and stirred for 10 hours.
After allowing to cool, the reaction mixture was dissolved in 50 mL of acetone and cooled in an ice bath, 7.6 g of triethylamine (manufactured by Wako Pure Chemical Industries) was added, and 6.8 g of acrylic acid chloride (manufactured by Tokyo Chemical Industry) was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and then an aqueous sodium hydrogen carbonate solution (2 g of sodium hydrogen carbonate + 100 mL of water) was added. After 150 ml of ethyl acetate was added for liquid separation, the organic layer was washed with 100 mL of 0.1N aqueous hydrochloric acid solution and dried with 10 g of magnesium sulfate, and then the filtrate was concentrated to obtain a crude product of M-18. .
The resulting crude product was purified by silica gel column chromatography to obtain 13.3 g of M-18 (3 step yield: 55%).

The ¹ H NMR data of the obtained M-18 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ6.4 (d, 1H), δ6.3 (d, 1H), δ6.2 (dd, 1H), 6.1 (dd, 1H), δ5.8 (d , 1H), δ5.8 (d, 1H), δ5.3 (dddd, 1H), δ4.4 (dd, 1H), δ4.3 (dd, 1H), δ3.6 (t, 2H), δ3. 5-3.3 (m, 2H), δ 1.6-1.5 (m, 2H), δ 1.4-1.1 (m, 10H), δ 0.8 (t, 3H)

(Synthesis of M-19)
In the same manner as M-18, the crude product of M-18 was purified from 12.0 g of n-decanol (manufactured by Tokyo Chemical Industry) by silica gel column chromatography to obtain 14.6 g of M-19 (3-step yield) 57%).

The ¹ H NMR data of the obtained M-19 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ6.4 (d, 1H), δ6.3 (d, 1H), δ6.2 (dd, 1H), 6.1 (dd, 1H), δ5.8 (d , 1H), δ5.8 (d, 1H), δ5.3 (dddd, 1H), δ4.4 (dd, 1H), δ4.3 (dd, 1H), δ3.6 (t, 2H), δ3. 5-3.3 (m, 2H), δ 1.6-1.5 (m, 2H), δ 1.4-1.1 (m, 14H), δ 0.8 (t, 3H)

(Synthesis of M-20)
In the same manner as M-18, the crude product of M-20 from 12.0 g of geraniol (manufactured by Tokyo Chemical Industry) was purified by silica gel column chromatography to obtain 13.4 g of M-20 (3 step yield: 51%). ).

The ¹ H NMR data of the obtained M-20 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ 6.5 (d, 1 H), δ 6.4 (d, 1 H), δ 6.2 (dd, 1 H), 6.1 (dd, 1 H), δ 5.8 (d , 1H), δ5.8 (d, 1H), δ5.4-5.3 (m, 2H), δ5.1-5.0 (m, 1H) δ4.4 (dd, 1H), δ4.3 (Dd, 1H), δ 4.0 (dd, 1H), δ 4.0 (dd, 1H) δ 2.2-1.9 (m, 4H), δ 1.7 (s, 3H), δ 1.7 (s , 3H), δ 1.6 (s, 3H)

(Synthesis of M-21)
In the same manner as M-4, the crude product obtained from 15.0 g of 1,2-tetradecanediol (manufactured by Tokyo Chemical Industry) was purified by silica gel column chromatography to obtain 15.4 g of M-21. (Yield 70%)

The ¹ H NMR data of the obtained M-21 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ 6.9 (d, 1 H), δ 6.8 (d, 1 H), δ 6.3 (dd, 1 H), δ 6.2 (dd, 1 H), δ 5.7 (d , 1H), δ5.7 (d, 1H), δ5.3 (tdd, 1H), δ4.6 (dd, 1H), δ4.3 (dd, 1H), δ1.6 (td, 2H), δ1 4-1.2 (m, 20H), δ 0.7 (t, 3H)

(Synthesis of M-22)
In the same manner as M-7, the crude product of M-22 obtained in 2 steps from 8.0 g of 9-decenoic acid (manufactured by Tokyo Chemical Industry) was purified by silica gel column chromatography, and 11.4 g of M-22 was purified. Obtained (2 step yield 69%).

The ¹ H NMR data of the obtained M-22 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ 6.5 (d, 1 H), δ 6.4 (d, 1 H), δ 6.2 (d, 1 H), 6.1 (d, 1 H), δ 5.9 (d , 1H), δ5.9 (d, 1H), δ5.8-5.7 (m, 1H), δ5.5-5.4 (m, 1H) δ5.0 (d, 1H), δ4.9 (D, 1H), δ4.5-4.2 (m, 4H), δ2.4 (t, 2H), δ2.0 (t, 2H), δ1.6 (t, 2H), δ1.4- 1.2 (m, 8H)

(Synthesis of M-23)
In the same manner as M-18, a crude product of M-23 was purified from 9.1 g of n-heptanol (manufactured by Tokyo Chemical Industry) by silica gel column chromatography to obtain 11.7 g of M-23 (3-step yield). 50%).

The ¹ H NMR data of the obtained M-23 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ6.4 (d, 1H), δ6.3 (d, 1H), δ6.2 (dd, 1H), 6.1 (dd, 1H), δ5.8 (d , 1H), δ5.8 (d, 1H), δ5.3 (dddd, 1H), δ4.4 (dd, 1H), δ4.3 (dd, 1H), δ3.6 (t, 2H), δ3. 5-3.3 (m, 2H), δ 1.6-1.5 (m, 2H), δ 1.4-1.1 (m, 8H), δ 0.9 (t, 3H)

(Synthesis of M-24)
In the same manner as M-5, the crude product of M-24 obtained in 3 steps from 15.0 g of n-hexanoic acid (manufactured by Tokyo Chemical Industry) was purified by silica gel column chromatography, and 9.2 g of M-24 was obtained. Obtained (3 step yield 24%).

The ¹ H NMR data of the obtained M-24 is shown.
¹ H NMR (300 MHz, CDCl ₃ ) δ 6.4 (d, 1 H), δ 6.4 (d, 1 H), δ 6.2-6.1 (m, 2 H), δ 5.8 (d, 1 H), δ 5 .8 (d, 1H) δ 5.4 (dddd, 1H), δ 4.5-4.2 (m, 4H), δ 2.3 (t, 2H), δ 1.6 (t, 2H), δ 1.4 -1.2 (m, 6H), δ0.8 (t, 3H)

<Photopolymerization initiator>
P-1: 2,4,6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (Lucirin TPO-L: manufactured by BASF)

<Nonionic surfactant>
W-1: Fluorosurfactant (Dainippon Ink & Chemicals, Inc .: MegaFuck F780F)

[Comparative Example 1]
A composition of Comparative Example 1 was prepared in the same manner except that M-1 was replaced with M-23 in Example 1.

[Comparative Example 2]
A composition of Comparative Example 2 was prepared in the same manner except that M-1 was replaced with M-24 in Example 1.

[Comparative Example 3]
A composition of Comparative Example 3 was prepared in the same manner except that M-1 was replaced with M-25 in Example 1.

[Comparative Example 4]
A composition of Comparative Example 4 was prepared in the same manner except that M-1 was replaced with M-26 in Example 1.

[Comparative Example 5]
A composition of Comparative Example 5 was prepared in the same manner except that M-1 was replaced with M-27 in Example 1.

[Comparative Example 6]
A composition of Comparative Example 6 was prepared in the same manner except that M-1 was replaced with M-29 in Example 1.

<Evaluation of internal contamination>
The composition prepared above was spin-coated on a glass substrate so that the film thickness was 3.0 μm. The spin-coated coated base film was set in a nanoimprint apparatus using an ORC high pressure mercury lamp (lamp power 2000 mW / cm ² ) as a light source. Next, the inside of the apparatus was evacuated (vacuum degree: 1 Torr, about 133 Pa) and held for 30 seconds.
At this time, another opposing glass substrate was installed at a distance of 1 mm from the glass substrate in the apparatus, and the contamination level in the apparatus was evaluated as follows by observing the cloudiness of the surface.
A: There is no cloudiness on the surface of the opposing glass, and no contamination is observed. B: The surface of the opposing glass is slightly clouded, but almost no contamination is observed. C: The surface of the opposing glass is cloudy and slightly contaminated. D: Opposite The composition is clearly attached to the glass surface, and contamination is seen. E: After a large amount of the composition is clearly attached to the surface of the opposing glass, the attached matter disappeared.

(Curing by light irradiation)
The composition prepared above was spin-coated on a glass substrate so that the film thickness was 3.0 μm. The spin-coated coated base film was set in a nanoimprint apparatus using an ORC high pressure mercury lamp (lamp power 2000 mW / cm ² ) as a light source. Next, after the inside of the apparatus was evacuated (vacuum degree: 10 Torr, about 1.33 kPa), nitrogen purge (1.5 atm: mold pressing pressure) was performed to replace the inside of the apparatus with nitrogen.
This was exposed under conditions of an illuminance of 10 mW / cm ² and an exposure amount of 240 mJ / cm ² . The curability of the obtained cured layer was evaluated as follows.
○: Tack is not seen in the resist pattern.
X: Tack is seen in the resist pattern.

  It turned out that the composition of Examples 1-22 hardly causes the contamination in an apparatus, since all have low volatility.

  On the other hand, the compositions of Comparative Examples 1 to 5 were all highly volatile and resulted in in-device contamination. In Comparative Example 6, the contamination disappeared after the opposing glass was severely contaminated. This is presumed to be because the volatility of M-28 is too high, and does not solve the problem.

2. Preparation of curable composition for optical nanoimprints The above (meth) acrylate M-1 (70% by mass), the following low-viscosity polymerizable monomer R-1 (10% by mass), and the following silane coupling agent C-1 (20 Mass%), the photopolymerization initiator P-1 (2 mass% based on the total amount of the polymerizable monomer), and the following antioxidant A-1 (0.5 mass based on the total amount of the polymerizable monomer). %) And the following release agent S-1 (1% by mass relative to the total amount of the polymerizable monomer) were added to prepare a curable composition for optical nanoimprinting of Example 23.

[Examples 24-32]
In Example 23, the composition of Examples 24-32 was prepared like Example 21 except having changed the said curable composition for optical nanoimprint into the compound of following Table 7 and Table 8, respectively.

<Low viscosity polymerizable monomer>
R-1: Nonanediol diacrylate

<Silane coupling agent>
C-1: 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical)
C-2: 3-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical)

<Antioxidant>
A-1: Sumilizer GA80 (manufactured by Sumitomo Chemical Co., Ltd.)
A-2: Irganox 1035FF (manufactured by Ciba)

<Release agent>
S-1: Modified silicone KF-410 (manufactured by Shin-Etsu Chemical)

[Comparative Example 7]
A composition of Comparative Example 7 was prepared in the same manner except that M-1 was replaced with M-24 in Example 23.

[Comparative Example 8]
A composition of Comparative Example 8 was prepared in the same manner except that M-4 was replaced with M-26 in Example 25.

[Comparative Example 9]
A composition of Comparative Example 9 was prepared in the same manner as in Example 28, except that M-10 was replaced with M-28.

[Comparative Example 10]
The (meth) acrylate M-28 (10% by mass), the low-viscosity polymerizable monomer R-1 (80% by mass), the silane coupling agent C-1 (10% by mass), and the photopolymerization initiator. P-1 (2% by mass with respect to the total amount of the polymerizable monomer), the antioxidant A-1 (0.2% by mass with respect to the total amount of the polymerizable monomer), and the antioxidant A- 2 (0.2% by mass with respect to the total amount of the polymerizable monomer) The release agent S-1 (1% by mass with respect to the total amount of the polymerizable monomer) was added, and the composition of Comparative Example 10 was added. Prepared.

[Comparative Example 11]
The (meth) acrylate M-28 (15% by mass), the (meth) acrylate M-29 (75% by mass), the silane coupling agent C-1 (10% by mass), and the photopolymerization initiator P-1. (2% by mass with respect to the total amount of the polymerizable monomer), the antioxidant A-1 (0.2% by mass with respect to the total amount of the polymerizable monomer), the antioxidant A-2 (polymerization) The composition of Comparative Example 11 was prepared by adding the release agent S-1 (1% by mass with respect to the total amount of the polymerizable monomer).

<Evaluation of composition viscosity>
The viscosity of the composition (before curing) was measured at 25 ± 0.2 ° C. using a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd.
The rotation speed during measurement is 100 rpm for 0.5 mPa · s to less than 5 mPa · s, 50 rpm for 5 mPa · s to less than 10 mPa · s, 20 rpm for 10 mPa · s to less than 30 mPa · s, and 30 mPa · s to less than 60 mPa · s. Were performed at 10 rpm, and classified and evaluated as follows according to the viscosity range.
A: Less than 12 mPa · s B: 12 mPa · s or more and less than 18 mPa · s C: 18 mPa · s or more and less than 30 mPa · s D: 30 mPa · s or more

<Evaluation of internal contamination>
The composition prepared above was spin-coated on a glass substrate so that the film thickness was 3.0 μm. The spin-coated coated base film was set in a nanoimprint apparatus using an ORC high pressure mercury lamp (lamp power 2000 mW / cm ² ) as a light source. Next, the inside of the apparatus was evacuated (vacuum degree: 1 Torr, about 133 Pa) and held for 30 seconds.
At this time, another opposing glass substrate was installed at a distance of 1 mm from the glass substrate in the apparatus, and the contamination level in the apparatus was evaluated as follows by observing the cloudiness of the surface.
A: There is no cloudiness on the surface of the opposing glass, and no contamination is observed. B: The surface of the opposing glass is slightly clouded, but almost no contamination is observed. C: The surface of the opposing glass is cloudy and slightly contaminated. D: Opposite The composition is clearly attached to the glass surface, and contamination is seen. E: After a large amount of the composition is clearly attached to the surface of the opposing glass, the attached matter disappeared.

<Observation of pattern accuracy>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm. The spin-coated coated base film is set in a nanoimprint apparatus using an ORC high pressure mercury lamp (lamp power: 2000 mW / cm ² ) as a light source, the mold pressure is 0.8 kN, the degree of vacuum during exposure is 5 Torr, and a line of 10 μm. / 240 mJ / cm ² from the surface of a mold having a space pattern and a groove depth of 4.0 μm made of polydimethylsiloxane (made by Toray Dow Corning, SILPOT184 cured at 80 ° C. for 60 minutes) After exposure, the mold was released to obtain a resist pattern. The obtained resist pattern was completely cured by heating in an oven at 230 ° C. for 30 minutes.
The pattern shape after the transfer was observed with a scanning electron microscope or an optical microscope, and the pattern shape was evaluated as follows.
A: Almost the same as the pattern of the original plate that is the basis of the pattern shape of the mold. B: There is a portion that is partly different from the pattern shape of the original plate that is the basis of the pattern shape of the mold (the range of the original pattern is less than 5%). C: There is a part (a range of 5% or more and less than 10% of the pattern of the original plate) that is partly different from the original pattern shape of the mold pattern shape. D: The original pattern shape of the mold pattern shape. There is a different part (the original pattern and a range of 10% or more and less than 20%) E: The mold pattern shape is clearly different from the original pattern, or the pattern film thickness is 20% or more different from the original pattern

  Each of the curable compositions for optical nanoimprints of Examples 23 to 32 had a low viscosity, and a pattern with high pattern accuracy could be created after curing. In addition, since it has low volatility, it has been found that the composition can be formed without causing contamination in the apparatus, and is a composition excellent in nanoimprint suitability.

  Comparative Examples 7 and 8 had a low viscosity, and a pattern with high pattern accuracy could be created after curing, but contamination occurred in the apparatus.

  In Comparative Example 9, the pattern could be formed without causing contamination in the apparatus, but the viscosity was high and the pattern accuracy after curing was low.

  In Comparative Example 10, the viscosity was high, the pattern accuracy after curing was low, and the apparatus was contaminated.

  Comparative Example 11 had a low viscosity, but the pattern accuracy was low. In the evaluation result of the contamination in the apparatus, it disappeared after a large amount of the composition adhered to the facing glass, so it was estimated that the highly volatile M-27 volatilized under vacuum and the composition of the composition changed. .

  According to the present invention, it has become possible to provide a compound having low viscosity and low volatility. As a result, when used as a curable composition, it is possible to provide a curable composition that has excellent curability and does not contaminate the inside of the apparatus. Furthermore, when used as a curable composition for nanoimprints, it is possible to provide a curable composition for nanoimprints that has excellent pattern accuracy and does not contaminate the inside of the apparatus.

Claims (12)

A compound having a molecular weight of 310 or more, represented by the following general formula (1), the following general formula (2), the following general formula (3), the following general formula (4) or the following general formula (5).

(In the general formulas (1), (2), (3), (4) and (5), R ¹ and R ² each represent a hydrogen atom or a methyl group. In the general formula (1), R ³ Represents a hydrocarbon group having 4 to 10 carbon atoms, in formula (2), R ⁴ represents an alkyl group having 8 to 14 carbon atoms, and in formula (3), R ⁵ represents a group having 4 to 15 carbon atoms. In general formula (4), R ⁶ represents a linear alkyl group having 2 to 10 carbon atoms, and R ⁷ represents an unsaturated hydrocarbon group having 2 to 12 carbon atoms. Or a (meth) acryloyloxyethyl group, wherein R ⁸ represents a hydrocarbon group having 6 to 15 carbon atoms in the general formula (5). The compound represented by general formula (1) according to claim 1, wherein R ³ is an aliphatic hydrocarbon group having 4 to 10 carbon atoms, or a compound represented by general formula (2). , R ⁴ is an alkyl group having 8 to 14 carbon atoms, a compound represented by the general formula (3-1), a compound represented by the general formula (3-2), and a general formula (4-1) A compound represented by formula (4-2), a compound represented by formula (5), wherein R ⁸ is an aliphatic hydrocarbon group having 6 to 15 carbon atoms, Or the following compound.
General formula (3-1)

(In General Formula (3-1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ⁵¹ represents an alkyl group having 4 to 8 carbon atoms.)
Formula (3-2)

(In general formula (3-2), R ¹ and R ² each independently represents a hydrogen atom or a methyl group. R ⁵² represents an alkyl group having 5 to 9 carbon atoms.)
General formula (3-3)

(In General Formula (3-3), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ⁵³ is a hydrocarbon group having 5 to 12 carbon atoms in total, and —CH═ CH -, - CH = C ( CH 3) -, - C (CH 3) = C (CH 3) -, - CH = CH 2, -CH = CH (CH 3), - C (CH 3) = CH ₂ and a group consisting of a combination of at least one group selected from —C (CH ₃ ) ═CH (CH ₃ ) and at least one of an alkyl group and an alkylene group.
Formula (4-1)

(In General Formula (4-1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ⁶¹ represents a linear alkyl group having 2 to 8 carbon atoms.)
General formula (4-2)

(In General Formula (4-2), R ¹ and R ² each independently represents a hydrogen atom or a methyl group. R ⁷¹ represents an unsaturated hydrocarbon group having 2 to 12 carbon atoms or (meth) acryloyloxy. Represents an ethyl group, and R ⁷² represents a methyl group or an ethyl group.)

In claim 1, a compound represented by the general formula (1), R ³ is a straight chain alkyl group having 4-8 carbon atoms, a compound represented by the general formula (2) , Compounds wherein R ⁴ is an alkyl group having 10 to 12 carbon atoms, compounds represented by general formula (3-1), compounds represented by general formula (3-2), and general formula (3-3) A compound represented by formula (4-1), a compound represented by formula (5), wherein R ⁸ is a linear alkyl group having 6 to 13 carbon atoms, or Any of the following compounds.
General formula (3-1)

(In General Formula (3-1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ⁵¹ represents an alkyl group having 4 to 8 carbon atoms.)
Formula (3-2)

(In general formula (3-2), R ¹ and R ² each independently represents a hydrogen atom or a methyl group. R ⁵² represents an alkyl group having 5 to 9 carbon atoms.)
General formula (3-3)

(In General Formula (3-3), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ⁵³ is a hydrocarbon group having 5 to 12 carbon atoms in total, and —CH═ CH -, - CH = C ( CH 3) -, - C (CH 3) = C (CH 3) -, - CH = CH 2, -CH = CH (CH 3), - C (CH 3) = CH ₂ and a group consisting of a combination of at least one group selected from —C (CH ₃ ) ═CH (CH ₃ ) and at least one of an alkyl group and an alkylene group.
Formula (4-1)

(In General Formula (4-1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ⁶¹ represents a linear alkyl group having 2 to 8 carbon atoms.)

Any of the following compounds.

A curable composition comprising the compound according to any one of claims 1 to 4 and a photopolymerization initiator. It hardens | cures by light irradiation, The curable composition of Claim 5 characterized by the above-mentioned. The curable composition according to claim 5, which is cured by heating. The curable composition according to any one of claims 5 to 7, which is used for nanoimprinting. Hardened | cured material which hardened the composition of any one of Claims 5-8. Applying the compound according to any one of claims 1 to 4 and a curable composition for nanoimprint containing a photopolymerization initiator on a substrate to form a layer, and forming a layer on the layer formed in the layer The manufacturing method of the hardened | cured material characterized by including the process of light-irradiating the process formed and the layer formed in the said layer shape. The method for producing a cured product according to claim 10, further comprising a step of heating the formed layer after irradiation with light. The member for liquid crystal display devices containing the hardened | cured material of Claim 9.