JP2012231072A - Curable composition for imprint, pattern formation method and pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition for imprint being excellent in pattern formability regardless of an atmosphere in which a pattern is formed and also having fewer pattern defects.SOLUTION: A curable composition for imprint contains (A) a compound having a carbon-carbon multiple bond, (B) a compound having a Si-H bond with a molecular weight of 1500 or less, and (C) a photoinitiator; or a curable composition for imprint contains (AB) a compound having a carbon-carbon multiple bond and a Si-H bond with a molecular weight of 1500 or less, and (C) a photoinitiator.

Description

  The present invention relates to a curable composition for imprints. More specifically, semiconductor integrated circuits, flat screens, micro electro mechanical systems (MEMS), sensor elements, optical recording media such as high-density memory disks, optical components such as diffraction gratings and relief holograms, nano devices, optical devices, Optical films and polarizing elements for manufacturing flat panel displays, thin film transistors for liquid crystal displays, organic transistors, color filters, overcoat layers, pillar materials, rib materials for liquid crystal alignment, microlens arrays, immunoassay chips, DNA separation chips The present invention relates to a curable composition for imprinting for forming a fine pattern using light irradiation, which is used for producing a microreactor, nanobiodevice, optical waveguide, optical filter, photonic liquid crystal, and the like.

  The nanoimprint method has been developed by developing an embossing technique that is well-known in optical disc production, and mechanically pressing a mold master (generally called a mold, stamper, or template) with a concavo-convex pattern onto a resist. This is a technology that precisely deforms and transfers fine patterns. Once the mold is made, it is economical because nanostructures and other microstructures can be easily and repeatedly molded, and it is economical, and since it is a nano-processing technology with less harmful waste and emissions, it has recently been applied to various fields. Is expected.

  The nanoimprint method includes two methods: a thermal imprint method using a thermoplastic resin as a material to be processed (for example, see Non-Patent Document 1) and an optical imprint method using a curable composition (for example, see Non-Patent Document 2). Street technology has been proposed. In the case of the thermal nanoimprint method, the mold is pressed on a polymer resin heated to a temperature higher than the glass transition temperature, and the mold is released after cooling to transfer the fine structure to the resin on the substrate. Since this method can be applied to various resin materials and glass materials, application to various fields is expected. For example, Patent Documents 1 and 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 or a transparent substrate and the curable composition for optical nanoimprint is photocured, it is not necessary to heat the material transferred when the mold is pressed, and imprinting at room temperature is possible. It 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 a case where a 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, high-density recording media, optical films, and structural members in flat panel displays. The second technology is to build a multilayer structure by simultaneous integral molding of microstructure and nanostructure and simple interlayer alignment, and apply this to the production of μ-TAS (Micro-Total Analysis System) and biochips. It is what. The third technique is used for processing a substrate by a method such as etching using the formed pattern as a mask. In this technology, high-precision alignment and high integration enable high-density semiconductor integrated circuit fabrication, liquid crystal display transistor fabrication, and magnetic media for next-generation hard disks called patterned media instead of conventional lithography technology. It can be applied to processing. In recent years, efforts have been made to put the nanoimprint method relating to these applications into practical use.

  As an application example of the nanoimprint method, first, an application example for manufacturing 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. However, it has become difficult to satisfy three requirements of fine pattern resolution, apparatus cost, and throughput for further miniaturization requirements. On the other hand, nanoimprint lithography (optical nanoimprint method) has been proposed as a technique for performing fine pattern formation at low cost. For example, Patent Document 1 and Patent Document 3 listed below disclose nanoimprint technology in which a silicon wafer is used as a stamper and a fine structure of 25 nm or less is formed by transfer. In this application, a pattern forming property of a level of several tens of nm and a high etching resistance for functioning as a mask during substrate processing are required.

  An application example of the nanoimprint method to the production of the next generation hard disk drive (HDD) will be described. HDDs have increased in capacity by increasing the surface recording density. However, when the recording density is increased, so-called magnetic field spreading from the side surface of the magnetic head becomes a problem. Since the magnetic field spread does not become smaller than a certain value even if the head is made smaller, a phenomenon called sidelight occurs as a result. When side writing occurs, writing to an adjacent track occurs during recording, and already recorded data is erased. Further, due to the magnetic field spread, a phenomenon such as reading an excessive signal from an adjacent track occurs during reproduction. In order to solve such a problem, technologies such as discrete track media and bit patterned media have been proposed which are solved by filling the spaces between tracks with a nonmagnetic material and physically and magnetically separating the tracks. The application of nanoimprinting has been proposed as a method for forming a magnetic or nonmagnetic pattern in the production of these media. Also in this application, a pattern forming property of several tens of nm level and high etching resistance for functioning as a mask during substrate processing are required.

Next, an application example of the nanoimprint method to a flat display such as a liquid crystal display (LCD) or a plasma display (PDP) will be described.
With the trend toward larger and higher definition LCD substrates and PDP substrates, the optical nanoimprint method has recently attracted attention as an inexpensive lithography that replaces the conventional photolithography method used in the manufacture of thin film transistors (TFTs) and electrode plates. Yes. Therefore, it has become necessary to develop a photo-curable resist that replaces the etching photoresist used in the conventional photolithography method.
Further, as a structural member such as an LCD, application of the optical nanoimprint method to the transparent protective film material described in Patent Document 4 and Patent Document 5, the spacer described in Patent Document 5, and the like has begun to be studied. 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”.
In addition, a spacer that defines a cell gap in a liquid crystal display is also a kind of permanent film. In conventional photolithography, a photocurable composition comprising a resin, a photopolymerizable monomer, and an initiator has been widely used. (For example, see Patent Document 6). The spacer is generally a pattern having a size of about 10 μm to 20 μm by photolithography after applying the photocurable composition after forming the color filter on the color filter substrate or after forming the protective film for the color filter. And is further heated and cured by post-baking.
The nanoimprint method can also be used to create an antireflection structure generally called moth eye. By forming innumerable fine irregularities made of a transparent material on the surface of the transparent molded article at a pitch equal to or less than the wavelength of light, an antireflection structure in which the refractive index of light changes in the thickness direction can be formed. Since the refractive index of such an antireflection structure continuously changes in the thickness direction, there is no refractive index interface, and theoretically it can be made non-reflective. Further, since the wavelength dependency is small and the antireflection performance against oblique light is high, the antireflection performance superior to that of the multilayer antireflection film is provided.

In addition, microelectromechanical systems (MEMS), sensor elements, optical components such as diffraction gratings and relief holograms, nanodevices, optical devices, optical films and polarizing elements for the production of flat panel displays, thin film transistors for liquid crystal displays, organic transistors , Color filter, overcoat layer, pillar material, rib material for liquid crystal alignment, microlens array, immunoassay chip, DNA separation chip, microreactor, nanobiodevice, optical waveguide, optical filter, photonic liquid crystal, etc. Nanoimprint lithography is also useful in applications.
In these permanent film applications, the formed pattern will eventually remain in the product, so the durability of the film, mainly heat resistance, light resistance, solvent resistance, scratch resistance, high mechanical properties against external pressure, hardness, etc. And strength-related performance is required.
As described above, most of the patterns conventionally formed by the photolithography method can be formed by nanoimprinting, and attention has been paid as a technique capable of forming a fine pattern at low cost.

  In order to use nanoimprint in the industry, good pattern formability is required, but for example, Patent Document 7 also discusses it. However, there is a problem that pattern formability changes depending on the atmosphere in which the pattern is formed.

US Pat. No. 5,772,905 US Pat. No. 5,956,216 US Pat. No. 5,259,926 JP 2005-197699 A Japanese Patent Laying-Open No. 2005-301289 Japanese Patent Laid-Open No. 2004-240241 JP 2006-310565 A

S. Chou et al .: Appl. Phys. Lett. Vol. 67, 3114 (1995) M. Colbun et al,: Proc.SPIE, Vol. 3676,379 (1999)

  An object of the present invention is to solve the above-described problems, and is a curable composition for imprints that has excellent pattern formability and few pattern defects regardless of the atmosphere in which the pattern is formed. The purpose is to provide.

Under such circumstances, the inventors of the present application have examined, and by adopting a compound containing a Si-H bond, chain transfer occurs during photocuring, the mobility of active species is improved, and curing is smooth. I found it going. In addition, it was found that by adopting a compound containing a Si—H bond, inhibition of polymerization by oxygen in the air can be suppressed, so that the pattern forming property does not change regardless of the atmosphere in which the pattern is formed. As a result, the present invention has been completed.
Specifically, the above problem has been achieved by the following means.

(1) (A) a compound having a carbon-carbon multiple bond, (B) a compound having a Si—H bond having a molecular weight of 1500 or less, and (C) a curable composition for imprints containing a photopolymerization initiator, or (AB) A curable composition for imprints containing a compound having a carbon-carbon multiple bond and a Si—H bond having a molecular weight of 1500 or less, and (C) a photopolymerization initiator.
(2) The curable composition for imprints according to (1), which contains substantially no solvent.
(3) The curable composition for imprints according to (1) or (2), wherein the viscosity at 25 ° C. of all components excluding the solvent is 100 mPa · s or less.
(4) At least one of (A) a compound having a carbon-carbon multiple bond and (AB) a compound having a carbon-carbon multiple bond and a Si—H bond having a molecular weight of 1500 or less has two carbon-carbon multiple bonds. The curable composition for imprints according to any one of (1) to (3), which is a compound having the above.
(5) (A) a compound having a carbon-carbon multiple bond, or (AB) a compound having a carbon-carbon multiple bond and a Si—H bond having a molecular weight of 1500 or less has a (meth) acryl group, (1) The curable composition for imprints according to any one of to (4).
(6) At least one of (A) a compound having a carbon-carbon multiple bond, and (AB) a compound having a carbon-carbon multiple bond and a Si—H bond having a molecular weight of 1500 or less has two or more Si—H bonds. The curable composition for imprints according to any one of (1) to (5), which is a compound to be contained.
(7) (A) a compound having a carbon-carbon multiple bond, (B) a compound having a Si—H bond having a molecular weight of 1500 or less, and (AB) a carbon-carbon multiple bond and a Si—H bond having a molecular weight of 1500 or less. The curable composition for imprints according to any one of (1) to (6), wherein at least one of the compounds having an aromatic group is contained.
(8) The curable composition for imprints according to any one of (1) to (7), further comprising a compound having a carbon-carbon multiple bond and a silicon atom.
(9) The curable composition for imprints according to any one of (1) to (8), further comprising a compound having a carbon-carbon multiple bond and a fluorine atom.
(10) At least one of (B) a compound having a Si—H bond having a molecular weight of 1500 or less, and (AB) a compound having a carbon-carbon multiple bond and a Si—H bond having a molecular weight of 1500 or less are —SiH (CH ₃ ) The curable composition for imprints according to any one of (1) to (9), which has _two structures.
(11) A pattern forming method using the curable composition for imprints according to any one of (1) to (10).
(12) A step of forming a pattern forming layer by applying the curable composition for imprints according to any one of (1) to (10) on a substrate;
Pressing the mold against the surface of the pattern forming layer;
Irradiating the pattern forming layer with light;
A pattern forming method comprising:
(13) A pattern obtained by the pattern forming method according to (11) or (12).
(14) An electronic device including the pattern according to (13).
(15) A method for manufacturing an electronic device, comprising the pattern forming method according to (11) or (12).

  According to the present invention, it is possible to provide a curable composition for imprints that has excellent pattern formability and few pattern defects regardless of the atmosphere in which the pattern is formed.

  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.

In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. The monomer in the present invention is distinguished from oligomers and polymers, and refers to a compound having a weight average molecular weight of 2,000 or less.
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. In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

[Curable composition for imprints of the present invention]
The first embodiment of the curable composition for imprints of the present invention includes (A) a compound having a carbon-carbon multiple bond, (B) a compound having a Si—H bond, and (C) a photopolymerization initiator. contains. The second embodiment of the curable composition for imprints of the present invention contains (AB) a compound having a carbon-carbon multiple bond and a Si—H bond, and (C) a photopolymerization initiator.

(A) Compound having carbon-carbon multiple bond (A) As a compound having carbon-carbon multiple bond, (meth) acryl group, vinyl group (preferably vinyl ester group, vinyl ether group), allyl group (preferably , Allyl ester group, allyl ether group) and a polymerizable group-containing compound (polymerizable compound) are preferable, and a (meth) acrylic group-containing compound is more preferable. The component (A) preferably contains a compound having two or more carbon-carbon multiple bonds, more preferably 2 to 10, and still more preferably 2 to 4.
(A) The compound having a carbon-carbon multiple bond preferably has an aromatic group or an alicyclic hydrocarbon group, more preferably has an aromatic group, and more preferably has a benzene ring or a naphthalene ring.
Further, (A) the compound having a carbon-carbon multiple bond is preferably 50 to 98% by mass of the total polymerizable component excluding the solvent contained in the curable composition for imprints of the present invention, 70 More preferably, it is -95 mass%.
(A) The molecular weight of the compound having a carbon-carbon multiple bond is preferably 100 to 500, and more preferably 150 to 350.
(A) The viscosity of the compound having a carbon-carbon multiple bond is preferably 1 to 200 mPa · s, and more preferably 2 to 100 mPa · s. When a plurality of compounds having carbon-carbon multiple bonds are contained, the viscosity of the mixture is preferably in the above range.
Hereinafter, preferred examples of the compound (A) having a carbon-carbon multiple bond used in the present invention will be described in more detail. Of course, it goes without saying that compounds other than these may be used.

Compound having (meth) acrylic group First, as the compound (A) having a carbon-carbon multiple bond, a polymerizable compound having one (meth) acrylic group (monofunctional polymerizable compound) can be used. Specifically, 2-acryloyloxyethyl phthalate, 2-acryloyloxy 2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (Meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acrylic acid dimer, benzyl (meth) acrylate, 1- or 2-naphthyl (meth) Acrylate, butanediol mono (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, ethylene oxide modified (hereinafter referred to as “EO”) cresol (meth) acrylate, dipropylene glycol (meth) ) Acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclohenta Nyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, methoxy Dipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonyl Phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, epichlorohydrin (hereinafter referred to as “ECH”) modified phenoxy acrylate, phenoxyethyl (Meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (Meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meta ) Acrylate, tert-butyl (meth) acrylate, tribromophenyl (meth) acrylate, EO-modified tribromophenyl (meth) acrylate, and tridodecyl (meth) acrylate.

In the present invention, it is also preferable to use a polyfunctional polymerizable compound having two (meth) acryl groups as the compound (A) having a carbon-carbon multiple bond.
Examples of the bifunctional polymerizable compound having two (meth) acrylic groups that can be preferably used in the present invention include diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, and di (meth) acrylate. ) Acrylic isocyanurate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, EO-modified 1,6-hexanediol di (meth) acrylate, ECH-modified 1,6- Hexanediol di (meth) acrylate, allyloxypolyethylene glycol acrylate, 1,9-nonanediol di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, modified bisphenol A di (Meth) acrylate, EO-modified bisphenol F di (meth) acrylate, ECH-modified hexahydrophthalic acid diacrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO-modified neopentyl glycol di Acrylate, propylene oxide (hereinafter referred to as “PO”) modified neopentyl glycol diacrylate, caprolactone modified hydroxypivalate ester neopentyl glycol, stearic acid modified pentaerythritol di (meth) acrylate, ECH modified phthalic acid di (meth) acrylate, Poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol-tetramethylene glycol) di (me ) Acrylate, polyester (di) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ECH-modified propylene glycol di (meth) acrylate, silicone di (meth) acrylate, triethylene glycol di (meth) acrylate , Tetraethylene glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, neopentyl glycol modified trimethylol propane di (meth) acrylate, tripropylene glycol di (meth) acrylate, EO modified tripropylene glycol di ( (Meth) acrylate, triglycerol di (meth) acrylate, dipropylene glycol di (meth) acrylate, divinylethylene urea, divinyl Rupropylene urea is exemplified.

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

  In the present invention, as the compound (A) having a carbon-carbon multiple bond, a polyfunctional polymerizable compound having three or more (meth) acryl groups can also be used. Specifically, ECH-modified glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, pentaerythritol triacrylate, EO-modified phosphate triacrylate, trimethylolpropane tri (meta) ) Acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexa ( (Meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate Rate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate And pentaerythritol tetra (meth) acrylate.

  Among these, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like are preferably used in the present invention.

  Among the (meth) acrylate compounds, acrylate compounds are preferred from the viewpoint of curability.

  As the compound (A) having a carbon-carbon multiple bond used in the present invention, a vinyl ether compound is also preferable. As the vinyl ether compound, known compounds can be appropriately selected. For example, 2-ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, diethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylol Propane trivinyl ether, trimethylol ethane trivinyl ether, hexanediol divinyl ether, tetra Tylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene vinyl ether , Trimethylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether, pentaerythritol triethylene vinyl ether, pentaerythritol tetraethylene vinyl ether, 1,1,1-to Scan [4- (2-vinyloxy ethoxy) phenyl] ethane, bisphenol A divinyloxyethyl carboxyethyl ether.

  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, the reaction of a polyhydric alcohol or polyhydric phenol with acetylene, or They can be synthesized by reacting a polyhydric alcohol or polyhydric phenol with a halogenated alkyl vinyl ether, and these can be used singly or in combination of two or more.

The polymerizable compound used in the present invention contains 30 to 100% by mass of (meth) acrylate containing at least one of an aromatic group, an alicyclic hydrocarbon group, a fluorine atom and a Si atom in another polymerizable compound. Preferably, it contains 70-100 mass%, More preferably, it contains 90-100 mass%.
As a more preferred embodiment, a polymerizable compound containing an aromatic group (preferably a phenyl group, a naphthyl group, and more preferably a naphthyl group) is a 50 to 100% by mass of a (meth) acrylate polymerizable compound in all components of the polymerizable compound. It is preferable to contain, More preferably, it is 70-100 mass%, More preferably, it contains 90-99.5 mass%.

（一般式中、Ｚは芳香族基を含有する基を表し、Ｒ¹は水素原子、アルキル基またはハロゲン原子を表す。但し、重合性化合物（Ａｘ）が２５℃において液体であるとき、２５℃における粘度が５００ｍＰａ・ｓ以下である。）
Ｒ¹は、好ましくは、水素原子またはアルキル基であり、水素原子またはメチル基が好ましく、硬化性の観点から、水素原子がさらに好ましい。Ｚは、好ましくは置換基を有していても良いアラルキル基、置換基を有していても良いアリール基、または、これらの基が連結基を介して結合した基である。ここでいう連結基は、ヘテロ原子を含む連結基を含んでいてもよく、好ましくは、−ＣＨ₂−、−Ｏ−、−Ｃ（＝Ｏ）−、−Ｓ−およびこれらの組み合わせからなる基である。Ｚに含まれる芳香族基としてはフェニル基、ナフチル基が好ましい。Ｚの分子量としては９０〜３００であることが好ましく、より好ましくは１２０〜２５０である。 As the polymerizable compound having an aromatic group used in the present invention, a monofunctional (meth) acrylate compound represented by the following general formula (I) or a polyfunctional (meth) acrylate represented by the following general formula (II) Compounds are preferred.

(In the general formula, Z represents a group containing an aromatic group, and R ¹ represents a hydrogen atom, an alkyl group or a halogen atom. However, when the polymerizable compound (Ax) is a liquid at 25 ° C., it is 25 ° C. Viscosity at 500 mPa · s or less.)
R ¹ is preferably a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom from the viewpoint of curability. Z is preferably an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a group in which these groups are bonded via a linking group. The linking group here may include a linking group containing a hetero atom, and preferably a group consisting of —CH ₂ —, —O—, —C (═O) —, —S—, and combinations thereof. It is. The aromatic group contained in Z is preferably a phenyl group or a naphthyl group. The molecular weight of Z is preferably 90 to 300, more preferably 120 to 250.

When the polymerizable compound represented by formula (I) is a liquid at 25 ° C., the viscosity at 25 ° C. is preferably 2 to 500 mPa · s, more preferably 3 to 200 mPa · s, and more preferably 3 to 100 mPa · s. Most preferred. Even when the polymerizable compound is liquid at 25 ° C. or solid, the melting point is preferably 60 ° C. or less, more preferably 40 ° C. or less, and further preferably liquid at 25 ° C. .
Z is preferably a group represented by -Z ¹ -Z ² . Here, Z ¹ is a single bond or a hydrocarbon group, and the hydrocarbon group may include a linking group containing a hetero atom in the chain. Z ² is an aromatic group which may have a substituent and has a molecular weight of 90 or more.
Z ¹ is preferably a single bond or an alkylene group, and the alkylene group may contain a linking group containing a hetero atom in the chain. Z ¹ is more preferably an alkylene group that does not contain a linking group containing a hetero atom in the chain, and more preferably a methylene group or an ethylene group. Examples of the linking group containing a hetero atom include —O—, —C (═O) —, —S—, and a group composed of a combination of these with an alkylene group. Moreover, it is preferable that carbon number of a hydrocarbon group is 1-3.

Z ² is also preferably a group in which two or more aromatic groups are linked directly or via a linking group. The linking group in this case is also preferably a group consisting of —CH ₂ —, —O—, —C (═O) —, —S—, and combinations thereof.

  Examples of the substituent that the aromatic group of the polymerizable compound represented by the general formula (I) may have include, for example, a halogen atom (fluorine atom, chloro atom, bromine atom, iodine atom). A linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, Examples thereof include an alkylthio group, an arylthio group, a heterocyclic oxy group, an acyloxy group, an amino group, a nitro group, a hydrazino group, and a heterocyclic group. A group further substituted with these groups is also preferred.

The addition amount of the polymerizable compound represented by formula (I) in the photocurable composition is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, and 30 to 80%. It is particularly preferable that the content is% by mass.
Specific examples of the compound represented by the general formula (I) having no substituent on the aromatic ring include benzyl (meth) acrylate, phenethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 1- Or 2-naphthyl (meth) acrylate, 1- or 2-naphthylmethyl (meth) acrylate, 1- or 2-naphthylethyl (meth) acrylate, 1- or 2-naphthoxyethyl (meth) acrylate is preferable.

（一般式（ＩＩ）中、Ｒ¹は水素原子、アルキル基またはハロゲン原子を表し、Ｘ¹は単結合または炭化水素基であり、該炭化水素基は、その鎖中にヘテロ原子を含む連結基を含んでいてもよい。Ｙ¹は分子量１５以上の置換基を表し、ｎ１は１〜３の整数を表す。Ａｒは、芳香族連結基を表し、フェニレン基またはナフチレン基が好ましい。） As the compound represented by the general formula (I), a compound having a substituent on the aromatic ring represented by the following general formula (II) is also preferable.

(In the general formula (II), R ¹ represents a hydrogen atom, an alkyl group or a halogen atom, X ¹ is a single bond or a hydrocarbon group, and the hydrocarbon group is a linking group containing a hetero atom in the chain. Y ¹ represents a substituent having a molecular weight of 15 or more, n1 represents an integer of 1 to 3. Ar represents an aromatic linking group, and is preferably a phenylene group or a naphthylene group.)

R ¹ has the same meaning as R ¹ in the formula, the preferred range is also the same.
X ¹ has the same meaning as Z ¹ described above, and the preferred range is also the same.
Y ¹ is a substituent having a molecular weight of 15 or more, and examples thereof include an alkyl group, an alkoxy group, an aryloxy group, an aralkyl group, an acyl group, an alkoxycarbonyl group, an alkylthio group, an arylthio group, a halogen atom, and a cyano group. These substituents may have further substituents.
When n1 is 2, X ¹ is preferably a single bond or a hydrocarbon group having 1 carbon atom.
In particular, the preferred aspect at n1 is 1, X ¹ is an alkylene group having 1 to 3 carbon atoms.

  The compound represented by the general formula (II) is more preferably a compound represented by any one of (IV) and (V).

一般式（ＩＶ）中、Ｒ¹は水素原子、アルキル基またはハロゲン原子を表す。Ｘ²は単結合、または、炭化水素基であり、該炭化水素基は、その鎖中にヘテロ原子を含む連結基を含んでいてもよい。Ｙ²は分子量１５以上の芳香族基を有さない置換基を表し、ｎ２は１〜３の整数を表す。
Ｒ¹は、上記一般式のＲ¹と同義であり、好ましい範囲も同義である。
Ｘ²は、炭化水素基である場合、炭素数１〜３の炭化水素基であることが好ましく、置換または無置換の炭素数１〜３のアルキレン基であることが好ましく、無置換の炭素数１〜３のアルキレン基であることがより好ましく、メチレン基、エチレン基であることがさらに好ましい。このような炭化水素基を採用することにより、より低粘度で低揮発性を有する光硬化性組成物とすることが可能になる。
Ｙ²は分子量１５以上の芳香族基を有さない置換基を表し、Ｙ²の分子量の上限は１５０以下であることが好ましい。Ｙ²としては、メチル基、エチル基、イソプロピル基、ｔｅｒｔ−ブチル基、シクロヘキシル基などの炭素数１〜６のアルキル基、フロロ基、クロロ基、ブロモ基などのハロゲン原子、メトキシ基、エトキシ基、シクロヘキシルオキシ基などの炭素数１〜６のアルコキシ基、シアノ基が好ましい例として挙げられる。
ｎ２は、１〜２の整数であることが好ましい。ｎ２が１の場合、置換基Ｙはパラ位にあるのが好ましい。また、粘度の観点から、ｎ２が２のときは、Ｘ²は単結合もしくは炭素数１の炭化水素基が好ましい。 Compound represented by general formula (IV)

In the general formula (IV), R ¹ represents a hydrogen atom, an alkyl group or a halogen atom. X ² is a single bond or a hydrocarbon group, and the hydrocarbon group may contain a linking group containing a hetero atom in the chain. Y ² represents a substituent having a molecular weight of 15 or more aromatic groups, n2 represents an integer of 1 to 3.
R ¹ has the same meaning as R ¹ in the formula, the preferred range is also the same.
When X ² is a hydrocarbon group, it is preferably a hydrocarbon group having 1 to 3 carbon atoms, preferably a substituted or unsubstituted alkylene group having 1 to 3 carbon atoms, and an unsubstituted carbon number. It is more preferably an alkylene group of 1 to 3, more preferably a methylene group or an ethylene group. By employing such a hydrocarbon group, a photocurable composition having a lower viscosity and lower volatility can be obtained.
Y ² represents a substituent having no aromatic group having a molecular weight of 15 or more, and the upper limit of the molecular weight of Y ² is preferably 150 or less. Y ² is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or a cyclohexyl group, a halogen atom such as a fluoro group, a chloro group or a bromo group, a methoxy group or an ethoxy group. Preferred examples include C1-C6 alkoxy groups such as cyclohexyloxy group, and cyano groups.
n2 is preferably an integer of 1 to 2. When n2 is 1, the substituent Y is preferably in the para position. From the viewpoint of viscosity, when n2 is 2, X ² is preferably a single bond or a hydrocarbon group having 1 carbon atom.

From the viewpoint of achieving both low viscosity and low volatility, the molecular weight of the (meth) acrylate compound represented by the general formula (IV) is preferably 175 to 250, and more preferably 185 to 245.
Moreover, it is preferable that the viscosity in 25 degreeC of the (meth) acrylate compound represented by general formula (IV) is 50 mPa * s or less, and it is more preferable that it is 20 mPa * s or less.
The compound represented by the general formula (IV) can be preferably used as a reaction diluent.

  The addition amount of the compound represented by the general formula (IV) in the photocurable composition is preferably 10% by mass or more from the viewpoint of the viscosity of the composition or the pattern accuracy after curing, and is 15% by mass or more. More preferably, it is particularly preferably 20% by mass or more. On the other hand, from the viewpoint of tackiness after curing and mechanical strength, the addition amount is preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

Although the compound represented by general formula (IV) is illustrated below, it cannot be overemphasized that this invention is not limited to these.

（一般式（Ｖ）中、Ｒ¹は水素原子、アルキル基またはハロゲン原子を表し、Ｘ³は単結合、または、炭化水素基であり、該炭化水素基は、その鎖中にヘテロ原子を含む連結基を含んでいてもよい。Ｙ³は芳香族基を有する置換基を表し、ｎ３は１〜３の整数を表す。）
Ｒ¹は、上記一般式のＲ¹と同義であり、好ましい範囲も同義である。
Ｙ³は、芳香族基を有する置換基を表し、芳香族基を有する置換基としては芳香族基が単結合、あるいは連結基を介して一般式（Ｖ）の芳香環に結合している様態が好ましい。連結基としては、アルキレン基、ヘテロ原子を有する連結基（好ましくは−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）Ｏ−、）あるいはこれらの組み合わせが好ましい例として挙げられ、アルキレン基または−Ｏ−ならびにこれらの組み合わせからなる基がより好ましい。芳香族基を有する置換基としてはフェニル基を有する置換基であることが好ましい。フェニル基が単結合または上記連結基を介して結合している様態が好ましく、フェニル基、ベンジル基、フェノキシ基、ベンジルオキシ基、フェニルチオ基が特に好ましい。Ｙ³の分子量は好ましくは、２３０〜３５０である。
ｎ３は、好ましくは、１または２であり、より好ましくは１である。 Compound represented by general formula (V)

(In the general formula (V), R ¹ represents a hydrogen atom, an alkyl group or a halogen atom, X ³ is a single bond or a hydrocarbon group, and the hydrocarbon group contains a hetero atom in the chain. may contain a linking group .Y ³ represents a substituent having an aromatic group, n3 is an integer of 1-3.)
R ¹ has the same meaning as R ¹ in the formula, the preferred range is also the same.
Y ³ represents a substituent having an aromatic group. As the substituent having an aromatic group, the aromatic group is bonded to the aromatic ring of the general formula (V) through a single bond or a linking group. Is preferred. Preferred examples of the linking group include an alkylene group, a linking group having a hetero atom (preferably —O—, —S—, —C (═O) O—, or a combination thereof), and an alkylene group or — A group consisting of O- and combinations thereof is more preferred. The substituent having an aromatic group is preferably a substituent having a phenyl group. A mode in which the phenyl group is bonded through a single bond or the above linking group is preferable, and a phenyl group, a benzyl group, a phenoxy group, a benzyloxy group, and a phenylthio group are particularly preferable. The molecular weight of Y ³ is preferably 230 to 350.
n3 is preferably 1 or 2, more preferably 1.

  The addition amount of the compound represented by the general formula (V) in the photocurable composition used in the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, and 30% by mass. The above is particularly preferable. On the other hand, from the viewpoint of tackiness after curing and mechanical strength, the addition amount is preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less.

Although the compound represented by general formula (V) is illustrated below, it cannot be overemphasized that this invention is not limited to these.

式中Ａｒ₂は芳香族基を有するｎ価の連結基を表し、好ましくはフェニレン基を有する連結基である。Ｘ₁、Ｒ¹は前述と同義である。ｎは１〜３を表し、好ましくは１である。 Polyfunctional (meth) acrylate compound represented by general formula (II)

In the formula, Ar ₂ represents an n-valent linking group having an aromatic group, and preferably a linking group having a phenylene group. X ₁ and R ¹ are as defined above. n represents 1-3, and is preferably 1.

（一般式（ＶＩ）中、Ｘ⁶は（ｎ６＋１）価の連結基であり、Ｒ¹は、それぞれ、水素原子、アルキル基、ハロゲン原子である。Ｒ²およびＲ³は、それぞれ、置換基であり、ｎ４およびｎ５は、それぞれ、０〜４の整数である。ｎ６は１または２であり、Ｘ⁴およびＸ⁵は、それぞれ、炭化水素基であり、該炭化水素基は、その鎖中にヘテロ原子を含む連結基を含んでいてもよい。） The compound represented by the general formula (II) is preferably a compound represented by the general formula (VI) or (VII).
Compound represented by general formula (VI)

(In General Formula (VI), X ⁶ is a (n6 + 1) -valent linking group, R ¹ is a hydrogen atom, an alkyl group, or a halogen atom. R ² and R ³ are each a substituent. There, n4 and n5 are each an integer of 0 to 4 .N6 is 1 or 2, X ⁴ and X ⁵ are each a hydrocarbon group, the hydrocarbon group in the chain (It may contain a linking group containing a hetero atom.)

X ⁶ represents a single bond or a (n6 + 1) -valent linking group, and preferably an alkylene group, —O—, —S—, —C (═O) O—, or a combination thereof. It is a linking group. The alkylene group is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms. An unsubstituted alkylene group is preferred.
n6 is preferably 1. When n6 is 2, a plurality of R ¹ , X ⁵ , and R ² may be the same or different.
X ⁴ and X ⁵ are each preferably an alkylene group containing no linking group, more preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, A methylene group is preferred.
R ¹ has the same meaning as R ¹ in the formula, the preferred range is also the same.
R ² and R ³ each represent a substituent, preferably an alkyl group, a halogen atom, an alkoxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, or a nitro group. As an alkyl group, a C1-C8 alkyl group is preferable. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable. As an alkoxy group, a C1-C8 alkoxy group is preferable. As the acyl group, an acyl group having 1 to 8 carbon atoms is preferable. As the acyloxy group, an acyloxy group having 1 to 8 carbon atoms is preferable. As an alkoxycarbonyl group, a C1-C8 alkoxycarbonyl group is preferable.
n4 and n5 are each an integer of 0 to 4, when n4 or n5 is 2 or more, R ² and R ³ existing in plural numbers, respectively, may be the same or different.

（Ｘ⁶は、アルキレン基、−Ｏ−、−Ｓ−および、これらのうちの複数が組み合わさった連結基であり、Ｒ¹は、それぞれ、水素原子、アルキル基、ハロゲン原子である。）
Ｒ¹は、上記一般式のＲ¹と同義であり、好ましい範囲も同義である。
Ｘ⁶がアルキレン基である場合、炭素数１〜８のアルキレン基が好ましく、より好ましくは炭素数１〜３のアルキレン基である。また、無置換のアルキレン基が好ましい。
Ｘ⁶としては、−ＣＨ₂−、−ＣＨ₂ＣＨ₂−、−Ｏ−、−Ｓ−が好ましい。 The compound represented by the general formula (VI) is preferably a compound represented by the following general formula (VIII).

(X ⁶ is an alkylene group, —O—, —S—, or a linking group in which a plurality of these are combined, and R ¹ is a hydrogen atom, an alkyl group, or a halogen atom, respectively.)
R ¹ has the same meaning as R ¹ in the formula, the preferred range is also the same.
When X < ⁶ > is an alkylene group, a C1-C8 alkylene group is preferable, More preferably, it is a C1-C3 alkylene group. An unsubstituted alkylene group is preferred.
The _{^{X 6, -CH 2 -, -}} CH 2 CH 2 -, - O -, - S- it is preferred.

  Although there is no restriction | limiting in particular in content of the compound represented by general formula (VI) in the photocurable composition used for this invention, From a viewpoint of a photocurable composition viscosity, in all polymerizable compounds, 1 -100 mass% is preferable, 5-70 mass% is more preferable, 10-50 mass% is especially preferable.

Although the compound represented by general formula (VI) is illustrated below, it cannot be overemphasized that this invention is not limited to these. R ¹ in the following formula has the same meaning as R ¹ in the general formula (VI), and the preferred range is also the same, and particularly preferably a hydrogen atom.

（式中、Ａｒは置換基を有していてもよいアリーレン基を表し、Ｘは単結合または有機連結基を表し、Ｒ¹は水素原子またはメチル基を表し、ｎは２または３を表す。） The polymerizable compound represented by the following general formula (VIII)

(In the formula, Ar represents an arylene group which may have a substituent, X represents a single bond or an organic linking group, R ¹ represents a hydrogen atom or a methyl group, and n represents 2 or 3. )

  In the general formula, the arylene group includes a hydrocarbon-based arylene group such as a phenylene group and a naphthylene group; a heteroarylene group in which indole, carbazole and the like are linked groups, preferably a hydrocarbon-based arylene group, More preferred is a phenylene group from the viewpoint of viscosity and etching resistance. The arylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an alkoxy group, a hydroxyl group, a cyano group, an alkoxycarbonyl group, an amide group, and a sulfonamide group.

  Examples of the organic linking group for X include an alkylene group, an arylene group, and an aralkylene group, which may contain a hetero atom in the chain. Among these, an alkylene group and an oxyalkylene group are preferable, and an alkylene group is more preferable. X is particularly preferably a single bond or an alkylene group.

R ¹ is a hydrogen atom or a methyl group, preferably a hydrogen atom.
n is 2 or 3, preferably 2.

  The polymerizable compound (VIII) is preferably a polymerizable compound represented by the following general formula (Ia) or (Ib) from the viewpoint of reducing the composition viscosity.

（式中、Ｘ¹、Ｘ²は、それぞれ独立に単結合または炭素数１〜３の置換基を有していてもよいアルキレン基を表し、Ｒ¹は水素原子またはメチル基を表す。）

(In formula, X < ¹ >, X < ² > represents the alkylene group which may have a single bond or a C1-C3 substituent each independently, and R < ¹ > represents a hydrogen atom or a methyl group.)

In the general formula (Ia), X ¹ is preferably a single bond or a methylene group, and more preferably a methylene group from the viewpoint of viscosity reduction.
The preferable range of X ^{2 is the same as} the preferable range of X ¹ .
Wherein R ¹ is as in formula and R ¹ synonymous, and preferred ranges are also the same.

  When the polymerizable compound is liquid at 25 ° C., it is preferable that generation of foreign matters can be suppressed even when the addition amount is increased.

Specific examples of the polymerizable compound represented by formula (VIII) are shown. R ¹ is as in formula and R ¹ synonymous represents a hydrogen atom or a methyl group. The present invention is not limited to these specific examples.

Although the more preferable specific example of the polymeric compound which has an aromatic group used with the photocurable composition used by this invention below is given, this invention is not limited to these.
Examples of the polymerizable compound having an aromatic group include benzyl (meth) acrylate which is unsubstituted or has a substituent on an aromatic ring, and phenethyl (meth) which is unsubstituted or has a substituent on an aromatic ring. Acrylate, unsubstituted or substituted phenoxyethyl (meth) acrylate on the aromatic ring, unsubstituted 1- or 2-naphthyl (meth) acrylate, unsubstituted or substituted on the aromatic ring, unsubstituted Or 1- or 2-naphthylmethyl (meth) acrylate having a substituent on the aromatic ring, 1- or 2-naphthylethyl (meth) acrylate having no substituent or a substituent on the aromatic ring, 1- or 2-naphthoxyethyl (meth) acrylate, resorcinol di (meth) acrylate, m-xylylene di (meth) acrylate, naphthalene Meth) acrylate, ethoxylated bisphenol A diacrylate is preferred, benzyl acrylate having a substituent on the unsubstituted or an aromatic ring, 1 or 2-naphthyl methyl acrylate, m- xylylene acrylate, are more preferred.
Preferred examples of the polymerizable compound having an alicyclic group used in the photocurable composition used in the present invention include isoboronyl (meth) acrylate, 1- or 2-adamantyl (meth) acrylate, 2-alkyl-2-adamantyl ( Monofunctional (meth) acrylates such as (meth) acrylate, tricyclodecanyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,3-adamantandi Polyfunctional (meth) acrylates, such as (meth) acrylate, are mentioned.

  Moreover, in this invention, it is preferable to contain the compound which has a carbon-carbon multiple bond and at least one among a fluorine atom and a silicon atom for the purpose of improving peelability from a mold. In the present invention, one or more of (A) a compound having a carbon-carbon multiple bond, (B) a compound having a Si-H bond, and (AB) a compound having a carbon-carbon multiple bond and a Si-H bond, In addition to the compound, a compound having a carbon-carbon multiple bond and a fluorine atom, a compound having a carbon-carbon multiple bond and a silicon atom, a carbon-carbon multiple bond, a fluorine atom, and Although it may contain at least one compound having both silicon atoms, component (A) is preferably applicable.

  The compound having a carbon-carbon multiple bond and a fluorine atom and / or a silicon atom in the present invention comprises at least one fluorine atom, a silicon atom, or a group having both a fluorine atom and a silicon atom, and a polymerizable functional group. Is a compound having at least one of As the polymerizable functional group, a (meth) acryloyl group and a vinyl ether group are preferable, and a (meth) acryloyl group is more preferable.

  The compound having a carbon-carbon multiple bond and a fluorine atom and / or a silicon atom may be a low molecular compound or a polymer.

  When the compound having the carbon-carbon multiple bond and the fluorine atom and / or the silicon atom is a polymer, the repeating unit having at least one of the fluorine atom and the silicon atom and the side chain as a copolymerization component are polymerizable. It may have a repeating unit having a group. Further, the repeating unit having at least one of the fluorine atom and the silicon atom may have a polymerizable group at its side chain, particularly at the terminal. In this case, the skeleton of the repeating unit having at least one of the fluorine atom and the silicon atom is not particularly limited as long as it does not contradict the gist of the present invention. For example, it has a skeleton derived from an ethylenically unsaturated bond-containing group. It is preferable to have a (meth) acrylate skeleton. Moreover, the repeating unit which has a silicon atom may form the repeating unit by the silicon atom itself like a siloxane structure (for example, dimethylsiloxane structure). The weight average molecular weight is preferably 2000-100000, more preferably 3000-70000, and particularly preferably 5000-40000.

The content of the compound having a carbon-carbon multiple bond and a fluorine atom and / or a silicon atom in the curable composition for imprints of the present invention is not particularly limited. From the viewpoint of lowering the viscosity, the total polymerizable compound is preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass, further preferably 0.5 to 10% by mass, and 0.5 to 5% by mass is particularly preferred.
In the present invention, the compound having a carbon-carbon multiple bond and a fluorine atom (including a compound having both a fluorine atom and a silicon atom) is preferably 0.1 to 10% by mass in the total polymerizable compound. 0.5 to 5% by mass is more preferable. Further, the compound having a carbon-carbon multiple bond and a silicon atom (including a compound having both a fluorine atom and a silicon atom) is preferably 1 to 50% by mass in the total polymerizable compound, and 5 to 45% by mass. % Is more preferable.

Compound having carbon-carbon multiple bond and fluorine atom The group having a fluorine atom contained in the compound having carbon-carbon multiple bond and fluorine atom is preferably a fluorine-containing group selected from a fluoroalkyl group and a fluoroalkyl ether group.
As said fluoroalkyl group, a C2-C20 fluoroalkyl group is preferable and a 4-8 fluoroalkyl group is more preferable. Preferable fluoroalkyl groups include trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, hexafluoroisopropyl group, nonafluorobutyl group, tridecafluorohexyl group, and heptadecafluorooctyl group.

  In the present invention, the compound having a carbon-carbon multiple bond and a fluorine atom is preferably a compound having a carbon-carbon multiple bond having a trifluoromethyl group structure and a fluorine atom. By having a trifluoromethyl group structure, the effects of the present invention are exhibited even with a small addition amount (for example, 10% by mass or less), so that compatibility with other components is improved, and line edge roughness after dry etching is improved. In addition to the improvement, the repeat pattern formability is improved.

As in the case of the fluoroalkyl group, the fluoroalkyl ether group preferably has a trifluoromethyl group, and preferably contains a perfluoroethyleneoxy group or a perfluoropropyleneoxy group. A fluoroalkyl ether unit having a trifluoromethyl group such as — (CF (CF ₃ ) CF ₂ O) — and / or a trifluoromethyl ether group having a trifluoromethyl group at the terminal thereof are preferred.

  The number of total fluorine atoms contained in the compound having a carbon-carbon multiple bond and a fluorine atom is preferably 6 to 60, more preferably 9 to 40, and still more preferably 12 to 40, particularly per molecule. The number is preferably 12-20.

  The compound having a carbon-carbon multiple bond and a fluorine atom has a fluorine atom having a fluorine content of 20 to 60% as defined below. When such a compound is a monomer, the fluorine content is preferably 20 to 60%, more preferably 35 to 60%. When such a compound is a polymer having a polymerizable group, the fluorine content is more preferably 20 to 50%, still more preferably 20 to 40%. By adjusting the fluorine content to an appropriate range, compatibility with other components is excellent, mold contamination can be reduced, line edge roughness after dry etching is improved, and repeat pattern formation is improved. In the present specification, the fluorine content is represented by the following formula.

  Preferable examples of the group having a fluorine atom of the compound having a carbon-carbon multiple bond and a fluorine atom include a compound having a partial structure represented by the following general formula (I). By adopting a compound having such a partial structure, the pattern forming property is excellent even when repeated pattern transfer is performed, and the temporal stability of the composition is improved.

一般式（Ｉ）中、ｎは１〜８の整数を表し、好ましくは４〜６の整数である。 Formula (I)

In general formula (I), n represents an integer of 1 to 8, preferably an integer of 4 to 6.

  Another preferred example of the compound having a carbon-carbon multiple bond and a fluorine atom is a compound having a partial structure represented by the following general formula (II). Of course, you may have both the partial structure represented by general formula (I), and the partial structure represented by general formula (II).

一般式（ＩＩ）中、Ｌ¹は単結合または炭素数１〜８のアルキレン基を表し、Ｌ²は炭素数１〜８のアルキレン基を表し、ｍ１およびｍ２はそれぞれ、０または１を表し、ｍ１およびｍ２の少なくとも一方は１である。ｍ３は１〜３の整数を表し、ｐは１〜８の整数を表し、ｍ３が２以上のとき、それぞれの、−Ｃ_pＦ_2p+1は同一であってもよいし異なっていてもよい。
前記Ｌ¹およびＬ²は、それぞれ、炭素数１〜４のアルキレン基であることが好ましい。また、前記アルキレン基は、本発明の趣旨を逸脱しない範囲内において置換基を有していてもよい。前記ｍ３は、好ましくは１または２である。前記ｐは４〜６の整数が好ましい。 Formula (II)

In the general formula (II), L ¹ represents a single bond or an alkylene group having 1 to 8 carbon atoms, L ² represents an alkylene group having 1 to 8 carbon atoms, m1 and m2 each represents 0 or 1, At least one of m1 and m2 is 1. m3 represents an integer of 1 to 3, p represents an integer of 1 to 8, and when m3 is 2 or more, each -C _p F _{2p + 1} may be the same or different. .
L ¹ and L ² are each preferably an alkylene group having 1 to 4 carbon atoms. Further, the alkylene group may have a substituent within a range not departing from the gist of the present invention. The m3 is preferably 1 or 2. The p is preferably an integer of 4-6.

  Specific examples of the compound having a carbon-carbon multiple bond and a fluorine atom used in the photocurable composition used in the present invention are listed below, but the present invention is not limited thereto.

（一般式（ＩＩＩ）中、Ｒ¹は水素原子、アルキル基、ハロゲン原子またはシアノ基を表し、水素原子またはアルキル基が好ましく、水素原子またはメチル基がより好ましく、水素原子であることがさらに好ましい。
Ａは（ａ１＋ａ２）価の連結基を表し、好ましくはアルキレン基および／またはアリーレン基を有する連結基であり、さらにヘテロ原子を含む連結基を含有していても良い。ヘテロ原子を有する連結基としては−Ｏ−、−Ｃ（＝Ｏ）Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−が挙げられる。これらの基は本発明の趣旨を逸脱しない範囲内において置換基を有していても良いが、有していない方が好ましい。Ａは、炭素数２〜５０であることが好ましく、炭素数４〜１５であることがより好ましい。
ａ１は１〜６の整数を表し、好ましくは１〜３、さらに好ましくは１または２である。
ａ２は２〜６の整数を表し、好ましくは２または３、さらに好ましくは２である。
Ｒ²およびＲ³はそれぞれ単結合または炭素数１〜８のアルキレン基を表す。ｍ１およびｍ２はそれぞれ、０または１を表し、ｍ３は１〜３の整数を表す。）
ａ１が２以上のとき、それぞれのＡは同一であってもよいし、異なっていても良い。
ａ２が２以上のとき、それぞれのＲ²、Ｒ³、ｍ１、ｍ２、ｍ３は同一であっても良いし、異なっていても良い。
Ｒｆはフロロアルキル基、フロロアルキルエーテル基を表し、好ましくは炭素数１〜８のフロロアルキル基、炭素数３〜２０のフロロアルキルエーテル基である。
炭素−炭素多重結合とフッ素原子を有する化合物がポリマーの場合、前記炭素−炭素多重結合とフッ素原子を有する化合物を繰り返し単位として含有するポリマーが好ましい。 Examples of the compound having a carbon-carbon multiple bond and a fluorine atom include trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, perfluorobutyl-hydroxypropyl (meta Fluorine atoms such as) acrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, etc. And monofunctional polymerizable compounds. Examples of the compound having a carbon-carbon multiple bond and a fluorine atom include 2,2,3,3,4,4-hexafluoropentanedi (meth) acrylate, 2,2,3,3,4,4, A polyfunctional polymerizable compound having two or more polymerizable functional groups having a di (meth) acrylate having a fluoroalkylene group such as 5,5-octafluorohexane di (meth) acrylate is also preferred.
A compound having two or more fluorine-containing groups such as a fluoroalkyl group or a fluoroalkyl ether group in one molecule can also be preferably used.
A compound having two or more fluoroalkyl groups or fluoroalkyl ether groups in one molecule is preferably a polymerizable compound represented by the following general formula (III).

(In the general formula (III), R ¹ represents a hydrogen atom, an alkyl group, a halogen atom or a cyano group, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom. .
A represents a (a1 + a2) -valent linking group, preferably a linking group having an alkylene group and / or an arylene group, and may further contain a linking group containing a hetero atom. Examples of the linking group having a hetero atom include —O—, —C (═O) O—, —S—, and —C (═O) —. These groups may have a substituent within a range not departing from the gist of the present invention, but preferably do not have a substituent. A preferably has 2 to 50 carbon atoms, and more preferably 4 to 15 carbon atoms.
a1 represents an integer of 1 to 6, preferably 1 to 3, and more preferably 1 or 2.
a2 represents an integer of 2 to 6, preferably 2 or 3, and more preferably 2.
R ² and R ³ each represent a single bond or an alkylene group having 1 to 8 carbon atoms. m1 and m2 each represents 0 or 1, and m3 represents an integer of 1 to 3. )
When a1 is 2 or more, each A may be the same or different.
When a2 is 2 or more, each R ² , R ³ , m1, m2, m3 may be the same or different.
Rf represents a fluoroalkyl group or a fluoroalkyl ether group, preferably a fluoroalkyl group having 1 to 8 carbon atoms or a fluoroalkyl ether group having 3 to 20 carbon atoms.
When the compound having a carbon-carbon multiple bond and a fluorine atom is a polymer, a polymer containing the compound having the carbon-carbon multiple bond and the fluorine atom as a repeating unit is preferable.

Specific examples of the compound having a carbon-carbon multiple bond and a fluorine atom used in the photocurable composition used in the present invention are listed below, but the present invention is not limited thereto. R ¹ in the following formula is each a hydrogen atom, an alkyl group, a halogen atom, or a cyano group.

Compound having a carbon-carbon multiple bond and a silicon atom The functional group having a silicon atom in the compound having a carbon-carbon multiple bond and a silicon atom includes a trialkylsilyl group, a chain siloxane structure, a cyclic siloxane structure, and a cage shape. Examples thereof include a siloxane structure. From the viewpoint of compatibility with other components and mold releasability, a functional group having a trimethylsilyl group or a dimethylsiloxane structure is preferable.

Examples of polymerizable compounds having silicon atoms include 3-tris (trimethylsilyloxy) silylpropyl (meth) acrylate, trimethylsilylethyl (meth) acrylate, (meth) acryloxymethylbis (trimethylsiloxy) methylsilane, and (meth) acryloxymethyltris. (Trimethylsiloxy) silane, 3- (meth) acryloxypropylbis (trimethylsiloxy) methylsilane, polysiloxane having a (meth) acryloyl group at the terminal or side chain (for example, X-22-164 series manufactured by Shin-Etsu Chemical Co., Ltd., X -22-174DX, X-22-2426, X-22-2475), etc. Among the examples of silane coupling agents described later, those corresponding to compounds having carbon-carbon multiple bonds and silicon atoms Also adopt You can.

(B) Compound having Si-H bond with molecular weight of 1500 or less (B) The compound having Si-H bond used in the present invention is a compound having one or more Si-H bonds in the molecule. A compound having 2 or more Si—H bonds is preferable, and a compound having 2 to 10 Si—H bonds in the molecule is more preferable.
The compound having (B) Si—H bond used in the present invention is preferably 0.5 to 30% by mass among all polymerizable components contained in the curable composition for imprints of the present invention, It is more preferable that it is 3-20 mass%.
The compound (B) having a Si—H bond used in the present invention preferably has a —SiH (Me ₂ ) structure. By having such a structure, the temporal stability of the composition becomes better.
(B) The compound having a Si—H bond preferably has an aromatic group, and more preferably has a benzene ring.
(B) The compound having a Si—H bond is preferably composed of a carbon atom, a hydrogen atom, an oxygen atom and a silicon atom.
The compound (B) having a Si—H bond may be a polymer compound or a non-polymer compound, but is preferably a non-polymer compound. In order to suppress volatilization when the curable composition is placed on the substrate, the boiling point at 1 atm of the compound having (B) Si—H bond is preferably 200 ° C. or more.
The molecular weight of such a non-polymer compound is preferably 100-1500, more preferably 200-1000, and even more preferably 200-500. 200-1500 are preferable and, as for the weight average molecular weight of a polymer compound, 300-1000 are more preferable. By setting the molecular weight to an appropriate range, volatilization when installed on the substrate can be suppressed and the mobility of the active species can be maintained, so that the curability is good.

Specific examples shown below are preferred as non-polymer compounds.

Specific examples shown below are preferred polymer compounds.

  In the above, n and m are each an integer. n is preferably 1 to 100, and more preferably 3 to 20. m is preferably 1 to 100, and more preferably 3 to 20.

上記式中、＊は他の基と連結する部位であり、好ましくは、アルキレン基と結合する。ｎ１は０〜２の整数であり、ｎ２は１〜３の整数である。但し、ｎ１とｎ２の合計は３である。
（ＡＢ）炭素−炭素多重結合およびＳｉ−Ｈ結合を有する化合物は、炭素原子、水素原子、酸素原子およびシリコン原子から構成されることが好ましい。
また、（ＡＢ）炭素−炭素多重結合およびＳｉ−Ｈ結合を有する化合物として芳香族基を含む化合物も好ましい。
（ＡＢ）炭素−炭素多重結合およびＳｉ−Ｈ結合を有する化合物の分子量は、１００〜１５００が好ましく、２００〜１０００がより好ましく、２００〜５００が更に好ましい。 (AB) Compound having carbon-carbon multiple bond and Si-H bond In the present invention, in place of (A) compound having carbon-carbon multiple bond and (B) compound having Si-H bond, or In addition to these, (AB) a compound having a carbon-carbon multiple bond and a Si—H bond may be included.
The compound having (AB) carbon-carbon multiple bond and Si—H bond used in the present invention is a compound having one or more Si—H bonds in the molecule, and two Si—H bonds in the molecule. A compound having the above is preferable, more preferably a compound having 2 to 10 Si—H bonds in the molecule, and particularly preferably a compound having 2 to 5 Si—H bonds in the molecule.
The compound having (AB) carbon-carbon multiple bond and Si—H bond used in the present invention is 0.5 to 20% by mass of the total polymerizable component contained in the curable composition for imprints of the present invention. It is preferable that it is 3-15 mass%.
The compound having (AB) carbon-carbon multiple bond and Si—H bond used in the present invention preferably has a —SiH (Me ₂ ) structure. By having such a structure, the temporal stability of the composition becomes better.
(AB) A compound having a carbon-carbon multiple bond and a Si—H bond includes (meth) acryl group, vinyl group (preferably vinyl ester group, vinyl ether group), allyl group (preferably allyl ester group, allyl ether). Group), and a compound having a (meth) acryl group is more preferable. The (meth) acryloyloxy group preferably has a partial structure bonded to a silicon atom via an alkylene group. 1-10 are preferable, as for carbon number of the alkylene group in this case, 1-6 are more preferable, and 1-4 are more preferable.
(AB) The compound having a carbon-carbon multiple bond and a Si—H bond preferably has a partial structure shown below.

In the above formula, * is a site linked to another group, preferably bonded to an alkylene group. n1 is an integer of 0 to 2, and n2 is an integer of 1 to 3. However, the sum of n1 and n2 is 3.
(AB) The compound having a carbon-carbon multiple bond and a Si—H bond is preferably composed of a carbon atom, a hydrogen atom, an oxygen atom and a silicon atom.
A compound containing an aromatic group is also preferred as the compound (AB) having a carbon-carbon multiple bond and a Si—H bond.
(AB) The molecular weight of the compound having a carbon-carbon multiple bond and a Si—H bond is preferably 100 to 1500, more preferably 200 to 1000, and still more preferably 200 to 500.

(AB) Specific examples of the compound having a carbon-carbon multiple bond and a Si—H bond include the following compounds. Needless to say, the present invention is not limited to these examples. Of these, (AB1) to (AB6) are more preferable.

  In the curable composition for imprints of the present invention, the total content of (B) a compound having a Si—H bond and (AB) a compound having a carbon-carbon multiple bond and a Si—H bond is ( 0.1 to 100 parts by weight is preferable with respect to 100 parts by weight of A) a compound having a carbon-carbon multiple bond and (AB) a compound having a carbon-carbon multiple bond and a Si—H bond, 50 parts by weight is more preferable, 0.5 to 30 parts by weight is further preferable, and 2 to 20 parts by weight is most preferable. By setting it as such a range, both high curability and high film strength can be achieved.

  A particularly preferred embodiment of the curable composition for imprints of the present invention is a component in which 60 to 98% by mass of the component excluding the solvent is (meth) acrylate, and the total amount of the compound having an Si—H bond is excluded from the solvent. The total amount of the compound having a carbon-carbon multiple bond and a fluorine atom is 0.1 to 5% by mass of the component excluding the solvent, and the photopolymerization initiator is the component excluding the solvent. Of 0.1 to 7% by mass.

(Photopolymerization initiator)
The curable composition of the present invention contains a photopolymerization initiator. Compared with a curable composition containing a metal catalyst such as platinum, it is excellent in curability and can be patterned with high productivity. As the photopolymerization initiator used in the present invention, any compound can be used as long as it is a compound that generates an active species that polymerizes the above-described polymerizable compound by light irradiation. As the photopolymerization initiator, a radical polymerization initiator and a cationic polymerization initiator are preferable, and a radical polymerization initiator is more preferable. In the present invention, a plurality of photopolymerization initiators may be used in combination.

Content of the photoinitiator used for this invention is 0.01-15 mass% in all the compositions except a solvent, for example, Preferably it is 0.1-12 mass%, More preferably, it is 0. 2 to 7% by mass. When using 2 or more types of photoinitiators, the total amount becomes the said range.
When the content of the photopolymerization initiator is 0.01% by mass or more, the sensitivity (fast curability), resolution, line edge roughness, and coating strength tend to be improved, which is preferable. On the other hand, when the content of the photopolymerization initiator is 15% by mass or less, light transmittance, colorability, handleability and the like tend to be improved, which is preferable.

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. Among these, acetophenone compounds, acylphosphine oxide compounds, and oxime ester compounds are preferred from the viewpoints of curing sensitivity and absorption characteristics.
Preferred examples of the acetophenone compound include hydroxyacetophenone compounds, dialkoxyacetophenone compounds, and aminoacetophenone compounds. Irgacure (R) 2959 (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, preferably available from BASF as a hydroxyacetophenone compound, Irgacure® 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure® 500 (1-hydroxycyclohexyl phenyl ketone, benzophenone), Darocur® 1173 (2-hydroxy-2-methyl-1-phenyl) -1-propan-1-one).
The dialkoxyacetophenone compound is preferably Irgacure (registered trademark) 651 (2,2-dimethoxy-1,2-diphenylethane-1-one) available from BASF.
As the aminoacetophenone compound, Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1), Irgacure (registered trademark) 379 (available from BASF Corporation) is preferable. EG) (2-dimethylamino-2- (4methylbenzyl) -1- (4-morpholin-4-ylphenyl) butan-1-one, Irgacure® 907 (2-methyl-1 [4- Methylthiophenyl] -2-morpholinopropan-1-one.
As the acylphosphine oxide-based compound, preferably Irgacure (registered trademark) 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Irgacure (registered trademark) 1800 (bis (2, 6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) available from BASF, Lucirin TPO-L (2,4,4) 6-trimethylbenzoylphenylethoxyphosphine oxide).
Irgacure (registered trademark) OXE01 (1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), Irgacure (registered trademark), preferably available from BASF as an oxime ester compound Trademark) OXE02 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime).
The cationic photopolymerization initiator used in the present invention is preferably a sulfonium salt compound, an iodonium salt compound, an oxime sulfonate compound, and the like, and 4-methylphenyl [4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl). Examples include borate (PI2074 manufactured by Rhodea), 4-methylphenyl [4- (2-methylpropyl) phenyliodonium hexafluorophosphate (IRGACURE250 manufactured by BASF), IRGACURE PAG103, 108, 121, 203 (manufactured by Ciba). .

  In the present invention, “light” includes not only light having a wavelength in the ultraviolet, near-ultraviolet, far-ultraviolet, visible, infrared, etc., and electromagnetic waves but also radiation. Examples of the radiation include microwaves, electron beams, EUV, and X-rays. 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 the entire surface can be exposed after forming a pattern for the purpose of increasing the film strength and etching resistance.

(Other ingredients)
The curable composition of the present invention includes a surfactant, an antioxidant, a solvent, and a polymer as long as the effects of the present invention are not impaired according to various purposes in addition to the above-described polymerizable compound and photopolymerization initiator. It may contain other components such as components, pigments and dyes. The curable composition of the present invention preferably contains at least one selected from a surfactant and an antioxidant.

-Surfactant-
The curable composition of the present invention preferably contains a surfactant. The content of the surfactant used in the present invention is, for example, 0.001 to 5% by mass, preferably 0.002 to 4% by mass, and more preferably 0.005 to 5% in the entire composition. 3% by mass. When using 2 or more types of surfactant, the total amount becomes the said range. When the surfactant is in the range of 0.001 to 5% by mass in the composition, the effect of coating uniformity is good, and deterioration of mold transfer characteristics due to excessive surfactant is unlikely to occur.

The surfactant is preferably a nonionic surfactant, and preferably contains at least one of a fluorine-based surfactant, a Si-based surfactant, and a fluorine / Si-based surfactant. It is more preferable to include both a Si-based surfactant or a fluorine / Si-based surfactant, and most preferable to include a fluorine / Si-based surfactant. The fluorine-based surfactant and the Si-based surfactant are preferably nonionic surfactants.
Here, the “fluorine / Si-based surfactant” refers to one having both the requirements of both a fluorine-based surfactant and a Si-based surfactant.
By using such a surfactant, a silicon wafer for manufacturing a semiconductor element, a glass square substrate for manufacturing a liquid crystal element, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, a tantalum alloy film, a silicon nitride film, Striation that occurs when the curable composition for imprinting of the present invention is applied to a substrate on which various films such as an amorphous silicone film, an indium oxide (ITO) film doped with tin oxide, and a tin oxide film are formed. In addition, it is possible to solve the problem of poor application such as a scale-like pattern (unevenness of drying of the resist film). In addition, the fluidity of the composition of the present invention into the cavity of the mold recess is improved, the peelability between the mold and the resist is improved, the adhesion between the resist and the substrate is improved, the viscosity of the composition is decreased, etc. Is possible. In particular, the curable composition for imprints of the present invention can significantly improve the coating uniformity by adding the surfactant, and the coating using a spin coater or slit scan coater does not depend on the substrate size. Good applicability is obtained.

Examples of nonionic fluorosurfactants that can be used in the present invention include trade names Fluorard FC-430 and FC-431 (manufactured by Sumitomo 3M Co., Ltd.), trade names Surflon S-382 (Asahi Glass ( EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 (manufactured by Tochem Products), trade names PF-636, PF-6320, PF -656, PF-6520 (all OMNOVA Solutions, Inc.), trade names FT250, FT251, DFX18 (all manufactured by Neos), trade names Unidyne DS-401, DS-403, DS-451 ( All are made by Daikin Industries, Ltd.) and trade names Megafuk 171, 172, 173, 178K, 178A, F780F (all Dainippon Ink Chemical Industry Co., Ltd.).
Examples of the nonionic Si-based surfactant include trade name SI-10 series (manufactured by Takemoto Yushi Co., Ltd.), MegaFac Paintad 31 (manufactured by Dainippon Ink & Chemicals, Inc.), KP -341 (manufactured by Shin-Etsu Chemical Co., Ltd.).
Examples of the fluorine / Si surfactant include trade names X-70-090, X-70-091, X-70-092, X-70-093 (all Shin-Etsu Chemical Co., Ltd. )), And trade names Megafuk R-08 and XRB-4 (both manufactured by Dainippon Ink & Chemicals, Inc.).

-Antioxidant-
Furthermore, the curable composition of the present invention preferably contains a known antioxidant. Content of the antioxidant used for this invention is 0.01-10 mass% with respect to a polymeric compound, for example, Preferably it is 0.2-5 mass%. When two or more kinds of antioxidants are used, the total amount is within the above 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, by adding an antioxidant, there is an advantage that coloring of a cured film can be prevented and a reduction in film thickness due to decomposition can be reduced. Examples of such antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, 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.

  Commercially available products of the antioxidants include trade names Irganox 1010, 1035, 1076, 1222 (above, manufactured by Ciba Geigy Co., Ltd.), trade names Antigene P, 3C, FR, Sumilyzer S, and Sumilizer GA80 (Sumitomo Chemical Co., Ltd.). Product name) ADK STAB AO70, AO80, AO503 (manufactured by ADEKA Corporation) and the like. These may be used alone or in combination.

-Polymerization inhibitor-
Furthermore, the curable composition of the present invention preferably contains a polymerization inhibitor. By including a polymerization inhibitor, it tends to be possible to suppress changes in viscosity, generation of foreign matter, and deterioration of pattern formation over time. As content of a polymerization inhibitor, it is 0.001-1 mass% with respect to all the polymeric compounds, More preferably, it is 0.005-0.5 mass%, More preferably, it is 0.008-0.05 mass. %. By blending an appropriate amount of the polymerization inhibitor, it is possible to suppress a change in viscosity over time while maintaining high curing sensitivity. The polymerization inhibitor may be contained in advance in the polymerizable compound to be used, or may be further added to the composition.
Preferred polymerization inhibitors that can be used in the present invention include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -Tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine cerium salt, phenothiazine, phenoxazine, 4-methoxynaphthol, 2,2,6 , 6-Tetramethylpiperidine-1-oxyl free radical, 2,2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, nitrobenzene, dimethyl And aniline. Particularly effective in the absence of oxygen, phenothiazine, 4-methoxynaphthol, 2,2,6,6-tetramethylpiperidine-1-oxyl free radical, 2,2,6,6-tetramethylpiperidine, 4- Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical is preferred.

-Solvent-
A solvent can be used for the photocurable composition used in the present invention according to various needs. A preferable solvent is a solvent having a boiling point of 80 to 200 ° C. at normal pressure. Any solvent can be used as long as it can dissolve the composition, but a solvent having any one or more of an ester structure, a ketone structure, a hydroxyl group, and an ether structure is preferable. Specifically, preferred solvents are propylene glycol monomethyl ether acetate, cyclohexanone, 2-heptanone, gamma butyrolactone, propylene glycol monomethyl ether, ethyl lactate alone or a mixed solvent, and a solvent containing propylene glycol monomethyl ether acetate. preferable.
The content of the solvent in the photocurable composition used in the present invention is optimally adjusted depending on the viscosity of the component excluding the solvent and the target film thickness. From the viewpoint of pattern formation, the content of the solvent is 30. It is preferably at most 10 mass%, more preferably at most 10 mass%, still more preferably at most 5 mass%, and most preferably contains substantially no solvent. “Substantially not containing a solvent” means, for example, that a solvent is not actively added in a manufacturing process, and does not mean that a solvent that is unintentionally mixed in a manufacturing process or the like is excluded.

-Polymer component-
In the composition of the present invention, for the purpose of further increasing the crosslinking density, a polyfunctional oligomer having a molecular weight higher than that of the other polyfunctional polymerizable compound may be blended within a range that achieves the object of the present invention. Examples of the polyfunctional oligomer having photoradical polymerizability include various acrylate oligomers such as polyester acrylate, urethane acrylate, polyether acrylate, and epoxy acrylate. The addition amount of the oligomer component is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, further preferably 0 to 10% by mass, and most preferably 0 to 5% by mass with respect to the component excluding the solvent of the composition. %.
The curable composition of the present invention may further contain a polymer component from the viewpoint of improving dry etching resistance, imprint suitability, curability and the like. The polymer component is preferably a polymer having a polymerizable functional group in the side chain. As a weight average molecular weight of the said polymer component, 2000-100000 are preferable from a compatible viewpoint with a polymeric compound, and 5000-50000 are more preferable. The addition amount of the polymer component is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, still more preferably 0 to 10% by mass, and most preferably 2% by mass or less, relative to the component excluding the solvent of the composition. It is. In the composition except for the solvent in the composition of the present invention, if the content of the compound having a molecular weight of 2000 or more is 30% by mass or less, the pattern forming property is improved. It is preferable not to contain a resin component except for an agent and a trace amount of additives.

  In addition to the above components, the curable composition of the present invention may include a release agent, a silane coupling agent, an ultraviolet absorber, a light stabilizer, an antiaging agent, a plasticizer, an adhesion promoter, and a thermal polymerization initiator. , Colorants, elastomer particles, photoacid growth agents, photobase generators, basic compounds, flow regulators, antifoaming agents, dispersants, and the like may be added.

  The curable composition of the present invention can be prepared by mixing the above-described components. Mixing and dissolution of the curable composition is usually performed in the range of 0 ° C to 100 ° C. Moreover, after mixing each said component, it is preferable to filter with a filter with the hole diameter of 0.003 micrometer-5.0 micrometers, for example. Filtration may be performed in multiple stages or repeated many times. Moreover, the filtered liquid can be refiltered. The material of the filter used for filtration may be polyethylene resin, polypropylene resin, fluorine resin, nylon resin or the like, but is not particularly limited.

  In the curable composition of the present invention, the viscosity of the mixed liquid of all components excluding the solvent is preferably 100 mPa · s or less, more preferably 1 to 70 mPa · s, still more preferably 2 to 50 mPa · s, most preferably 3 to 30 mPa · s.

[Pattern formation method]
Next, the formation method of the pattern (especially fine uneven | corrugated pattern) using the curable composition for imprints of this invention is demonstrated. In the pattern forming method of the present invention, a step of forming a pattern forming layer by placing the curable composition for imprints of the present invention on a substrate or a support (base material), and pressing a mold on the surface of the pattern forming layer A fine uneven | corrugated pattern can be formed by hardening the composition of this invention through the process to perform and the process of irradiating the said pattern formation layer with light.
Here, the curable composition for imprints of the present invention is preferably further heated and cured after light irradiation. Specifically, a layer (pattern forming layer) comprising at least a pattern forming layer comprising the composition of the present invention on a base material (substrate or support) and drying as necessary. To form a pattern receptor (with a pattern-forming layer provided on the substrate), press the mold against the surface of the pattern-receiving layer of the pattern receptor, and transfer the mold pattern. The concavo-convex pattern forming layer is cured by light irradiation. The optical imprint lithography according to the pattern forming method of the present invention can be laminated and multiple patterned, and can be used in combination with ordinary thermal imprint.

  The curable composition for imprints of the present invention can form a fine pattern with low cost and high accuracy by an optical nanoimprint method. For this reason, what was formed using the conventional photolithographic technique can be formed with further high precision and low cost. For example, the composition of the present invention is applied to a substrate or a support, and a layer made of the composition is exposed, cured, and dried (baked) as necessary to be used for a liquid crystal display (LCD), It can also be applied as a permanent film such as an overcoat layer or an insulating film, an etching resist for a semiconductor integrated circuit, a recording material, or a flat panel display. In particular, the pattern formed using the curable composition for imprints of the present invention is excellent in etching property, and can be preferably used as an etching resist for dry etching using fluorocarbon or the like.

  In permanent films (resist for structural members) used in liquid crystal displays (LCDs) and resists used in substrate processing of electronic materials, ions of metals or organic substances in the resist are used so as not to hinder the operation of the product. It is desirable to avoid contamination with sexual impurities as much as possible. For this reason, the concentration of the ionic impurities of the metal or organic matter in the curable composition for imprints of the present invention is preferably 1000 ppm or less, desirably 10 ppm or less, more preferably 100 ppb or less.

Hereinafter, a pattern forming method (pattern transfer method) using the curable composition for imprints of the present invention will be specifically described.
In the pattern forming method of the present invention, first, a pattern forming layer is formed by applying the composition of the present invention on a substrate.
As a method for applying the curable composition for imprints of the present invention onto a substrate, a generally well-known application method can be adopted.
As an application method of the present invention, for example, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spin coating method, slit scanning method, ink jet method, etc. A coating or droplet can be applied on the substrate. Moreover, although the film thickness of the pattern formation layer which consists of a composition of this invention changes with uses to be used, it is about 0.03 micrometer-30 micrometers. Further, the composition of the present invention may be applied by multiple coating. In the method of installing droplets on a substrate by an inkjet method or the like, the amount of droplets is preferably about 1 pl to 20 pl, and the droplets are preferably arranged on the substrate at intervals. Furthermore, you may form other organic layers, such as a planarization layer, for example between a base material and the pattern formation layer which consists of a composition of this invention. Thereby, since the pattern formation layer and the substrate are not in direct contact with each other, it is possible to prevent adhesion of dust to the substrate, damage to the substrate, and the like. In addition, the pattern formed with the composition of this invention is excellent in adhesiveness with an organic layer, even when it is a case where an organic layer is provided on a base material.

  The substrate (substrate or support) on which the curable composition for imprints of the present invention is applied can be selected depending on various applications, for example, quartz, glass, optical film, ceramic material, deposited film, magnetic Film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, polymer substrate such as SOG (Spin On Glass), polyester film, polycarbonate film, polyimide film, TFT array substrate, PDP electrode plate, glass, There are no particular restrictions on transparent plastic substrates, conductive substrates such as ITO or metal, insulating substrates, semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. Further, the shape of the substrate is not particularly limited, and may be a plate shape or a roll shape. In addition, as described later, a light transmissive or non-light transmissive material can be selected as the base material depending on the combination with the mold.

Next, in the pattern forming method of the present invention, a mold is pressed against the surface of the pattern forming layer in order to transfer the pattern to the pattern forming layer. Thereby, the fine pattern previously formed on the pressing surface of the mold can be transferred to the pattern forming layer.
Alternatively, the composition of the present invention may be applied to a mold having a pattern and the substrate may be pressed.
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, a light transmissive material is selected as at least one of a molding material and / or a base material. In optical imprint lithography applied to the present invention, a curable composition of the present invention is applied onto a substrate to form a pattern forming layer, a light-transmitting mold is pressed against this surface, and the back surface of the mold Then, the pattern forming layer is cured by irradiating light. Moreover, a curable composition is apply | coated on a transparent base material, a mold is pressed, light can be irradiated from the back surface of a base material, and a curable composition can also be hardened.
The light irradiation may be performed with the mold attached or after the mold is peeled off. In the present invention, the light irradiation is preferably performed with the mold in close contact.

As the mold that can be used in the present invention, a mold having a pattern to be transferred is used. The pattern on the mold can be formed 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.

  In the present invention, the non-light-transmitting mold material used when a light-transmitting substrate is used is not particularly limited as long as it has a predetermined strength. Specific examples include ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. There are no particular restrictions. Further, the shape of the mold is not particularly limited, and 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 pattern forming method of the present invention may be a mold that has been subjected to a release treatment in order to improve the peelability between the curable composition and the mold surface. Examples of such molds include those that have been treated with a silicon-based or fluorine-based silane coupling agent, such as OPTOOL DSX manufactured by Daikin Industries, Ltd., Novec EGC-1720 manufactured by Sumitomo 3M Co., Ltd. Commercially available release agents can also be suitably used.

  When performing photoimprint lithography using the composition of the present invention, it is usually preferable to perform the mold pressure at 10 atm or less in the pattern forming method of the present invention. By setting the mold pressure to 10 atm or less, the mold and the substrate are hardly deformed and the pattern accuracy tends to be improved. Further, it is preferable from the viewpoint that the apparatus can be reduced because the pressure is low. As the mold pressure, it is preferable to select a region in which the uniformity of mold transfer can be ensured within a range in which the residual film of the curable composition on the mold convex portion is reduced.

In the pattern forming method of the present invention, the irradiation amount of the light irradiation in the step of irradiating the pattern forming layer may be sufficiently larger than the irradiation amount necessary for curing. The irradiation amount necessary for curing is appropriately determined by examining the consumption of unsaturated bonds of the curable composition 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 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. May be. In the pattern forming method of the present invention, the preferable degree of vacuum at the time of light irradiation is in the range of 10 ⁻¹ Pa to normal pressure.

  The light used for curing the curable composition of the present invention is not particularly limited, and examples thereof include high energy ionizing radiation, light having a wavelength in the region of near ultraviolet, far ultraviolet, visible, infrared, or radiation. . 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. The radiation includes, for example, 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 lights, or may be lights having different wavelengths (mixed lights).

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 . If it is less than 5 mJ / cm ² , the exposure margin becomes narrow, photocuring becomes insufficient, and problems such as adhesion of unreacted substances to the mold tend to occur. On the other hand, if it exceeds 1000 mJ / cm ² , the permanent film may be deteriorated due to decomposition of the composition.
Further, during exposure, in order to prevent inhibition of radical polymerization by oxygen, an inert gas such as nitrogen or argon may be flowed to control the oxygen concentration to less than 100 mg / L.

  In the pattern formation method of this invention, after hardening a pattern formation layer by light irradiation, it may include the process of applying the heat | fever to the pattern hardened | cured as needed and further making it harden | cure. As heat which heat-hardens the composition of this invention after light irradiation, 150-280 degreeC is preferable and 200-250 degreeC is more preferable. In addition, the time for applying heat is preferably 5 to 60 minutes, and more preferably 15 to 45 minutes.

[pattern]
As described above, the pattern formed by the pattern forming method of the present invention can be used as a permanent film (resist for a structural member) or an etching resist used in a liquid crystal display (LCD) or the like. In addition, the permanent film is bottled in a container such as a gallon bottle or a coated bottle after manufacture, and is transported and stored. In this case, in order to prevent deterioration, the container is filled with inert nitrogen or argon. It may be replaced. Further, at the time of transportation and storage, the temperature may be normal temperature, but the temperature may be controlled in the range of −20 ° C. to 0 ° C. in order to prevent the permanent film from being altered. Of course, it is preferable to shield from light so that the reaction does not proceed.

The pattern formed by the pattern forming method of the present invention is also useful as an etching resist. When the imprint composition of the present invention is used as an etching resist, first, a silicon wafer or the like on which a thin film such as SiO ₂ is formed as a substrate is used, and the pattern forming method of the present invention is used on the substrate. A nano-order fine pattern is formed. Thereafter, a desired pattern can be formed on the substrate by etching using an etching gas such as hydrogen fluoride in the case of wet etching or CF _{4 in} the case of dry etching. The curable composition of the present invention has particularly good etching resistance against dry etching.

  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.

  A polymerizable compound shown in the following table, a compound having a Si—H bond, and a polymerization initiator are mixed, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (as a polymerization inhibitor) (Manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the polymerizable compound so as to be 100 ppm (0.01% by mass). The adjusted composition was filtered with a 0.1 μm tetrafluoroethylene filter to obtain a curable composition. All of the obtained curable compositions had a viscosity at 25 ° C. of 50 mPa · s or less.

<Polymerizable compound>

A1: Viscoat # 160, manufactured by Osaka Organic Chemical Co., Ltd.
A2: Synthesis from 2-bromomethylnaphthalene and acrylic acid by a conventional method A3: Aldrich A4: Synthesis from α, α'-dichloro-m-xylene and acrylic acid by a conventional method A5: Osaka Organic Chemical Co., Ltd. Made by IBXA
A6: Shin-Nakamura Chemical Co., Ltd., A-DCP
A7: manufactured by Gelest, SIA0210
A8: M-309 manufactured by Toa Gosei Co., Ltd.
A9: synthesized by the method described in JP 2010-239121 A

<Compound having Si-H bond>

B1: SIP6826 manufactured by Gelest
B2: SIB1090 manufactured by Gelest
B3: SIT 8665 manufactured by Gelest
AB1: Synthesis according to the method described in EP1424339 A2: Synthesis according to the method described in EP1424339

<Photopolymerization initiator>
C1: 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one (manufactured by BASF, Darocur 1173)
C2: (2-dimethylamino-2- (4methylbenzyl) -1- (4-morpholin-4-ylphenyl) butan-1-one (manufactured by BASF, Irgacure 379EG)
<Comparative compound>
Z1: Compound synthesized by the method described in Example 1 of JP2010-109092A

(Evaluation)
The following evaluation was performed about the obtained curable composition of each Example and a comparative example. The results are shown in the table below.

<Pattern formation method>
The mold has a rectangular line / space pattern (1/1) with a line width of 30 nm and a groove depth of 70 nm, and the pattern surface is treated with OPTOOL DSX (manufactured by Daikin Industries). The line edge roughness is A mold that was 2.5 nm was used.
(Condition 1)
The curable composition was applied onto a silicon substrate by a spin coating method to form a pattern forming layer having a thickness of 1.5 μm. The mold is placed on this under a nitrogen stream, and cured with a mercury lamp light containing 365 nm light while pressing the mold against the composition at a pressure of 1 MPa with an exposure illuminance of 10 mW / cm ² and an exposure dose of 200 mJ / cm ² . After curing, the mold was slowly peeled off to obtain a pattern.
(Condition 2)
A pattern was formed using the same method as in condition 1 except that the nitrogen flow was changed to the atmospheric condition in condition 1.

<Pattern evaluation>
The pattern shape and pattern defect of the obtained pattern were observed with a scanning electron microscope and evaluated as follows.
(Shape evaluation)
A: A rectangular pattern faithful to the mold was obtained.
B: The pattern top was rounded, but the pattern height was faithful.
C: The pattern top was rounded and the pattern height was low.
(Defect assessment)
Pattern defects such as pattern peeling, cracking and crushing were observed.
a: No pattern defect was observed.
b: Defects were found in some of the region patterns, but they were less than 5% of the total pattern area.
c: Pattern defects were observed in a region of 5% or more with respect to the total pattern area.

上記割合は、炭素−炭素多重結合を有する化合物１００重量部に対する、Ｓｉ−Ｈ結合を有する化合物の含有量の割合である。

The said ratio is a ratio of content of the compound which has a Si-H bond with respect to 100 weight part of compounds which have a carbon-carbon multiple bond.

  It turned out that the composition of an Example is excellent in both pattern shape and defect performance irrespective of pattern formation conditions. On the other hand, when the composition of the comparative example was subjected to pattern formation in the atmosphere, the pattern shape and the defect performance were deteriorated.

Claims (15)

(A) a compound having a carbon-carbon multiple bond, (B) a compound having a Si—H bond having a molecular weight of 1500 or less, and (C) a curable composition for imprints containing a photopolymerization initiator, or (AB ) A curable composition for imprints containing a compound having a carbon-carbon multiple bond and a Si-H bond having a molecular weight of 1500 or less, and (C) a photopolymerization initiator. The curable composition for imprints according to claim 1, which contains substantially no solvent. The curable composition for imprints according to claim 1 or 2, wherein the viscosity at 25 ° C of all components excluding the solvent is 100 mPa · s or less. (A) Compound having carbon-carbon multiple bond, and (AB) Compound having at least one carbon-carbon multiple bond having a molecular weight of 1500 or less and Si-H bond having two or more carbon-carbon multiple bonds The curable composition for imprints according to any one of claims 1 to 3, wherein The compound (A) having a carbon-carbon multiple bond, or (AB) a compound having a carbon-carbon multiple bond and a Si-H bond having a molecular weight of 1500 or less has a (meth) acryl group. The curable composition for imprints according to any one of the above. (A) a compound having a carbon-carbon multiple bond, and (AB) a compound in which at least one of a compound having a carbon-carbon multiple bond and a Si-H bond having a molecular weight of 1500 or less contains two or more Si-H bonds The curable composition for imprints according to any one of claims 1 to 5, wherein (A) a compound having a carbon-carbon multiple bond, (B) a compound having a Si—H bond having a molecular weight of 1500 or less, and (AB) a compound having a carbon-carbon multiple bond and a Si—H bond having a molecular weight of 1500 or less. The curable composition for imprints according to any one of claims 1 to 6, wherein at least one kind contains an aromatic group. Furthermore, the curable composition for imprints of any one of Claims 1-7 containing the compound which has a carbon-carbon multiple bond and a silicon atom. Furthermore, the curable composition for imprints of any one of Claims 1-8 containing the compound which has a carbon-carbon multiple bond and a fluorine atom. At least one of (B) a compound having a Si—H bond having a molecular weight of 1500 or less and (AB) a compound having a carbon-carbon multiple bond and a Si—H bond having a molecular weight of 1500 or less is —SiH (CH ₃ ) _2. The curable composition for imprints according to claim 1, having a structure. A pattern forming method using the curable composition for imprints according to claim 1. Applying the curable composition for imprints according to any one of claims 1 to 10 on a substrate to form a pattern forming layer;
Pressing the mold against the surface of the pattern forming layer;
Irradiating the pattern forming layer with light;
A pattern forming method comprising: A pattern obtained by the pattern forming method according to claim 11. An electronic device comprising the pattern according to claim 13. The manufacturing method of an electronic device containing the pattern formation method of Claim 11 or 12.