JP2011082347A - Curable composition for imprint, method of manufacturing cured product, and the cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition for imprint excellent in mold releasability and resistance to repetitive patterning. <P>SOLUTION: The curable composition for imprint contains: (A) a mold release agent; (B) a polymerizable monomer; and (C) a photopolymerization initiator. The (A) mold release agent has: at least (1) one kind of skeleton selected from a poly(meth)acrylic acid ester skeleton, poly(meth)acrylamide skeleton and a polystyrene skeleton; and (2) a polysiloxane skeleton. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a curable composition for imprints. Furthermore, it is related with the manufacturing method and hardened | cured material of hardened | cured material using this curable composition for imprints.

  When forming a pattern by the photoimprint method, it has been reported that the photocuring of the composition containing an acrylate monomer and a photoinitiator can be utilized (nonpatent literature 1, patent literature 1). In this document, although there is a description regarding pattern formation in the imprint method, there is no detailed description regarding an improvement in mold releasability from an industrially important mold. Particularly in recent years, as molds of processing substrates increase and patterns become finer, further improvement in mold releasability is required.

As a measure for improving mold releasability in the imprint process, it has been reported that silicones (polydimethylsiloxane and modified products thereof) are used (Patent Documents 2, 3, and 4).
Patent Document 2 proposes to use an unsubstituted polydimethylsiloxane as a release agent (layer) during thermal nanoimprinting. However, when an unsubstituted polydimethylsiloxane, which is said to be effective to some extent for improving the releasability in the thermal nanoimprint method, is applied to the optical nanoimprint method, the compatibility with the polymerizable monomer necessary for curing is poor, Layer separation is likely to occur during storage, resulting in coating unevenness, which is problematic in practice.
Patent Documents 3 and 4 propose the use of modified polydimethylsiloxane (hereinafter also referred to as modified silicone) in order to control the compatibility with the polymerizable monomer when applied to optical nanoimprinting. However, for example, Patent Document 3 describes that it is preferable that the silicone compound is non-reactive in order to improve releasability, but there is no description regarding specific selection criteria for the modifying group itself. Similarly, Patent Document 4 does not describe a specific selection criterion for the modifying group itself.

  On the other hand, when utilizing nanoimprint in industry, it is important that not only mold releasability for each transfer but also a good pattern can be formed repeatedly and stably. Among them, particularly in mass production, it is required to maintain a high yield even when pattern formation is performed continuously, that is, to maintain good pattern formability even when repeated pattern transfer is performed ( Repeated patterning resistance) is also required.

JP 2007-186570 A JP 2002-184719 A JP-A-2005-84561 JP 2008-19292 A

J.Vac.Sci.Technol.B 16 (6), Nov / Dec 1996

  As described above, mold releasability has been studied conventionally, but it is not sufficient. In addition, Patent Documents 2 to 4 did not discuss repeated pattern resistance. As a result of studies by the present inventor, it can be said that the curable composition for imprints disclosed in known documents is sufficient. I found that there was no. An object of the present invention is to solve the problems of the conventional prior art and to provide a curable composition for imprints excellent in releasability and resistance to repeated patterning.

  When the curable composition for imprints containing an unsubstituted polydimethylsiloxane as a release agent is applied to optical imprinting, compatibility during storage becomes a problem. However, polydimethylsiloxane polyether-modified products and aralkyl-modified products, which are conventionally used release agents to ensure compatibility during storage, have been insufficient as a release effect. Under such circumstances, the present inventors have further studied, and as a result, a release agent having a polysiloxane structure and further having a poly (meth) acrylate structure, a poly (meth) acrylamide structure or a polystyrene structure is used. As a result, the inventors have found that the above problems can be solved, and have completed the present invention. Specifically, it was achieved by the following means.

（式（１−１−１）中、Ｒ¹¹は水素原子またはメチル基を表し、Ｒ¹²は炭素数１〜１０の炭化水素基を表す。）
一般式（１−１−２）

（式（１−１−２）中、Ｒ¹¹は水素原子またはメチル基を表し、Ｒ¹³は炭素数１〜１０の炭化水素基を表し、前記Ｒ¹³はＲ¹³が結合しているＮ原子を含んで環を形成していてもよい。）
一般式（１−１−３）

（式（１−１−３）中、Ｒ¹¹は水素原子またはメチル基を表し、Ｒ¹⁴はそれぞれ独立に炭素数１〜１０の炭化水素基を表し、ｎ１１は０〜３の整数を表す。）
一般式（１−２）

（式（１−２）中、Ｌ¹およびＬ²はそれぞれ独立に炭素数１〜１０の２価の炭化水素基を表し、Ｒ¹⁵〜Ｒ¹⁸はそれぞれ独立にメチル基、フェニル基またはアラルキル基を表し、ｎ１２は１０以上の整数を表す。）
一般式（２−１）

（式中（２−１）、Ａは下記一般式（２−２）を表し、Ｒ²¹〜Ｒ²³はそれぞれ独立にメチル基、フェニル基またはアラルキル基を表し、Ｒ²⁴およびＲ²⁵はそれぞれ独立に炭化水素基を表し、ｎ２１は１０以上の整数を表し、ｎ２２は１以上の整数を表す。）
一般式（２−２）

（式（２−２）中、ａは前記一般式（２−１）のＡが連結しているＳｉ原子との結合位置を示し、Ｒ³¹は、水素原子またはメチル基を表し、Ｒ³²は炭素数１〜１０の炭化水素基を表し、Ｌ³は単結合または炭素数１〜１０の２価の炭化水素基を表す。）
［９］ 前記離型剤が、（１）ポリ（メタ）アクリル酸エステル構造、ポリ（メタ）アクリルアミド構造およびポリスチレン構造からなる群から選ばれる構造の少なくとも１種由来の構造の共重合割合基が４０〜６０重量％の離型剤である、［１］〜［８］のいずれか１項に記載のインプリント用硬化性組成物。
［１０］ 前記（Ａ）離型剤の含有量が０．０１質量％〜５質量％の範囲であることを特徴とする、［１］〜［９］のいずれか１項に記載のインプリント用硬化性組成物。
［１１］ 前記（Ｂ）重合性単量体の含有量が、６５質量％以上であることを特徴とする［１］〜［１０］のいずれか１項に記載のインプリント用硬化性組成物。
［１２］ 溶媒を除いた成分の粘度が３０ｍＰａ・ｓ以下である、［１］〜［１１］のいずれか１項に記載のインプリント用硬化性組成物。
［１３］ さらに、（Ｄ）シランカップリング剤を含有する、［１］〜［１２］のいずれか１項に記載のインプリント用硬化性組成物。
［１４］ 前記（Ｄ）シランカップリング剤が、炭素炭素不飽和結合とアミノ基を有するシランカップリング剤である、［１３］に記載のインプリント用硬化性組成物。
［１５］ ［１］〜［１４］のいずれか１項に記載のインプリント用硬化性組成物を基材上に適用してパターン形成層を形成する工程と、前記パターン形成層表面にモールドを押圧する工程と、前記パターン形成層に光を照射する工程と、を含むことを特徴とする硬化物の製造方法。
［１６］ さらに、光が照射された前記パターン形成層を加熱する工程を含むことを特徴とする［１５］に記載の硬化物の製造方法。
［１７］ 前記基材が、シリコン基板またはガラス基板である、［１５］または［１６］に記載の硬化物の製造方法。
［１８］ ［１］〜［１４］のいずれか１項に記載のインプリント用硬化性組成物を硬化させたこと、あるいは、［１５］〜［１７］のいずれか１項に記載の硬化物の製造方法で製造されたことを特徴とする硬化物。 [1] (A) a mold release agent, (B) a polymerizable monomer, and (C) a photopolymerization initiator, wherein (A) the mold release agent is (1) a poly (meth) acrylate structure A curable composition for imprints, comprising at least one kind selected from the group consisting of a poly (meth) acrylamide structure and a polystyrene structure, and (2) a polysiloxane structure.
[2] Structure of the structure derived from at least one of the structures selected from the group consisting of the (1) poly (meth) acrylate structure, the poly (meth) acrylamide structure and the polystyrene structure. The curable composition for imprints according to [1], which is a release agent having a ratio of 20 to 80% by weight.
[3] The (A) release agent is a structure selected from the group consisting of (1) a poly (meth) acrylate structure, a poly (meth) acrylamide structure, and a polystyrene structure, and the (2) polysiloxane structure. Is a curable composition for imprints according to [1] or [2], which is bonded via a linking group containing a sulfur atom.
[4] The release agent (A) is a release agent obtained by modifying polysiloxane with at least one selected from (meth) acrylic acid ester, (meth) acrylamide and styrene. [1] The curable composition for imprints according to any one of to [3].
[5] Polymer of polydimethylsiloxane having at least one monomer selected from the group consisting of (meth) acrylic acid ester, (meth) acrylamide and styrene, and a mercapto group as the (A) release agent. The curable composition for imprints according to any one of [1] to [4].
[6] The imprint curing agent according to [5], wherein the (A) release agent is a release agent having a structure ratio of 20 to 80% by weight of the structure derived from polydimethylsiloxane having the mercapto group. Sex composition.
[7] The curable composition for imprints according to any one of [4] to [6], wherein the (meth) acrylic acid ester is a (meth) acrylic acid ester having 4 to 16 carbon atoms.
[8] The release agent is represented by at least one of the group consisting of the following general formula (1-1-1), general formula (1-1-2), and general formula (1-1-3). A release agent (I) in which 20 to 80% of structural units and 20 to 80% of structural units represented by the following general formula (1-2) are linked in a chain form, or the following general formula (2-1) The curable composition for imprints according to any one of [1] to [7], which is a release agent (II) containing 90% or more of a structural unit represented by:
General formula (1-1-1)

(In formula (1-1-1), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a hydrocarbon group having 1 to 10 carbon atoms.)
General formula (1-1-2)

(In the formula (1-1-2), R ¹¹ represents a hydrogen atom or a methyl group, R ¹³ represents a hydrocarbon group having 1 to 10 carbon atoms, wherein R ¹³ is N atom to which R ¹³ is bonded May be included to form a ring.)
General formula (1-1-3)

(In formula (1-1-3), R ¹¹ represents a hydrogen atom or a methyl group, R ¹⁴ independently represents a hydrocarbon group having 1 to 10 carbon atoms, and n11 represents an integer of 0 to 3. )
General formula (1-2)

(In Formula (1-2), L ¹ and L ² each independently represent a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ^{15 to} R ¹⁸ each independently represent a methyl group, a phenyl group or an aralkyl group. And n12 represents an integer of 10 or more.)
General formula (2-1)

(In the formula (2-1), A represents the following general formula (2-2), R ^{21 to} R ²³ each independently represents a methyl group, a phenyl group or an aralkyl group, and R ²⁴ and R ²⁵ are each independently Represents a hydrocarbon group, n21 represents an integer of 10 or more, and n22 represents an integer of 1 or more.)
General formula (2-2)

(In the formula (2-2), a represents a bonding position with the Si atom to which A in the general formula (2-1) is linked, R ³¹ represents a hydrogen atom or a methyl group, and R ³² represents It represents a hydrocarbon group having 1 to 10 carbon atoms, L ³ represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms.)
[9] The release agent is a copolymerization proportion group having a structure derived from at least one of structures selected from the group consisting of (1) a poly (meth) acrylate structure, a poly (meth) acrylamide structure, and a polystyrene structure. The curable composition for imprints according to any one of [1] to [8], which is a release agent of 40 to 60% by weight.
[10] The imprint according to any one of [1] to [9], wherein the content of the release agent (A) is in the range of 0.01% by mass to 5% by mass. Curable composition.
[11] The curable composition for imprints according to any one of [1] to [10], wherein the content of the polymerizable monomer (B) is 65% by mass or more. .
[12] The curable composition for imprints according to any one of [1] to [11], wherein the viscosity of the component excluding the solvent is 30 mPa · s or less.
[13] The curable composition for imprints according to any one of [1] to [12], further comprising (D) a silane coupling agent.
[14] The curable composition for imprints according to [13], wherein the (D) silane coupling agent is a silane coupling agent having a carbon-carbon unsaturated bond and an amino group.
[15] A step of applying a curable composition for imprints according to any one of [1] to [14] onto a substrate to form a pattern forming layer, and a mold on the surface of the pattern forming layer. The manufacturing method of the hardened | cured material characterized by including the process of pressing, and the process of irradiating the said pattern formation layer with light.
[16] The method for producing a cured product according to [15], further comprising a step of heating the pattern forming layer irradiated with light.
[17] The method for producing a cured product according to [15] or [16], wherein the base material is a silicon substrate or a glass substrate.
[18] The cured curable composition for imprints according to any one of [1] to [14], or the cured product according to any one of [15] to [17]. A cured product produced by the production method of

  According to the present invention, it is possible to provide a curable composition for imprints excellent in releasability and repeated patterning resistance.

  Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. 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.

Further, in the present specification, “meth (acrylate)” represents “acrylate” and “methacrylate”, “meth (acryl)” represents “acryl” and “methacryl”, and “meth (acryloyl)” represents “ Represents “acryloyl” and “methacryloyl”. Further, in the present specification, “monomer” and “monomer” are synonymous. The monomer in the present invention is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 1,000 or less. In the present specification, “functional group” refers to a group involved in a polymerization reaction.
In addition, in the description of 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).
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.

The curable composition for imprints of the present invention can be widely applied to fields where optical nanoimprint lithography can be applied. According to the preferable aspect of this invention, there exists an advantage that it is easy to provide the curable composition for imprints which has the following characteristics.
(1) Since the solution fluidity at room temperature is excellent, the composition easily flows into the cavity of the mold recess, and the atmosphere is difficult to be taken in. Residues hardly remain after curing.
(2) The cured film after curing is excellent in mechanical properties, adhesion between the coating film and the substrate, and peelability between the coating film and the mold. A good pattern can be formed without causing surface roughness due to stringing (good pattern transfer accuracy).
(3) Since it is excellent in coating uniformity, it is suitable for the field of coating / microfabrication on large substrates.
(4) Since it has high mechanical properties such as light transmittance, residual film property, scratch resistance (curability) and solvent resistance, it can be suitably used as various permanent films.

  For this reason, the curable composition for imprints of the present invention includes, for example, semiconductor integrated circuits and liquid crystal display device members that have been difficult to develop (particularly, thin film transistors for liquid crystal displays, protective films for liquid crystal color filters, spacers, It can be suitably applied to other liquid crystal display device member microfabrication applications, etc., and other uses such as plasma display panel partition materials, flat screens, micro electromechanical systems (MEMS), sensor elements, optical disks, high density Magnetic recording media such as memory disks, optical components such as diffraction grating relief holograms, nanodevices, optical devices, optical films and polarizing elements, organic transistors, color filters, overcoat layers, pillar materials, liquid crystal alignment rib materials, micro Lens array, immunoassay chip, DNA separation chip, matrix Black reactor, nanobio devices, optical waveguides, can also be widely applied to manufacturing, such as an optical filter, photonic crystal.

  The curable composition for imprints of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) comprises (A) a release agent, (B) a polymerizable monomer, and (C) photopolymerization. An initiator, and the (A) release agent is (1) at least one selected from the group consisting of a poly (meth) acrylate structure, a poly (meth) acrylamide structure, and a polystyrene structure; And a polysiloxane structure. These will be described in detail below.

<(A) Release agent>
The release agent used in the present invention has (1) a structure selected from the group consisting of a poly (meth) acrylate structure, a poly (meth) acrylamide structure and a polystyrene structure, and (2) a polysiloxane structure. Features.

As a molecular weight of a mold release agent, it is preferable that a weight average molecular weight is 5,000-100,000, and it is more preferable that it is 10,000-60,000.
By setting the molecular weight to 5,000 or more, the effect of reducing the peeling force from the mold can be remarkably exhibited. By setting the molecular weight to 100,000 or less, (B) a polymerizable monomer (in) It is easy to ensure compatibility with the printing monomer).

  Hereinafter, the preferable ranges of the release agent will be described in the order of the structure (1), the structure (2), the entire release agent structure, and the release agent synthesis method.

((1) Structure selected from the group consisting of poly (meth) acrylic acid ester structure, poly (meth) acrylamide structure and polystyrene structure)
The poly (meth) acrylic acid ester structure, poly (meth) acrylamide structure and polystyrene structure in the release agent will be described.
The structure selected from the group consisting of the (1) poly (meth) acrylate structure, poly (meth) acrylamide structure and polystyrene structure may be one kind or plural.

More specifically, the (1) poly (meth) acrylate structure, poly (meth) acrylamide structure and polystyrene structure are more preferably the following structures.
The (1) poly (meth) acrylate structure, poly (meth) acrylamide structure and polystyrene structure are structures formed by polymerizing (meth) acrylate ester, (meth) acrylamide and styrene as monomers, respectively. Preferably there is.

Poly (meth) acrylate structure:
The poly (meth) acrylic acid ester structure is preferably a structure represented by the following general formula (1-1-1).

（式（１−１−１）中、Ｒ¹¹は水素原子またはメチル基を表し、Ｒ¹²は炭素数１〜１０の炭化水素基を表す。） General formula (1-1-1)

(In formula (1-1-1), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a hydrocarbon group having 1 to 10 carbon atoms.)

In formula (1-1-1), R ¹² is more preferably a methyl group, an ethyl group, a butyl group, a hexyl group or a decyl group.

  The (meth) acrylic acid ester for forming the poly (meth) acrylic acid ester structure is preferably a (meth) acrylic acid ester having 4 to 16 carbon atoms, more preferably 4 to 10 carbon atoms, and 4 carbon atoms. ~ 8 is more preferred. Examples of such (meth) acrylic acid esters include methyl methacrylate, ethyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, and tert-butylcyclohexyl methacrylate.

（式（１−１−２）中、Ｒ¹¹は水素原子またはメチル基を表し、Ｒ¹³は炭素数１〜１０の炭化水素基を表し、前記Ｒ¹³はＲ¹³が結合しているＮ原子を含んで環を形成していてもよい。） Poly (meth) acrylamide structure:
The poly (meth) acrylamide structure is preferably a structure represented by the following general formula (1-1-2).
General formula (1-1-2)

(In the formula (1-1-2), R ¹¹ represents a hydrogen atom or a methyl group, R ¹³ represents a hydrocarbon group having 1 to 10 carbon atoms, wherein R ¹³ is N atom to which R ¹³ is bonded May be included to form a ring.)

In Formula (1-1-2), R ¹³ is preferably a hydrogen atom, a methyl group, or an ethyl group when R ¹³ is bonded to an N atom to which R ¹³ is bonded to form a ring, and R ¹³ is bonded to R ^13. In the case of forming a ring containing the N atom, a morpholino group and a piperidino group are preferable.

  The (meth) acrylamide for forming the poly (meth) acrylamide structure is preferably (meth) acrylamide having 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 6 to 8 carbon atoms. Examples of such (meth) acrylamide include acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and acryloylmorpholine.

Polystyrene structure:
The polystyrene structure is preferably a structure represented by the following general formula (1-1-3).

（式（１−１−３）中、Ｒ¹¹は水素原子またはメチル基を表し、Ｒ¹⁴はそれぞれ独立に炭素数１〜１０の炭化水素基を表し、ｎ１１は０〜３の整数を表す。） General formula (1-1-3)

(In formula (1-1-3), R ¹¹ represents a hydrogen atom or a methyl group, R ¹⁴ independently represents a hydrocarbon group having 1 to 10 carbon atoms, and n11 represents an integer of 0 to 3. )

In formula (1-1-3), R ¹⁴ is preferably a hydrogen atom or a methyl group. n11 is preferably 0 to 3, and more preferably 0.

  Styrene for forming the polystyrene structure may be substituted or unsubstituted, preferably has 8 to 20 carbon atoms, more preferably has 8 to 16 carbon atoms, and particularly preferably has 8 to 12 carbon atoms. Examples of such substituted and unsubstituted styrene include styrene, 4-methylstyrene, 4-chlorostyrene, and 4-tert-butylstyrene.

  Among these, as the monomer for forming the (1) poly (meth) acrylic acid ester structure, poly (meth) acrylamide structure and polystyrene structure, compatibility is ensured and physical properties such as hydrophilicity and hydrophobicity are easily adjusted. A (meth) acrylic acid ester is preferable, and the (meth) acrylic acid ester is more preferably a (meth) acrylic acid ester having 4 to 16 carbon atoms from the viewpoint of imparting compatibility.

  The release agent has a structure ratio of a structure derived from at least one of the structures selected from the group consisting of (1) a poly (meth) acrylic ester structure, a poly (meth) acrylamide structure and a polystyrene structure. It is preferable from the viewpoint of improving releasability and repeated patterning resistance, and more preferably 40 to 60% by weight.

((2) Polysiloxane structure)
The mold release agent used in the present invention includes the (2) polysiloxane structure.
The polysiloxane structure (2) is not particularly limited, and a known polysiloxane structure can be used, and polydimethyl having a silicon atom in the main chain siloxane structure substituted with a methyl group, a phenyl group, or an aralkyl group. It preferably has a siloxane structure, more preferably has a polydimethylsiloxane structure in which the silicon atom in the main chain siloxane structure is substituted by a methyl group, a phenyl group or a phenylethyl group, and has a polydimethylsiloxane structure. Particularly preferred. The (2) polysiloxane structure is preferably a siloxane structure having a mercapto group. (However, the mercapto group may be directly substituted on the silicon atom of the siloxane structure or may be substituted via a linking group. The same applies hereinafter.) Further, the (2) polysiloxane structure has a mercapto group. More preferably, it has a polydimethylsiloxane structure.

Here, in the mold release agent, the group derived from polydimethylsiloxane preferably occupies 20 to 80% by weight, more preferably 30 to 60% by weight, and particularly preferably 40 to 60% by weight.
Furthermore, when using a polydimethylsiloxane having a mercapto group, it is preferable that the group derived from the polydimethylsiloxane having a mercapto group accounts for 20 to 80% by weight, more preferably 30 to 60% by weight, 40 to 60% by weight is particularly preferred. By setting the mass% of the polydimethylsiloxane structure in the release agent to 20% by mass or more, the effect of reducing the peeling force from the mold can be expressed more significantly, and by setting it to 80% by weight or less, It becomes easy to ensure compatibility with the (C) polymerizable monomer (imprinting monomer).

(Whole structure of release agent)
The composition ratio of the structure selected from the group consisting of (1) poly (meth) acrylate structure, poly (meth) acrylamide structure and polystyrene structure, and (2) polysiloxane structure is 20 to 80% by weight: 80 to 20% by weight is preferable from the viewpoint of improving releasability and resistance to repeated patterning, more preferably 40 to 60% by weight: 60 to 40% by weight, and more preferably 45 to 55% by weight: 55 to 45%. More preferably, it is% by weight.

Furthermore, other structural units may be included without departing from the spirit of the present invention. The other structural unit is preferably 0 to 10% by mass of the release agent, more preferably 0 to 5% by mass, and particularly preferably not included.
Examples of the other structural units include structural units derived from epoxy groups, oxetane groups, and vinyl ether groups.

  In the release agent of the present invention, the structure selected from the group consisting of (1) poly (meth) acrylate structure, poly (meth) acrylamide structure and polystyrene structure and (2) polysiloxane structure are randomly bonded. However, it is preferable that they are configured alternately or close to each other.

The arrangement of the structure (1) and the structure (2) in the whole mold release agent will be described.
In the release agent, a structure selected from the group consisting of (1) a poly (meth) acrylate structure, a poly (meth) acrylamide structure and a polystyrene structure, and (2) a polysiloxane structure contains a sulfur atom. It is preferable from the viewpoint of improving repeated patterning resistance that it is bonded via a linking group.
The linking group containing the sulfur atom is not particularly limited, for ^{example, -S -, - L 11 -S} -, - S-L 12 -, - L 13 -S-L 14 -, - SO 2 - , etc. (L ^{11 to} L ¹⁴ represent a divalent hydrocarbon group), and a linking group in which a plurality of these linking groups are combined may be used. Linking group including the sulfur ^{atom, -S -, - L 11 -S} -, - S-L 12 -, - is ^{preferably, -L 11 -S - - L 13} -S-L 14, - S-L ¹² -and -L ¹³ -SL ¹⁴ -are preferred. Further, the L ¹¹ ~L ¹⁴ is preferably an alkylene group having 1 to 6 carbon atoms, more preferably a propylene group or a hexylene group.

  (1) A type having a structure selected from the group consisting of a poly (meth) acrylic ester structure, a poly (meth) acrylamide structure and a polystyrene structure at the terminal of the (2) polysiloxane structure (hereinafter also referred to as a terminal type). Or (1) a type having a structure selected from the group consisting of a poly (meth) acrylate structure, a poly (meth) acrylamide structure and a polystyrene structure in the side chain of the (2) polysiloxane structure ( Hereinafter, it is also referred to as a side chain type).

  When the release agent used in the present invention is a terminal type, the structure selected from the group consisting of (1) poly (meth) acrylate structure, poly (meth) acrylamide structure and polystyrene structure is the above (2) poly A siloxane structure and a block polymer are preferably formed. Further, a type having a structure selected from the group consisting of (1) poly (meth) acrylate structure, poly (meth) acrylamide structure and polystyrene structure at both ends of the (2) polysiloxane structure (hereinafter referred to as both ends) Or (2) a type having a structure selected from the group consisting of (1) poly (meth) acrylate structure, poly (meth) acrylamide structure and polystyrene structure at one end of the polysiloxane structure ( Hereinafter, it is also referred to as a single-end type).

  The release agent used in the present invention preferably has a structure of a release agent (I) or a release agent (II). Hereinafter, it demonstrates in order.

Release agent (I):
The mold release agent used in the present invention is represented by at least one of the group consisting of the following general formula (1-1-1), general formula (1-1-2), and general formula (1-1-3). It is more preferable that the release unit is a release agent in which a structural unit represented by the following general formula (1-2) is linked in a chain.
Further, the release agent is a structure represented by at least one of the group consisting of the following general formula (1-1-1), general formula (1-1-2), and general formula (1-1-3). A release agent in which units 20 to 80% and structural units 20 to 80% represented by the following general formula (1-2) are linked in a chain (hereinafter also referred to as release agent (I)) It is particularly preferred.

（式（１−１−１）中、Ｒ¹¹は水素原子またはメチル基を表し、Ｒ¹²は炭素数１〜１０の炭化水素基を表す。）
一般式（１−１−２）

（式（１−１−２）中、Ｒ¹¹は水素原子またはメチル基を表し、Ｒ¹³は炭素数１〜１０の炭化水素基を表し、前記Ｒ¹³はＲ¹³が結合しているＮ原子を含んで環を形成していてもよい。）
一般式（１−１−３）

（式（１−１−３）中、Ｒ¹¹は水素原子またはメチル基を表し、Ｒ¹⁴はそれぞれ独立に炭素数１〜１０の炭化水素基を表し、ｎ１１は０〜３の整数を表す。） General formula (1-1-1)

(In formula (1-1-1), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a hydrocarbon group having 1 to 10 carbon atoms.)
General formula (1-1-2)

(In the formula (1-1-2), R ¹¹ represents a hydrogen atom or a methyl group, R ¹³ represents a hydrocarbon group having 1 to 10 carbon atoms, wherein R ¹³ is N atom to which R ¹³ is bonded May be included to form a ring.)
General formula (1-1-3)

(In formula (1-1-3), R ¹¹ represents a hydrogen atom or a methyl group, R ¹⁴ independently represents a hydrocarbon group having 1 to 10 carbon atoms, and n11 represents an integer of 0 to 3. )

（式（１−２）中、Ｌ¹およびＬ²はそれぞれ独立に炭素数１〜１０の２価の炭化水素基を表し、Ｒ¹⁵〜Ｒ¹⁸はそれぞれ独立にメチル基、フェニル基またはアラルキル基を表し、ｎ１２は１０以上の整数を表す。） General formula (1-2)

(In Formula (1-2), L ¹ and L ² each independently represent a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ^{15 to} R ¹⁸ each independently represent a methyl group, a phenyl group or an aralkyl group. And n12 represents an integer of 10 or more.)

In the general formula (1-2), L ¹ and L ² are each independently preferably a propylene group or a hexylene group. R ^{15 to} R ¹⁸ are each independently preferably a methyl group, a phenyl group, or a phenylethyl group, and more preferably a methyl group. n12 is preferably an integer of 0 to 2.

A structural unit represented by at least one of the group consisting of the general formula (1-1-1), the general formula (1-1-2) and the general formula (1-1-3), and the general formula The structural unit represented by (1-2) and other structural units are preferably bonded in a chain form at a ratio of 20 to 80:80 to 20: 0 to 10, and 40 to 60:60 to It is more preferable that they are bonded in a chain form at a ratio of 40: 0 to 5. The arrangement of these structural units may be random or alternating, but the general formula (1-1-1), the general formula (1-1-2), and the general formula (1-1-1- It is preferable that the structural unit represented by at least one of the group consisting of 3) and the structural unit represented by the general formula (1-2) are alternately or close to each other.
The release agent includes a structural unit represented by the general formula (1-1-1), a structural unit represented by the general formula (1-1-2), and the general formula (1-1- The structural unit represented by 3) and the structural unit represented by the general formula (1-2) may each include two or more types.

Among them, the general formula (1-1-1), the general formula (1-1-2), and the general formula (1-) are attached to both ends of the structural unit represented by the general formula (1-2). It is particularly preferable that the release agent is a double-end block copolymer in which at least one structural unit of the group consisting of 1-3) is bonded.
Moreover, when it is a mold release agent of a both-ends type block copolymer, the said general formula (1-1-1) couple | bonded with each terminal of the structural unit represented by the said General formula (1-2). ), The type and molecular weight of the structural unit represented by at least one of the group consisting of the general formula (1-1-2) and the general formula (1-1-3) may be the same or different. However, it is preferable that the same structural unit is bonded to both ends.

  Moreover, it is preferable that the said mold release agent is a mold release agent whose composition ratio of the structure derived from the polydimethylsiloxane which has the said mercapto group is 20 to 80 weight% as above-mentioned. That is, the release agent (I) is preferably a release agent having a structure ratio of the general formula (1-2) of 20 to 80% by weight.

  5000-100000 are preferable and, as for the weight average molecular weight of the said mold release agent (I), 10000-60000 are more preferable.

Release agent (II):
When the release agent is a side chain type, the structure selected from the group consisting of (1) poly (meth) acrylic acid ester structure, poly (meth) acrylamide structure and polystyrene structure is the side chain (2) The part which has a polysiloxane structure and the part which does not have the said (2) polysiloxane structure in the side chain may be included.
The mold release agent is preferably a structural unit represented by the following general formula (2-1), and a mold release agent (hereinafter referred to as 90% or more of the structural unit represented by the following general formula (2-1)). More preferably, it is also referred to as mold release agent (II).

（式中（２−１）、Ａは下記式（２−２）を表し、Ｒ²¹〜Ｒ²³はそれぞれ独立にメチル基、フェニル基またはアラルキル基を表し、Ｒ²⁴およびＲ²⁵はそれぞれ独立に炭化水素基を表し、ｎ２１は１０以上の整数を表し、ｎ２２は１以上の整数を表す。） General formula (2-1)

(In the formula (2-1), A represents the following formula (2-2), R ^{21 to} R ²³ each independently represents a methyl group, a phenyl group or an aralkyl group, and R ²⁴ and R ²⁵ each independently represent Represents a hydrocarbon group, n21 represents an integer of 10 or more, and n22 represents an integer of 1 or more.)

（式（２−２）中、ａは前記一般式（２−１）のＡが連結しているＳｉ原子との結合位置を表し、Ｒ³¹は水素原子またはメチル基を表し、Ｒ³²は炭素数１〜１０の炭化水素基を表し、Ｌ³は、単結合または炭素数１〜１０の２価の炭化水素基を表す。） General formula (2-2)

(In the formula (2-2), a represents the bonding position with the Si atom to which A in the general formula (2-1) is linked, R ³¹ represents a hydrogen atom or a methyl group, and R ³² represents carbon. A hydrocarbon group having 1 to 10 carbon atoms, and L ³ represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms.)

In general formula (2-1), R ^{21 to} R ²³ are preferably each independently a methyl group, a phenyl group, or a phenylethyl group, and more preferably a methyl group.
R ²⁴ and R ²⁵ are preferably each independently a methyl group.
n21 is preferably an integer of 10 or more, and more preferably 10 to 100.
n22 is preferably an integer of 1 or more, more preferably 1 to 10.
A preferred range for R ^{32 is the same as} the preferred range for R ¹² .
The preferred range of L ^{3 is the same as} the preferred range of L ¹ and L ² .

The release agent has a structure derived from polydimethylsiloxane having a mercapto group (for example, in the release agent (II), n22 repetitions in the case where R ²³ is a methyl group in the general formula (2-1)). Unit structure) and a structure derived from polydimethylsiloxane having no mercapto group (that is, in the release agent (II), R ²¹ and R ²² in the general formula (2-1) are methyl groups. The n21 repeating unit structure) may be random polymerization or block polymerization, but it is preferable that each structural position forms a block polymerization.

Moreover, it is preferable that the said mold release agent is a mold release agent whose composition ratio of the structure derived from the polydimethylsiloxane which has the said mercapto group is 20 to 80 weight% as above-mentioned. That is, in the release agent (II), when R ²³ is a methyl group in the general formula (2-1), the release agent has a composition ratio of n22 repeating unit structures of 20 to 80% by weight. Is preferred.

  The release agent (II) may contain two or more types of structural units represented by (2-1).

  5000-100000 are preferable and, as for the weight average molecular weight of mold release agent (II), 10000-60000 are more preferable.

  Among the arrangements of the structure (1) and the structure (2) in the mold release agent described above, the mold release agent used in the present invention is (B) a polymerizable monomer (imprint monomer described later). ), And a side chain type is preferable, and polydimethylsiloxane having a mercapto group in the side chain is more preferable.

(Method for synthesizing release agent)
The method for synthesizing the release agent is not particularly defined, but is usually obtained by modifying polysiloxane. The release agent in the present invention is preferably a release agent obtained by modifying polysiloxane with at least one selected from (meth) acrylic acid ester, (meth) acrylamide and styrene. The modification method is not particularly defined, but for example, polymerizing at least one monomer selected from (meth) acrylic acid ester, (meth) acrylamide and styrene and polydimethylsiloxane having a mercapto group. Is mentioned.
Specific examples of the method for synthesizing the release agent include the following methods.
(1) A synthesis method by polymerization of a polysiloxane having a mercapto group and at least one monomer selected from (meth) acrylic acid ester, (meth) acrylamide and styrene;
(2) a synthesis method by an enethiol reaction between a mercapto group-containing polysiloxane and at least one monomer (so-called macromonomer) selected from (meth) acrylic acid ester, (meth) acrylamide and styrene;
(3) Synthesis method by polymerization of polysiloxane having methacryloyloxy group and at least one monomer selected from (meth) acrylic acid ester, (meth) acrylamide and styrene;
(4) Synthesis by an addition reaction between a polymer component having a nucleophilic agent such as an amino group or a hydroxyl group and a polymer component having an electrophilic agent such as an epoxy group, oxetane group or isocyanate group.
Among these, the methods (1) and (3) are preferable because of the high degree of freedom in substrate selection.
In particular, as a method for synthesizing the side chain type release agent, graft polymerization is preferably performed in the methods (1) and (3).

  Examples of the polysiloxane having a mercapto group include polydimethylsiloxane having a mercapto group in the side chain of the polydimethylsiloxane structure (for example, KF-2001, KF-2004, manufactured by Shin-Etsu Chemical Co., Ltd.), and both polydimethylsiloxane structures. Examples include polydimethylsiloxane having a mercapto group at the terminal (for example, X-22-167B, manufactured by Shin-Etsu Chemical Co., Ltd.). From the viewpoint of compatibility with the imprinting monomer and reduction of mold release force, It is preferable to use polydimethylsiloxane having a mercapto group as a raw material.

  Examples of the polysiloxane having a methacryloyloxy group include a polydimethylsiloxane having a methacryloyloxy group at one end of the polydimethylsiloxane (for example, Silaplane FM-0711, FM-0721, FM-0725, manufactured by Chisso Corporation). It is done.

Although the example of the mold release agent used by this invention is shown below, this invention is not limited to these.

  The curable composition for imprints of the present invention preferably contains a release agent in the range of 0.01 to 5% by mass, and in the range of 0.5 to 3% by mass, in the components excluding the solvent. More preferred.

<(B) polymerizable monomer>
The curable composition for imprints of the present invention contains a polymerizable monomer for the purpose of improving the composition viscosity, film hardness, flexibility and the like. In the component excluding the solvent, the curable composition for imprints of the present invention preferably contains a polymerizable monomer in a proportion of 65% by weight or more, more preferably in the range of 80 to 99% by mass, More preferably, it is contained in the range of 90 to 99% by mass.

Examples of the polymerizable monomer include a polymerizable unsaturated monomer having 1 to 6 ethylenically unsaturated bond-containing groups; a compound having an oxirane ring (epoxy compound); a vinyl ether compound; a styrene derivative; and a fluorine atom. A compound having propylene ether or butenyl ether can be mentioned, and from the viewpoint of promoting curability during light irradiation, a polymerizable unsaturated monomer having 1 to 6 ethylenically unsaturated bond-containing groups is preferable. Monofunctional or polyfunctional (meth) acrylates are preferred.
Specifically, as the polymerizable monomer, those described in paragraph numbers 0066 to 0083 of JP-A-2009-206197 can be preferably employed.

  In the present invention, the polymerizable monomer preferably contains both a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate, and the total amount of the bifunctional and / or trifunctional (meth) acrylate is completely polymerized. It is preferably 40% by weight or more, more preferably 60% by weight or more of the ionic monomer. The upper limit is not particularly defined, but is usually 90% by weight or less, preferably 85% by weight or less.

<(C) Photopolymerization initiator>
The curable composition for imprints of the present invention contains a photopolymerization initiator. The photopolymerization initiator used in the present invention is preferably included in the total composition in an amount of 0.1 to 15% by mass, more preferably 0.2 to 12% by mass, and still more preferably 0.3 to 10%. % By mass. Two or more photopolymerization initiators may be used in combination, and when two or more photopolymerization initiators are used, the total amount is within the above range. When the content of the photopolymerization initiator is 0.1% by mass or more, the sensitivity (fast curability), resolution, line edge roughness, and coating film 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. In the past, in ink-jet compositions containing dyes and / or pigments and color filter compositions for liquid crystal displays, various addition amounts of preferred photopolymerization initiators and / or photoacid generators have been studied. No preferred photopolymerization initiator and / or photoacid generator addition amount for curable compositions for imprints such as for printing has been reported. That is, in a system containing dyes and / or pigments, these may act as radical trapping agents, affecting the photopolymerizability and sensitivity. In consideration of this point, the amount of the photopolymerization initiator added is optimized in these applications. On the other hand, in the composition of the present invention, the dye and / or pigment is not an essential component, and the optimum range of the photopolymerization initiator is different from that in the field of an ink jet composition or a liquid crystal display color filter composition. There is. As the photopolymerization initiator, a cationic polymerization initiator and a radical polymerization initiator are preferable, and a radical polymerization initiator is more preferable.

  As the photopolymerization initiator used in the present invention, one that has activity with respect to the wavelength of the light source to be used is blended, and one that generates appropriate active species is used.

  As the radical photopolymerization initiator used in the present invention, for example, a commercially available initiator can be used. As these examples, those described in paragraph No. 0086 of JP-A-2009-206197 can be preferably employed.

  Furthermore, in addition to the photopolymerization initiator, a photosensitizer may be added to the curable composition for imprints of the present invention to adjust the wavelength in the UV region. As typical sensitizers that can be used in the present invention, those described in paragraph No. 0087 of JP-A-2009-206197 can be preferably used.

  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.

<(D) Silane coupling agent>
The curable composition for imprints of the present invention preferably contains a silane coupling agent. Although not bound by any theory, by using the (A) mold release agent and the silane coupling agent in combination, a synergistic effect of improving repeated patterning resistance can be obtained.

As the silane coupling agent that can be used in the composition of the present invention, for example, those described in paragraph No. 0101 of JP-A-2009-206197 can be preferably employed.
The silane coupling agent used in the present invention particularly preferably has an alkoxysilyl group (silane coupling group) and an organic group having 4 or more carbon atoms. The upper limit of the carbon number of the organic group is not particularly defined, but is usually 20 or less.

The silane coupling agent preferably contains a polymerizable group. Preferred examples of the polymerizable group include radical polymerizable groups such as (meth) acrylate groups, styryl groups, allyl groups, and vinyl groups, and cationic polymerizable groups such as epoxy groups, oxetanyl groups, and vinyl ether groups.
Examples of the silane coupling agent having a cationic polymerizable group include silane coupling agents having an epoxy group represented below.

Among these silane coupling agents, a silane coupling agent having a radical polymerizable group is preferable, and a silane coupling agent having a carbon-carbon unsaturated bond is preferable. The carbon-carbon unsaturated bond may be a carbon-carbon double bond or a carbon-carbon triple bond, preferably a carbon-carbon double bond, and more preferably a (meth) acrylate group.
Examples of the silane coupling agent containing a carbon-carbon unsaturated bond include γ-acryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, Examples include 4-trimethoxysilylstyrene.

In the present invention, a silane coupling agent having both a carbon-carbon unsaturated bond and a nitrogen atom is preferable, and a silane coupling agent having a carbon-carbon unsaturated bond and an amino group (including derivatives in which an amino group is substituted) From the viewpoint of improving the resistance to repeated patterning, it is more preferable.
Examples of the silane coupling agent having both a carbon-carbon unsaturated bond and a nitrogen atom include the following structures. The silane coupling agent shown below can be easily adjusted by mixing a bifunctional or higher functional (meth) acrylate compound and a silane coupling agent having an aminopropyl group.

  100-1000 are preferable and, as for the molecular weight of the silane coupling agent used by this invention, 150-500 are more preferable.

  The silane coupling agent is, for example, preferably contained in the range of 0.1 to 20% by mass in the composition of the present invention, and more preferably in the range of 1 to 10% by mass.

<Other ingredients>
In the composition of the present invention, in addition to the above-described components, a polymer component, an antioxidant, a surfactant, another organometallic coupling agent, a polymerization inhibitor, an ultraviolet absorber, a light stabilizer, and an anti-aging agent Additives, plasticizers, adhesion promoters, thermal polymerization initiators, photobase generators, colorants, elastomer particles, photoacid multipliers, basic compounds, and other flow regulators, antifoaming agents, dispersants, etc. May be. About these additives, description of Unexamined-Japanese-Patent No. 2009-206197 can be referred to.

  Moreover, although a solvent can also be used for the curable composition for imprints of the present invention, it is preferably a substantially solvent-free composition. Here, “substantially solvent-free composition” means a composition that does not substantially contain an organic solvent in the composition, specifically, the organic solvent in the composition. It is preferable that content is 3 mass% or less in all the compositions. That is, since the composition of the present invention preferably contains other monofunctional and / or bifunctional monomers as described above as reactive diluents, the organic solvent for dissolving the components of the composition of the present invention is It is not always necessary to contain. In addition, if an organic solvent is not included, a baking process for the purpose of volatilization of the solvent is not necessary, so that there is a great merit that it is effective for simplifying the process. Therefore, in the composition of the present invention, the content of the organic solvent is preferably 3% by mass or less, more preferably 2% by mass or less, and it is particularly preferable not to contain it. As described above, the composition of the present invention does not necessarily contain an organic solvent. However, in the case of dissolving a compound that does not dissolve in the reactive diluent as the composition of the present invention, or when finely adjusting the viscosity. Any of these may be added. Organic solvents that can be preferably used in the composition of the present invention include those commonly used in curable compositions for imprints and photoresists, which dissolve and uniformly disperse the compounds used in the present invention. There is no particular limitation as long as it does not react with these components.

  As said organic solvent, description of the paragraph numbers 0122-0124 of Unexamined-Japanese-Patent No. 2009-206197 can be referred, for example.

(Properties of curable composition for imprints)
Moreover, it is preferable that the viscosity in 25 degreeC of the curable composition for imprints of this invention is 30 mPa * s or less. The viscosity in the present invention means a viscosity at 25 ° C. unless otherwise specified. The curable composition for imprints of the present invention can impart the ability to form a fine concavo-convex pattern before curing, application suitability and other processability by setting the viscosity at 25 ° C. to 30 mPa · s. Can impart excellent coating film properties in terms of resolution, line edge roughness, residual film characteristics, substrate adhesion, and other points. The lower limit is not particularly defined, but is usually 3 mPa · s or more. By setting it as 3 mPa * s or more, a problem of substrate coating suitability and a decrease in the mechanical strength of the film hardly occur. Specifically, unevenness on the surface is less likely to occur during application of the composition, and the composition is less likely to flow out of the substrate during application. On the other hand, when the photocurable composition of the present invention has a viscosity of 30 mPa · s or less, when the mold having a fine uneven pattern is brought into close contact with the photocurable composition, the composition flows into the cavity of the concave portion of the mold. It is easy, and since it is hard to take in air | atmosphere, it is hard to cause a bubble defect and it can suppress that a residue remains after photocuring in a mold convex part. As a viscosity of the curable composition for imprints of this invention, Preferably it is 3-20 mPa * s, More preferably, it is 3-18 mPa * s, More preferably, it is 3-6 mPa * s. The curable composition for imprints of the present invention is substantially a solvent-free solvent, and the viscosity of the composition is preferably 3 to 20 mPa · s.
Furthermore, it is preferable that the curable composition for imprints of the present invention does not contain a polymer component other than the (A) release agent, and the molecular weight of the component other than the (A) release agent is the composition. In order to easily adjust the viscosity to 30 mPa · s or less, the viscosity is preferably 100 to 1,000, and more preferably 120 to 500.

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

  Generally, in order to adjust the viscosity of the composition, it is possible to blend various monomers, oligomers and polymers having different viscosities. In order to design the viscosity of the curable composition for imprints of the present invention within the above range, the composition is diluted with a compound having a monomer viscosity of 10 mPa · s or less, and the viscosity of the composition is reduced. It is preferable to adjust.

[Method for producing cured product]
Next, the manufacturing method of the hardened | cured material (especially fine concavo-convex pattern) using the curable composition for imprints of this invention is demonstrated. In the method for producing a cured product of the present invention, a step of applying a curable composition for imprints of the present invention on a substrate or a support (base material) to form a pattern forming layer, and a mold on the surface of the pattern forming layer A fine concavo-convex pattern can be formed by curing the composition of the present invention through a step of pressure-contacting and a step of irradiating the pattern forming layer with light. In particular, in the present invention, in order to improve the degree of curing of the cured product, it is preferable to further include a step of heating the pattern forming layer after light irradiation.
The cured product obtained by the method for producing a cured product of the present invention is excellent in pattern accuracy and hardness, and in a more preferable embodiment, is excellent in light transmittance, and in particular, a protective film for liquid crystal color filters, a spacer, and other liquid crystal display devices. It can use suitably as a member for use.
Specifically, a layer formed of the composition of the present invention is applied (preferably coated) on at least a pattern forming layer made of the composition of the present invention on a substrate (substrate or support) and dried as necessary. A (pattern forming layer) is formed to produce a pattern receptor (with a pattern forming layer provided on a substrate), the mold is pressed against the pattern forming layer surface of the pattern receptor, and the mold pattern is transferred. Processing is performed, and the fine uneven pattern forming layer is cured by light irradiation and heating. Light irradiation and heating may be performed a plurality of times. The optical imprint lithography according to the pattern forming method (a method for producing a cured product) 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 imprint 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 on 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. Since the curable composition for imprints of the present invention is excellent in light transmittance after curing, it is particularly suitable for producing a permanent film such as an overcoat layer or an insulating film.

  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.

Below, the manufacturing method (pattern formation method (pattern transfer method)) of the hardened | cured material using the curable composition for imprints of this invention is described concretely.
In the manufacturing method of the hardened | cured material of this invention, first, the composition of this invention is applied on a base material, and a pattern formation layer is formed.
As a coating method when the curable composition for imprints of the present invention is coated on a substrate, generally known coating methods such as a dip coating method, an air knife coating method, a curtain coating method, and a wire bar coating are used. Method, gravure coating method, extrusion coating method, spin coating method, slit scanning method and the like. 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 0.05 micrometer-30 micrometers. Further, the composition of the present invention may be applied by multiple coating. In addition, you may form other organic layers, such as a planarization layer and an adhesive bond layer, for example between a base material and the pattern formation layer which consists of a composition of this invention. As a result, the pattern forming layer and the base material are not in direct contact with each other, so that adhesion of dust to the base material, damage to the base material, etc. can be prevented, or the adhesion between the pattern forming layer and the base material can be improved. Can do. 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) for applying the curable composition for imprints of the present invention 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, SOG (Spin On Glass), polyester film, polycarbonate film, polymer film such as polyimide film, TFT array substrate, PDP electrode plate, glass There are no particular restrictions on transparent plastic substrates, conductive substrates such as ITO and metals, insulating substrates, semiconductor fabrication substrates such as silicone, silicone nitride, polysilicon, silicone oxide, and amorphous silicone. Among them, the curable composition for imprints of the present invention preferably uses a substrate having reactivity with a silane coupling agent as the substrate, and uses a substrate that forms a siloxane bond with the silane coupling agent. More preferably, it is particularly preferable to use a substrate containing silicon atoms, particularly a silicon substrate or a glass substrate. 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.

Subsequently, in the manufacturing method of the hardened | cured material of this invention, in order to transcribe | transfer a pattern to a pattern formation layer, a mold is pressed on the pattern formation layer surface. Thereby, the fine pattern previously formed on the pressing surface of the mold can be transferred to the pattern forming layer.
The molding material that can be used in the present invention will be described. In imprint lithography using the composition of the present invention, a light-transmitting material is selected for at least one of a molding material and / or a base material. In the optical imprint lithography applied to the present invention, a pattern forming layer is formed by applying the curable composition for imprints of the present invention on a substrate, and a light-transmitting mold is pressed on this surface, Light is irradiated from the back surface of the mold to cure the pattern forming layer. Moreover, the curable composition for imprints can be applied to a light-transmitting substrate, pressed against a mold, and irradiated with light from the back surface of the substrate to cure the curable composition for imprints.
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 adhered.

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, deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicone, silicone nitride, polysilicon, silicone oxide, and amorphous silicone. There are no particular restrictions. 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 method for producing a cured product 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 for imprints and the mold surface. Examples of such molds include those that have been treated with a silane coupling agent such as silicone or fluorine, such as OPTOOL DSX manufactured by Daikin Industries, Ltd. or Novec EGC-1720 manufactured by Sumitomo 3M Co., Ltd. Commercially available release agents can also be suitably used.

  When photoimprint lithography is performed using the composition of the present invention, the mold pressure is usually preferably 10 atm or less, more preferably 3 atm or less in the method for producing a cured product 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 for imprints on the mold convex portion is reduced.

In the method for producing a cured product of the present invention, the irradiation amount of light irradiation in the step of irradiating the pattern forming layer with light 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 for imprints 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 bubble mixing, suppressing the decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the curable composition for imprinting. It may be irradiated with light. Moreover, the preferable vacuum degree at the time of light irradiation in the manufacturing method of the hardened | cured material of this invention is the range of 10 ^<-1 > Pa to normal pressure.

  The light used for curing the curable composition for imprints of the present invention is not particularly limited. For example, light or radiation having a wavelength in the region of high energy ionizing radiation, near ultraviolet, far ultraviolet, visible, infrared, or the like. Is mentioned. 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 manufacturing method of the hardened | cured material of this invention, after making a pattern formation layer harden | cure by light irradiation, it is preferable to include the process (post-baking process) which adds and heats the hardened pattern. The heating may be performed either before or after the mold is peeled from the pattern forming layer after light irradiation, but it is preferable to heat the pattern forming layer after the mold is peeled off. 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.

Moreover, the pattern formed by the manufacturing method of the hardened | cured material of this invention is useful also as an etching resist. When using the imprint composition of the present invention as an etching resist, first, for example, using a silicon wafer or the like on which a thin film such as SiO ₂ is formed as a substrate, the cured product of the present invention is produced on the substrate. A nano-order fine pattern is formed by the method. 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 for imprints of the present invention has particularly good etching resistance against dry etching.

  As described above, the cured product formed by the method for producing a cured product 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 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.

[Synthesis of release agent]
(Synthesis of S-1)
8 g of mercapto group-containing polydimethylsiloxane (KF-2001, manufactured by Shin-Etsu Chemical Co., Ltd.), 2 g of methyl methacrylate (MMA, manufactured by Tokyo Chemical Industry Co., Ltd.) as a monomer, and 20 ml of 2-butanone as an azo polymerization initiator. 601 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.05 g was mixed and stirred for 6 hours under reflux in a nitrogen gas atmosphere.
The molecular weight of the obtained polymer component was Mw = 25,000 (GPC measurement, polystyrene conversion).

(Synthesis of release agent of S-2 to S-16)
Except for changing the type and mixing ratio of mercapto group-containing polydimethylsiloxane and monomer, the synthesis was performed in the same manner as in S-1, and the molecular weight was measured using GPC.

(Synthesis of S-17)
4 g of methacryloyloxy group-containing polydimethylsiloxane (Silaplane FM-0711, manufactured by Chisso Corporation), 6 g of methyl methacrylate (MMA, manufactured by Tokyo Chemical Industry Co., Ltd.), 20 ml of 2-butanone as an azo polymerization initiator, V-601 0.05 g (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed and stirred for 6 hours under reflux in a nitrogen gas atmosphere.
The molecular weight of the obtained polymer component was Mw = 15000 (GPC measurement, polystyrene conversion).

(Synthesis of release agent of S-18 to S-20)
Except having changed the kind and mixing ratio of the methacryloyloxy group containing polydimethylsiloxane and monomer, it synthesize | combined by the same method as S-17, and measured the molecular weight using GPC.

  Below, the mixing ratio and molecular weight of the monomer of the release agent synthesized in this example are shown below.

[Preparation of curable compositions for imprints of Examples 1 to 16]
The following materials were used.
<Polymerizable monomer>
A-1: benzyl acrylate (Biscoat # 160, manufactured by Osaka Organic Chemical Industry Co., Ltd.). It is a monofunctional acrylate monomer.
A-2: Nonanediol diacrylate (Biscoat # 260, manufactured by Osaka Organic Chemical Industry Co., Ltd.). It is a bifunctional acrylate ester monomer.
A-3: Trimethylolpropane triacrylate (Aronix M309, manufactured by Toa Gosei Co., Ltd.). It is a trifunctional acrylate ester monomer.

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

<Silane coupling agent>
SC-1: γ-acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.). A silane coupling agent having an alkoxysilyl moiety and an acryloyl moiety (carbon-carbon unsaturated bond).
SC-2: 1-to-1 molar equivalent adduct of hexanediol diacrylate (Biscoat # 230, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.). A silane coupling agent having an alkoxysilyl moiety, an acryloyl moiety (carbon-carbon unsaturated bond) and an amino group moiety.

<Adjustment of curable composition for imprint>
Polymerizable monomers A-1 to A-3 and photopolymerization initiator P-1 were blended in the following weight ratio to prepare compositions 1 to 3.

  The release agent synthesized above was added to each of Compositions 1 to 3 prepared according to Table 5 as described in Table 6 below to prepare curable compositions for imprints in each Example.

[Preparation of curable compositions for imprints of Comparative Examples 1 to 4]
Similarly, in the compositions prepared according to Table 5 above, in Comparative Examples 2 and 4, polyether-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., KF-352A, side chain type) was used as a release agent. Carbinol-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-4039, side chain type) was used as a mold, and was added as described in Table 6 below. The curable composition for imprints of each comparative example was Prepared. Further, a curable composition for imprints of Comparative Example 1 was prepared in the same manner except that no release agent was added.

  In addition, the addition amount of the mold release agent and the addition amount of the silane coupling agent in the following Table 6 indicate the addition amount (parts by mass) with respect to 100 parts by mass of the composition. A mold release agent is mix | blended with the solution of methyl ethyl ketone, and the addition amount of a mold release agent represents a non volatile matter (solid content).

[Evaluation of curable composition for imprints]
About the curable composition for imprint of each Example and a comparative example, it measured according to the following evaluation method about the viscosity, pattern precision, repeated patterning tolerance, mold peeling force, and pencil hardness, and evaluated.

<Viscosity measurement>
The viscosity was measured at 25 ± 0.2 ° C. using a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd. The rotation speed at the time of measurement is 0.5 rpm to less than 5 mPa · s at 100 rpm, 5 mPa · s to less than 10 mPa · s is 50 rpm, 10 mPa · s to less than 30 mPa · s is 20 rpm, 30 mPa · s. More than s and less than 60 mPa · s was carried out at 10 rpm, more than 60 mPa · s and less than 120 mPa · s was carried out at 5 rpm, and more than 120 mPa · s was carried out at 1 rpm or 0.5 rpm. The results are shown in Table 6 below.

<Evaluation of pattern accuracy and repeated patterning resistance>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm. The spin-coated coated base film was set in an imprint apparatus using an ORC high pressure mercury lamp (lamp power 2000 mW / cm ² ) as a light source. Next, as a mold, polydimethylsiloxane having a line / space pattern of 10 μm and a groove depth of 4.0 μm (“SILPOT184” manufactured by Toray Dow Corning Co., Ltd. cured at 80 ° C. for 60 minutes) A material made of is used. After the inside of the apparatus was evacuated (the degree of vacuum was 10 Torr (about 1.33 kPa), the mold was pressure-bonded to the substrate, and nitrogen purge (1.5 atm: mold pressing pressure) was performed to replace the inside of the apparatus with nitrogen. The film was exposed from the back surface at an illuminance of 10 mW / cm ² and an exposure amount of 240 mJ / cm ^2. After the exposure, the mold was released to obtain a resist pattern.
The pattern shape after transfer was observed with an optical microscope, and the pattern shape was evaluated according to the following criteria. The results are shown in Table 6 below as pattern accuracy (first time).
This patterning operation was repeated 100 times using a mold repeatedly. The pattern shape after transfer was observed with an optical microscope for the 100th transfer pattern, and the pattern shape was evaluated according to the following criteria. The results are shown in Table 6 below as repeated patterning resistance (100th time).
A: It is almost the same as the pattern of the original plate from which the pattern shape of the mold is based.
B: The portion different from the pattern shape of the original plate that is the basis of the pattern shape of the mold is less than 5% of the patterning area.
C: The portion different from the pattern shape of the original plate that is the basis of the pattern shape of the mold is in the range of 5% or more and less than 10% of the patterning area.
D: The portion different from the pattern shape of the original plate that is the basis of the pattern shape of the mold is in the range of 10% or more and less than 20% of the patterning area, but is practically acceptable.
E: There are 20% or more of the patterning area which is different from the pattern shape of the original plate, which is the basis of the mold pattern shape, which is problematic in practice.

<Evaluation of mold release force>
As a mold, a glass substrate (2.5 × 2.5 mm square) that had been treated with a fluorosilane coupling agent was used, and the peeling force when peeling the mold and the substrate was measured with an imprint apparatus (prepared by the company). Exposing the curable composition (5 [mu] l) was placed on a glass substrate, after mold compression, ORC Co. high pressure mercury lamp with (lamp power 2000 mW / cm ²⁾ under the conditions of exposure amount 240 mJ / cm ² illuminance 10 mW / cm ² did. The substrate and the mold were separated at a speed of 20 μm / second, and the maximum peeling force at this time was measured to obtain the mold peeling force. The unit is [N (Newton)]. The results are shown in Table 6 below.

<Measurement of pencil hardness of cured film>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3 μm, and the mold was not pressed and exposed in a nitrogen atmosphere at an exposure amount of 240 mJ / cm ² , and then heated in an oven at 230 ° C. for 30 minutes. The film was cured.
Evaluation was made by changing the load to 500 g using a 3H pencil with reference to the test method of JIS-K5400.
The cured film after the test was evaluated by observing the degree of scratches on the surface of the cured film with an optical microscope. The results are shown in Table 6 below.
A: No scratches were observed on the cured film surface.
B: Scratches were observed on the surface of the cured film, but there is no practical problem.
C: Scratches where the cured film surface is scraped off are observed, and there is a problem in practical use.
D: Scratches enough to peel the cured film from the glass substrate were observed.

As apparent from Table 6 above, it was found that by using the composition of the present invention containing a specific release agent, the mold peeling force was greatly reduced and the repeated patterning resistance was remarkably improved.
On the other hand, from Comparative Example 1, it was found that when no release agent having a polysiloxane structure was included, the peel force was too high and the repeated patterning resistance was poor. From Comparative Examples 2 to 4, when a release agent (silicone oil) having the same structure as the release agent recommended in Patent Documents 3 and 4 is used, it is insufficient for reducing the peeling force and repeated patterning. It turned out that tolerance is comparable as the comparative example 1 without a mold release agent addition. That is, by using the composition of the present invention containing a specific release agent, it was found that not only the release property can be greatly improved, but also the repeated patterning resistance can be improved.
Furthermore, from Table 6 above, it was found that the preferred embodiment of the present invention was excellent in pencil hardness, and the surface hardness of the cured film could be improved.

Claims (18)

(A) a mold release agent, (B) a polymerizable monomer and (C) a photopolymerization initiator,
(A) the release agent is at least one selected from the group consisting of (1) a poly (meth) acrylate structure, a poly (meth) acrylamide structure and a polystyrene structure; and (2) a polysiloxane structure. A curable composition for imprints, comprising:   The composition ratio of the structure derived from at least one of the structures selected from the group consisting of the (1) poly (meth) acrylic acid ester structure, the poly (meth) acrylamide structure and the polystyrene structure is (A) the release agent. The curable composition for imprints of Claim 1 which is a 20-80 weight% mold release agent.   The (A) mold release agent is a structure selected from the group consisting of (1) a poly (meth) acrylate structure, a poly (meth) acrylamide structure, and a polystyrene structure, and (2) the polysiloxane structure is sulfur. The curable composition for imprints according to claim 1 or 2, which is bonded via a linking group containing an atom.   The (A) release agent is a release agent obtained by modifying polysiloxane with at least one selected from (meth) acrylic acid ester, (meth) acrylamide and styrene. The curable composition for imprints according to any one of the above.   The (A) release agent is a polymer of at least one monomer selected from the group consisting of (meth) acrylic acid ester, (meth) acrylamide and styrene, and polydimethylsiloxane having a mercapto group. The curable composition for imprints of any one of Claims 1-3.   The curable composition for imprints according to claim 5, wherein the (A) mold release agent is a mold release agent having a structure ratio of 20 to 80% by weight of the structure derived from the polydimethylsiloxane having the mercapto group. .   The curable composition for imprints according to any one of claims 4 to 6, wherein the (meth) acrylic acid ester is a (meth) acrylic acid ester having 4 to 16 carbon atoms. The release agent is a structural unit 20 represented by at least one of the group consisting of the following general formula (1-1-1), general formula (1-1-2), and general formula (1-1-3). Release agent (I) in which -80% and structural units 20-80% represented by the following general formula (1-2) are linked in a chain, or represented by the following general formula (2-1) The curable composition for imprints according to any one of claims 1 to 7, which is a release agent (II) containing 90% or more of the structural unit.
General formula (1-1-1)

(In formula (1-1-1), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a hydrocarbon group having 1 to 10 carbon atoms.)
General formula (1-1-2)

(In the formula (1-1-2), R ¹¹ represents a hydrogen atom or a methyl group, R ¹³ represents a hydrocarbon group having 1 to 10 carbon atoms, wherein R ¹³ is N atom to which R ¹³ is bonded May be included to form a ring.)
General formula (1-1-3)

(In formula (1-1-3), R ¹¹ represents a hydrogen atom or a methyl group, R ¹⁴ independently represents a hydrocarbon group having 1 to 10 carbon atoms, and n11 represents an integer of 0 to 3. )
General formula (1-2)

(In Formula (1-2), L ¹ and L ² each independently represent a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ^{15 to} R ¹⁸ each independently represent a methyl group, a phenyl group or an aralkyl group. And n12 represents an integer of 10 or more.)
General formula (2-1)

(In the formula (2-1), A represents the following general formula (2-2), R ^{21 to} R ²³ each independently represents a methyl group, a phenyl group or an aralkyl group, and R ²⁴ and R ²⁵ are each independently Represents a hydrocarbon group, n21 represents an integer of 10 or more, and n22 represents an integer of 1 or more.)
General formula (2-2)

(In the formula (2-2), a represents a bonding position with the Si atom to which A in the general formula (2-1) is linked, R ³¹ represents a hydrogen atom or a methyl group, and R ³² represents carbon. A hydrocarbon group having 1 to 10 carbon atoms, and L ³ represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms.)   The compositional ratio group of the structure derived from at least one of the structures selected from the group consisting of (1) a poly (meth) acrylate structure, a poly (meth) acrylamide structure and a polystyrene structure is 40 to 60 weights. The curable composition for imprints according to claim 1, which is a% release agent.   The curable composition for imprints according to any one of claims 1 to 9, wherein the content of the release agent (A) is in the range of 0.01% by mass to 5% by mass. .   11. The curable composition for imprints according to claim 1, wherein the content of the polymerizable monomer (B) is 65% by mass or more.   The curable composition for imprints according to any one of claims 1 to 11, wherein the viscosity of the component excluding the solvent is 30 mPa · s or less.   Furthermore, (D) The curable composition for imprints of any one of Claims 1-12 containing a silane coupling agent.   The curable composition for imprints according to claim 13, wherein the (D) silane coupling agent is a silane coupling agent having a carbon-carbon unsaturated bond and an amino group. Applying the curable composition for imprints according to any one of claims 1 to 14 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;
The manufacturing method of the hardened | cured material characterized by including.   Furthermore, the manufacturing method of the hardened | cured material of Claim 15 including the process of heating the said pattern formation layer irradiated with light.   The manufacturing method of the hardened | cured material of Claim 15 or 16 whose said base material is a silicon substrate or a glass substrate.   It hardened the curable composition for imprints of any one of Claims 1-14, or it manufactured with the manufacturing method of the hardened | cured material of any one of Claims 15-17. A cured product characterized by that.